Ingeniería de Nanomateriales PDF

Curso: Ingeniería de
Nanomateriales.
Ingeniería en Nanotecnología.
Facultad de Ingeniería, UABC
Profesor: Franklin Muñoz-Muñoz

Propósito del curso:
 Promover elaboración de proyectos o propuestas de
investigación. Así como su ejecución o puesta en marcha.
 Ofrecer las herramientas para aprender a presentar

proyectos o los productos derivados mediante
exposiciones, informes científicos, o artículos de
divulgación, de una manera eficiente.
Primera Clase:
Clase I. Conceptos Básicos.
Basado en:
Materials Science and Engineering
An Introduction, por William D. Callister, Jr.
Department of Metallurgical Engineering
The University of Utah.
John Wiley & Sons, Inc.
Capitulo 1.
Curso: síntesis de nanomateriales.
Conceptos básicos:
Que es un material?
Que son las propiedades?
Que es lo “nano”?
Que son las aplicaciones?
Que es la síntesis?
Y sobre todo,
que es un nano-material?
Los materiales son* elementos agrupados en un conjunto el cual
es, o puede ser, usado con algún fin especifico. Los elementos del
conjunto pueden tener naturaleza real (ser cosas), naturaleza virtual o ser
totalmente abstractos.
materiales de construcción
material educativo
materiales escolares
Materiales abstractos como el conocimiento divulgado en los libros, la
didáctica, apoyo multimedia y audiovisual
El material puede ser simple o complejo. Y también homogéneo o heterogéneo.
La palabra material adquiere diferentes significados según el contexto en el
que se encuentre:
En economía, material se refiere a un recurso utilizado en la alimentación de
un proceso productivo.
En ciencia, un material es cualquier conglomerado de materia o masa.
En ingeniería, un material es una sustancia (elemento o, más comúnmente,
compuesto químico) con alguna propiedad útil, sea mecánica, eléctrica, óptica,
térmica o magnética.
Para un artista material es su obra reciente.
Material puede referirse también a un conjunto de máquinas, o utensilios
utilizados para realizar un servicio o una profesión, como materiales de
construcción, material didáctico, materiales de escritura, material de laboratorio,
material de oficina o material rodante.
Los materiales son estudiados por las Ciencias e Ingenierías de Materiales.
En ciertas ocasiones es útil dividir las áreas del conocimiento en dos ramas.
La rama del conocimiento acerca de materiales no es la excepción.
Por un lado se considera a la ciencia de materiales como la sub-rama que

investiga las relaciones entre las estructuras, composiciones y las
propiedades fundamentales de los materiales.
En contraste, en el otro extremo se considera a la ingeniería en materiales

como el diseño de las propiedades a partir de la relación estructura-
composición-propiedades.
Es decir, la diferencia entre el científico y el ingeniero en materiales es su
objetivo final.
El fin del científico es desarrollar o sintetizar nuevos materiales.
El fin del ingeniero es crear nuevos productos o sistemas usando los

materiales disponibles o existentes, o bien, desarrollar técnicas para
procesar materiales.
Estructura y
Procesamiento Propiedades Desempeño
Composicion
Síntesis, propiedades y aplicaciones de nanomateriales

Jerarquía lineal del material definido por los principales subsistemas primitivos.
Es un hecho, en el área de Materiales no es siempre posible separar la sub-
rama científica de la sub-rama ingenieril.
El científico busca que estructura y que composición nos llevan a

determinadas propiedades.
Mientras el ingeniero busca que propiedades son las adecuadas para lograr
cierto desempeño.
Sin embargo todos dependen de la misma raíz: el procesamiento.
Por lo tanto, quienes trabajen en el área de materiales

deberán tener tanto entrenamiento científico como
entrenamiento ingenieril.
Pregunta: Que son las propiedades?
R. Una propiedad es la respuesta del material a un estimulo especifico.
Por ejemplo, la reflectividad (la capacidad de reflejar luz) es una propiedad de

una superficie metálica pulida.
El estimulo en este caso es la incidencia de luz.
La superconductividad es una propiedad a conducir corriente con cero

resistencia dada la aplicación de un campo eléctrico.
Importante: Una propiedad queda definida por el tipo y magnitud de la

respuesta a un estimulo especifico.
Pregunta: Que es la estructura?
En breve, la estructura de un material refiere al arreglo de sus componentes

internos.
•La estructura sub- atómica involucra a los electrones de los átomos, y a sus
interacciones con los núcleos.
•La estructura atómica es la organización de átomos o moléculas relativa a

sus vecinos.
•La estructura microscópica es aquella que puede ser observada por medio
de un microscopio.
•La estructura que puede ser discernida a simple vista se denomina

macroscópica.
Nota: No siempre la estructura refiere a arreglos cristalinos!

Virtualmente “todas” las propiedades de los materiales sólidos pueden
agruparse en seis distintas categorías:
•Mecánicas
•Eléctricas
•Térmicas
•Magnéticas
•Ópticas
•Deteriorativas
Sin embargo es también posible hablar de propiedades subjetivas (solo

pueden ser evaluadas por el hombre). Por ejemplo la estética.
Distintas propiedades ópticas del oxido de aluminio.
La diferencia se debe a su estructura, la cual es el
resultado de la forma en que fueron procesados.
Pregunta: Por qué o para que estudiar Ciencias
y/o Ingeniería de Materiales?
En épocas primitivas
el hombre se
conformaba con
tomar directamente
de la naturaleza los
materiales que esta
proveía.
Albrecht Durer : Adan y eva. Museo Del Prado

Sin embargo las necesidades humanas han cambiado desde aquellas épocas.
Hoy son necesarios engranes de transmisiones,

circuitos integrados, turbinas de jets, estructuras de
rascacielos, etc.
En muchos de estos dispositivos el diseño requerirá

la selección de un material apropiado.
Es común que los ingenieros civiles, mecánicos,

químicos o eléctricos tengan que tomar decisiones La bicicleta es una máquina
que sigue el estado del arte la
que conciernen al área de los materiales. evolución de los materiales
estructurales.
Ciencias y/o Ingeniería de Materiales nos sirven para dictar criterios de
selección a la hora de escoger de entre los 50,000 materiales disponibles
actualmente. La equivocación puede ser desastrosa!
Las condiciones de servicio son las que determinan las propiedades que se
requieren del material. Solo en contadas ocasiones un material posee todas
las características deseadas. Por lo tanto se deben establecer compromisos,
donde se sacrifica una propiedad por otra.
Clasificación tradicional de los materiales sólidos:
Metales.- Muchos electrones no localizados. Ejemplos, aluminio, acero,

bronce, estaño.
Cerámicas.- Son compuestos formados por elementos metálicos aleados
a elementos no metálicos. Típicamente son óxidos (Al 3O3 , SiO2 ),
carburos (SiC, WC, MoC, Ti2C ), nitruros (Si3 N4 , TiN, W 2N) y boruros
(NbB, BC, BN).
Polímeros.- Son basados en cadenas carbono-hidrogeno, con posible
contenido de otros elementos. Los Cauchos, gomas, plásticos, etc. Algunos
ejemplos: PVC, policarbonatos, nylon, lycra.
Clasificación avanzada de los materiales sólidos:
Compositos.
Nano-materiales.
Semiconductores.
Biomateriales.
Materiales inteligentes.
Etc.
que es un nano-material?
Alguien podría definir los Nanomateriales como materiales con alguna
característica morfológica de dimensiones de al menos de un decimo de micra
en alguna dirección.
Un decimo de micra= 1E-7 m = 100 nm
1 nanómetro = 1E-9 m
Sin embargo no existe consenso sobre el tamaño máximo o mínimo para ser
considerado nano-material.
Algunos pondrían el limite máximo como 30 nm. Otros 1 nm.
Buckminsterfullerene
Nanotubo de carbón
Microengranes
A escala macroscópica es
continua.
Material
A escala nanoscópica es
discreta.
Podemos considerar un material
cualquiera como nanomaterial
cuando:
En una propiedad en particular adquiere relevancia el carácter discreto de

la materia que lo compone. Ya sea cuando se reduce alguna de sus
dimensiones o grados de libertad.
T
T
La nanotecnología puede pensarse como una
extensión de la tecnología clásica
considerando los efectos que da la reducción
de dimensiones o grados de libertad sobre la
materia.
Tarea:
Realizar un ensayo de 800 palabras sobre nanotecnología. Fecha de
entrega 1 agosto 2015
Sugerencia: Usar el siguiente texto
Nanotecnology: The Future is Coming Sooner Than You Think
http://www.thenewatlantis.com/docLib/20120213_TheFutureisComingSoon
erThanYouThink.pdf
Disponibilidad de los materiales.
Basado en:
Enginnering Materials 1
An Introduction to, por Michael F. Ashby and David R.H. Jones.
Butterworth Heinemann.
Capitulo A.
Al seleccionar un material para una aplicación
en particular siempre debemos tener en
consideración dos importantes aspectos:
•Precio
•Disponibilidad
Disponibilidad de los materiales
Composición elemental de la corteza terrestre (hasta 1000 m de profundidad).

% Aproximado
Elemento
por peso
Oxigeno 46.6 Dada la abundancia de los
Silicio 27.7 elementos oxigeno y silicio
Aluminio 8.1 no es de sorprender que la
Fierro 5.0 mayoría de los minerales en
Calcio 3.6 la corteza terrestre sean
Sodio 2.8 silicatos.
Potasio 2.6 También son abundantes
Magnesio 2.1 los aluminosilicatos.
All others 1.5
Consumo anual de materiales por ciudadano en
EE.UU. 7.5 veces el promedio mundial!
El precio esta dado por el punto de equilibrio entre
disponibilidad y consumo.
El modelo de la oferta y la demanda describe la interacción en el mercado de

un determinado bien entre consumidores y productores, en relación con el
precio y las ventas de dicho bien.
Este modelo predice que, en un mercado libre y competitivo, el precio se

establecerá en función de la solicitud por los consumidores y la cantidad
proveída por los productores, generando un punto de equilibrio en el cual los
consumidores estarán dispuestos a adquirir todo lo que ofrecen los
productores al precio marcado por dicho punto.
Variación del precio del Cobre en 10 años.
http://www.metalprices.com/FreeSite/metals/cu/cu.asp
(a) (b)
años
El aumento en el precio del cobre (a) esta relacionado en la disminución

del metal disponible, como lo muestra la grafica (b).
Variación del precio del Cobre
http://www.metalprices.com/FreeSite/metals/cu/cu.asp
Las variaciones de corto periodo son relacionadas

en gran medida por la especulación, aunque
también influyen factores como problemas en la
distribución.
(Source: Castillon, D. 1992. Conservation of Natural Resources: A Resource Management Approach.
Dubuque, IA: William C. Brown Publishers, p. 320.)
“La actual concentración de minerales de cobre es aproximadamente un

sexto de lo que fue hace 100 años. Esto significa que es necesario
extraer y procesar seis veces más mineral para obtener la misma
cantidad de cobre que en épocas anteriores.
Por ejemplo, el consumo de acero crece al 2% anual. Es decir, su consumo
se duplica cada 35 Años.
El consumo de polímeros crece aproximadamente 5% por año. Se duplica

por lo tanto cada 14 Años. Sin embargo durante la epoca del “boom” de los
polimeros (1960s-1970s) el consumo se incrementaba al 18 % anual. Es
decir, se duplicaba cada 4 Años.
Moraleja, las tasas de consumo también son variables, lo que hace

entonces difícil predecir el consumo de los materiales.
Importaciones de el Reino Unido de materiales de ingeniería.
Porciento del total.
Fierro y acero 27
Madera 21
Cobre 13
Plásticos 9.7
Plata y platino 6.5
Aluminio 5.4
Caucho 5.1
Níquel 2.7
Zinc 2.4
Plomo 2.2
Estaño 1.6
Pulpa y papel 1.1
Vidrio 0.8
Tungsteno 0.3
Mercurio 0.2
Etc. 1.0
Aproximadamente el 20 % de las importaciones de una país son en materiales

ingenieriles.
La disponibilidad de un recurso depende de
•La localización.
•El tamaño de la reserva
•La energía ($) necesaria para extraerlo y procesarlo.

Cual es la diferencia entre la reserva y el recurso?
La reserva son los depósitos conocidos que pueden ser extraídos

provechosamente ($) a los precios actuales con la tecnología disponible.
El recurso (reserva potencial) incluye la actual reserva. Pero también

incluye todos los depósitos que pudieran llegar a ser disponibles dadas
las expectativas. Por ejemplo, incluye las reservan que no pueden ser
extraídas actualmente, pero con mejores precios, mejor tecnología o
mejor trasporte podría ser dispuesta en el futuro.
Mineral identificado Mineral no descubierto
Económicamente
Viable.
Reserva
Incrementar la exploración
Económicamente Incrementar la tecnología minera

No-Viable.
En pocas palabras, la reserva es como el dinero que tenemos en el banco.
La reserva potencial es como el potencial de dinero que podríamos ganar

en el transcurso de la vida.
Como se puede resolver la falta de disponibilidad de un
recurso?
Diseños eficientes. Usar solo la cantidad necesaria del recurso escaso.
Sustitución. Es la propiedad –no el material en si mismo- lo que el

diseñador necesita.
Reciclaje. Aunque costosa, el reciclaje es la solución a varios problemas,

como la contaminación.
Habíamos visto que virtualmente todas las propiedades de los materiales
sólidos pueden agruparse en seis distintas categorías:
•Mecánicas
•Eléctricas
•Térmicas
•Magnéticas
•Ópticas
•Deteriorativas
Sin embargo ahora vemos que también poseen propiedades económicas.
•Precio
•Disponibilidad
•Reciclabilidad.
Materiales peligrosos
Los materiales peligrosos pueden causar la muerte, lesiones severas,
deterioro crónico de la salud, daño a la propiedad, daño y deterioro del
ambiente.
El riego del empleo de materiales peligrosos ocurre durante el transporte,

uso, almacenaje o desecho.
Formas comunes de materiales peligrosos son los explosivos, los venenos,

las sustancia combustibles, materiales radioactivos.
Incluso materiales considerados inofensivos pueden ser peligrosos dado
un uso inapropiado.
Lo inverso también es cierto, un material considerado peligroso puede ser
inofensivo dado un uso apropiado.
Clasificación de los materiales peligrosos
Clase 1: Explosivos
Clase 2: Gases
Clase 3: Líquidos Inflamables
Clase 4: Sólidos inflamables
Clase 5: Sustancias oxidantes y
peróxidos orgánicos
Clase 6: Sustancias venenosas.
Sustancias infecciosas
Clase 7: Materiales radioactivos
Clase 8: Sustancias Corrosivas
Clase 9: Sustancias peligrosas varias
Clase 1: Explosivos Comprende de sustancias explosivas, artículos explosivos y
sustancias que producen efecto explosivo pirotécnico. Se subdivide en seis subclases:
1.1 Materiales y artículos que presentan riesgo de explosión de toda la masa (como la
nitroglicerina y la dinamita).
1.2 Materiales y artículos que presentan riesgo de proyección, pero no de explosión de
toda la masa.
1.3 Materiales y artículos que presentan riesgo de incendio y de que se produzcan
pequeños efectos de onda de choque o proyección, pero no un riesgo de explosión de
toda la masa.
1.4 Materiales y artículos que no presentan riesgos notables. Generalmente se limita a
daños en el embalaje.
1.5 Materiales muy poco sensibles que presentan riesgo de explosión de toda la masa
pero que la posibilidad de explosión es remota.
1.6 Materiales extremadamente insensibles que no presentan riesgo de explosión de
toda la masa.
Clase 2: Gases
Se refiere a cualquier tipo de gas comprimido, licuado o disuelto bajo presión. Se
distinguen tres subclases:
2.1 Gases inflamables. Incluyen generalmente a hidrocarburos procedentes de la

destilación del petróleo o de fuentes de gas natural (propano, hidrógeno).
2.2 Gases no inflamables, no venenosos y no corrosivos. Son gases que no se

queman con facilidad, y la combustión puede llevarse a cabo solo en condiciones
extremas (nitrógeno, helio).
2.3 Gases venenosos. Conformado por mezclas estables de gases, pero capaces de
reaccionar con los compuestos orgánicos de las células produciendo la muerte (Cloro,
fosgeno).
Clase 3: Líquidos Inflamables
Son líquidos, mezclas de líquidos, o líquidos conteniendo sólidos en solución o suspensión, que
liberan vapores inflamables a temperaturas relativamente bajas. Estas se clasifican de acuerdo al
Punto de Inflamabilidad, esto es, la temperatura más baja a la que el líquido desprende vapores en
cantidad suficiente para formar una mezcla inflamable en las proximidades de su superficie (gasolina).
3.1 Punto de inflamabilidad bajo (inferior a -18º C).
3.2 Punto de inflamabilidad medio (igual o superior a -18º C e inferior a 23º C)
3.3 Punto de inflamabilidad alto (igual o superior a 23º C e inferior a 61º C)
En esta clase también se incluyen igualmente las materias sólidas en estado fundido cuyo punto de
inflamación es superior a 61º C y que sean entregadas al transporte o transportadas en caliente a una
temperatura igual o superior a su punto de inflamación. También se incluyen las materias líquidas
explosivas desensibilizadas (materias líquidas explosivas preparadas en solución o en suspensión en
agua o en otros líquidos de modo que formen una mezcla líquida homogénea exenta de propiedades
explosivas).
Clase 4: Sólidos inflamables
Incluye a las sustancias espontáneamente inflamables y sustancias que en contacto
con el agua emiten gases inflamables. Son las sustancias que se encienden con
facilidad, y que en consecuencia representan un peligro de incendio bajo las
condiciones industriales normales.
4.1 Sólidos inflamables. Son sólidos que en condiciones normales de transporte son
inflamables y pueden favorecer incendios por fricción (magnesio, Fósforo rojo).
4.2 Sustancias que pueden presentar combustión espontánea. Son espontáneamente

inflamables en condiciones normales de transporte o al entrar en contacto con el aire
(Fósforo blanco).
4.3 Sustancia que en contacto con el agua despide gases inflamables o tóxicos (sodio,
potasio).
En cierta ocasiones la peligrosidad de los materiales puede
acrecentarse con el uso.
Por ejemplo, el uso de carbono y nitrógeno en ciertas circunstancias

podría generar cianuro (CN)2.
Esto no es raro en el uso de los acetonitrilos.

El cadmio es un metal extremadamente toxico.
Debido a su muy bajo limite de exposición
puede ocurrir envenenamiento en situaciones
donde el metal se encuentra en limites
detectables.
Han ocurrido muerte de soldadores que unen
aleaciones que no se conocía que tenían
cadmio.
Sin embargo este metal se sigue usando en
pinturas industriales que representan un peligro
al momento de ser sprayadas.
El cadmio también se usa en baterías
comerciales Ni-Cd, Zn-Cd…
El envenenamiento por cadmio no es irritante,
por lo tanto no hay alerta del individuo expuesto.
Cuando nos damos cuenta de la peligrosidad de los materiales?
R.- Desgraciadamente cuando lo vemos en las noticias.
Rainwater leaked into a room where hundreds of drums of dry swimming pool chemicals
were stored, causing an explosion. The explosion and resulting fire set off the sprinkler
system that soaked the remaining drums. The fire, explosions and chlorine releases
lasted three days. Over 25,000 people were evacuated, and 275 people went to the
hospital with skin burns and respiratory problems.
Twenty-three people were sent to the hospital after a chemical release at a resort casino.
Two cleaning agents were apparently mixed together in the basement of the building,
generating vapors that permeated part of the resort.
A massive explosion and fire occurred at an agricultural chemical packaging facility in

Arkansas, killing three firefighters and injuring a fourth. The likely cause was a supersack
of azinphos-methyl (an insecticide) being placed near a hot compressor exhaust pipe.
Una imagen dice mas que mil palabras!
Chernobyl.- Una
consecuencia del mal
manejo de materiales
En conclusión
Es un error del diseñador de materiales hacerlo solo

pensando en propiedades físicas. En necesario pensar
también en los factores económicos, la seguridad, en
ocasiones influyen los factores estéticos y en algunos
casos factores ambientales.
Curso: Ingeniería de
Nanomateriales.
Profesor: Franklin Muñoz Muñoz

Descripción Genérica de Unidad de Aprendizaje
Nombre: Ingeniería de Nanomateriales
Etapa: Disciplinaria
Área de conocimiento: Ingeniería aplicada
Competencia:
Diseñar, fabricar y caracterizar materiales nanoestructurados , apoyándose en la microestructura, propiedades mecánicas,
mecanismos de reforzamiento para aplicarlo en productos de escala manométrica con responsabilidad y cuidado al medio
ambiente.
Evidencia de desempeño:
Elegir y diseñar un material nanoestructurado adecuado para la fabricación de un producto base manométrica con una
aplicación particular.
Elaboró: Dr. Alejandro Martínez Ruiz
Contenido temático HC HL HT HPC HCL HE CR
2 4 2 8
 Introducción
 Síntesis, fabricación y procesamiento de materiales
 Estructuras de metales y cerámicas

 Estructuras de polímeros
 Compositos
 Imperfecciones en sólidos
 Difusión iónica y molecular en sólidos y liquídos
 Propiedades mecánicas, témicas y eléctricas
 Mecanismos de deformación y reforzamiento
 Fallas
 Diagramas de fase y Transformaciones de fase
 Tipos y aplicaciones de materiales
 Corrosión y degradación de materiales

Segunda Clase:
I. Conceptos Básicos.
Basado en:
An Introduction, por William D. Callister, Jr.
Department of Metallurgical Engineering
The University of Utah.
John Wiley & Sons, Inc.
Capitulo 1.
El concepto de material tiene diferentes usos según el contexto. De
acuerdo a la perspectiva con la que se analice el término, se puede llegar
a una u otra definición del mismo. El sentido del término siempre gira en
torno a una serie de complementos necesarios para llevar a cabo una
labor o elementos imprescindibles en una determinada acción.
El uso que se le da al término en la ingeniería, define a los materiales

como sustancias con cualidades útiles que pueden ser térmicas,
mecánicas o de otra clase*.
* Definición de wikipedia.
LOS materiales son estudiados por las Ciencias e Ingenierías de
Materiales.
En ciertas ocasiones es útil dividir las áreas del conocimiento en dos
ramas. La rama del conocimiento acerca de materiales no es la
excepción.
Por un lado se considera a la ciencia de materiales como la sub-rama que

investiga las relaciones entre las estructuras, composiciones y las
propiedades fundamentales de los materiales.
En contraste, en el otro extremo se considera a la ingeniería en

materiales como el diseño de las propiedades a partir de la relación
estructura-composición-propiedades.
Es decir, la diferencia entre el científico y el ingeniero en materiales es su
objetivo final.
El fin del científico es desarrollar o sintetizar nuevos materiales.
El fin del ingeniero es crear nuevos productos o sistemas (dispositivos)

usando los materiales disponibles o existentes, o bien, desarrollar técnicas
para procesar materiales.
Estructura y
Composicion
Ingeniería de nanomateriales
Jerarquía lineal del material definido por los principales subsistemas primitivos.
Pregunta: Que es la estructura?
En breve, la estructura de un material refiere al arreglo de sus componentes

internos.
•La estructura sub- atómica involucra a los electrones de los átomos, y a sus
interacciones con los núcleos.
•La estructura atómica es la organización de átomos o moléculas relativa a

sus vecinos.
•La estructura microscópica es aquella que puede ser observada por medio
de un microscopio.
•La estructura que puede ser discernida a simple vista se denomina

macroscópica.
Nota: No siempre la estructura refiere a arreglos cristalinos!

Pregunta: Que son las propiedades?
R. Una propiedad es la respuesta del material a un estimulo especifico.
Por ejemplo, la reflectividad (la capacidad de reflejar luz) es una propiedad de

una superficie metálica pulida.
El estimulo en este caso es la incidencia de luz.
La superconductividad es una propiedad a conducir corriente con cero

resistencia dada la aplicación de un campo eléctrico.
Importante: Una propiedad queda definida por el tipo y magnitud de la

respuesta a un estimulo especifico.
Virtualmente “todas” las propiedades de los materiales sólidos pueden
agruparse en seis distintas categorías:
•Mecánicas (respuesta a la aplicación de fuerzas)
•Eléctricas (respuesta a la aplicación de campo eléctrico)
•Térmicas (respuesta al calor)
•Magnéticas (respuesta a la aplicación de campo magnético)
•Ópticas (respuesta a la luz)
•Deteriorativas (respuesta al tiempo)
Sin embargo es también posible hablar de propiedades subjetivas (solo

pueden ser evaluadas por el hombre). Por ejemplo la estética.
También poseen propiedades económicas:
•Precio (respuesta a la oferta y demanda)
•Disponibilidad (respuesta a la magnitud de la reserva)
•Reciclabilidad (respuesta combinada de los dos anteriores)
Además poseen propiedades concernientes a la seguridad:
•Peligrosidad (respuesta al mal uso y/o manejo)
•Contaminante (respuesta que dará el material al ser expuesto

al ambiente, puede ser a corto o largo plazo).
Materia. El término materia tradicionalmente se refiere a la substancia de la
que todos los objetos están hechos.
Substancia. En el ámbito de las ciencias químicas, sustancia o substancia es

toda porción de materia que tiene la misma composición química y por lo tanto
comparte las mismas propiedades intensivas.
Coloquialmente las “sustancias” se dividen en sustancias puras y mezclas. Se
llama sustancia pura a aquella que no se puede descomponer en otras mediante
procedimientos físicos (como destilación, disolución, decantación, filtración,
separación ciclónica o magnética, etc.)
.
Proceso en el que no cambia la
naturaleza de las sustancias
ni se forman otras nuevas
Físico
Se llama mezcla al resultado de la combinación de varias sustancias puras, y es

posible la separación de éstas mediante procedimientos físicos
Se dice mezcla homogénea a aquella en la que las propiedades intensivas son
las mismas en toda la mezcla (por ejemplo, sal disuelta en agua).
Se dice mezclas heterogéneas a la que contiene dos o más sustancias

combinadas de tal forma que cada una conserva su identidad química.
Las mezclas heterogéneas o no uniformes son aquellas en las que la
composición de la muestra varía de un punto a otro. Muchas rocas pertenecen a
esta categoría. En un trozo de granito se pueden distinguir varios componentes,
que se diferencian entre ellos por el color.
Las sustancias puras no se pueden separar sin romper enlaces químicos. Es
posible que la sustancia pura se descomponga mediante procesos químicos. Si
ello es posible, se dice que la sustancia es compuesta; en caso contrario, se dice
que es una sustancia simple (o elemental).
Proceso en el que cambia

la naturaleza de la sustancias o se
forman otras nuevas.
Químico
Estados de agregación de la materia
1 Estado sólido
2 Estado líquido
3 Estado gaseoso
4 Estado plasmático
5 Condensado de Bose-Einstein
6 Condensado de Fermi
7 Supersólido
8 etc.
Los objetos en estado sólido se presentan como cuerpos de forma definida; sus átomos
a menudo se entrelazan formando estructuras estrechas definidas, lo que les confiere la
capacidad de soportar fuerzas sin deformación aparente. Son calificados generalmente
como duros y resistentes, y en ellos las fuerzas de atracción son mayores que las de
repulsión. En los sólidos cristalinos, la presencia de espacios intermoleculares pequeños
da paso a la intervención de las fuerzas de enlace, que ubican a las celdillas en formas
geométricas. En los amorfos o vítreos, por el contrario, las partículas que los constituyen
carecen de una estructura ordenada.
Las sustancias en estado sólido suelen presentar algunas de las siguientes
características:
Cohesión elevada.
Forma definida.
Incompresibilidad.
Resistencia a la fragmentación.
Fluidez muy baja o nula.
Algunos de ellos se subliman.
La Característica principal del estado liquido es la capacidad de fluir y adaptarse a la
forma del recipiente que lo contiene. En este caso, aún existe cierta unión entre los átomos
del cuerpo, aunque mucho menos intensa que en los sólidos.
El estado líquido presenta las siguientes características:

Cohesión menor al solido típico.
Movimiento energía cinética.
No poseen forma definida.
Toma la forma de la superficie o el recipiente que lo contiene.
En el frío se contrae (exceptuando el agua).
Posee fluidez a través de pequeños orificios.
Puede presentar difusión.
Volumen constante
Las moléculas en el estado gaseoso se encuentran prácticamente libres, de modo que son
capaces de distribuirse por todo el espacio en el cual son contenidos.
El estado gaseoso presenta las siguientes características:

Cohesión casi nula.
No tienen forma definida.
Su volumen es variable.
Examen
Como clasificaría los siguiente materiales en las anteriores categorías?
Solido, liquido, gas, sustancia, mezcla, homogénea, heterogénea?
La fibra de vidrio.
La arena de playa.
La madera.
La gelatina.
El humo de cigarro.
La vaselina.
La espuma de cerveza.
La lluvia.
Una nube.
El tequila.
El fuego.
Coloides y suspensiones
Una suspensión es una mezcla heterogénea formada por un sólido en polvo y/o
pequeñas partículas no solubles (fase dispersa) que se dispersan en un medio líquido (fase
dispersante o dispersora).
Las suspensiones se diferencian de los coloides o sistemas coloidales, principalmente en el
tamaño de las partículas de la fase dispersa. Las partículas en las suspensiones son
visibles a nivel macroscópico (mayores a 1 µm), y de los coloides a nivel microscópico
(entre 1 nm y 1 µm). Además al reposar las fases de una suspensión se separan, mientras
que las de un coloide no lo hacen. La suspensión es filtrable, mientras que el coloide no es
filtrable.
sistema coloidal, suspensión coloidal o dispersión coloidal es un sistema formado
por dos o más fases, principalmente: una continua, normalmente fluida, y otra dispersa
en forma de partículas; por lo general sólidas. La fase dispersa es la que se halla en
menor proporción. Normalmente la fase continua es un líquido, pero pueden encontrarse
coloides cuyos componentes se encuentran en otros estados de agregación.
El nombre de coloide proviene de la raíz griega kolas que significa «que puede
pegarse». Este nombre que hace referencia a una de las principales propiedades de los
coloides: su tendencia espontánea a agregar o formar coágulos.
Tipos de coloides
Fase dispersa
Gas Líquido Sólido
No es posible porque Aerosol líquido, Aerosol sólido,

Gas todos los gases Ejemplos: niebla, Ejemplos: humo, polvo
son solubles entre sí. bruma en suspensión
Emulsión,
Espuma, Sol,
Ejemplos: leche,
Fase continua Líquido Ejemplos: espuma de Ejemplos: pinturas, tinta
Salsa mayonesa,
afeitado, nata china
cremas cosméticas
Espuma sólida
Sol sólido o
(foam), Gel,
composite,
Sólido Ejemplos: piedra Ejemplos: gelatina, gom
Ejemplos: fibra de
pómez, aerogeles, inola, queso
vidrio, concreto,
merengue.
Materia granular
La materia granular o materia granulada es aquella que está formada por
un conjunto de partículas macroscópicas sólidas lo suficientemente grandes
para que la única fuerza de interacción entre ellas sea la de fricción.
Colectivamente, este tipo de materia presenta propiedades que pueden
semejar, dependiendo del tipo de fuerzas a las que esté sometida, a las de el
estado sólido, el estado líquido o un gas. Una característica importante es que
la materia granular tiende a disipar rápidamente la energía de sus partículas
debido a la fuerza de fricción. Esto da lugar a fenómenos de gran importancia
como las avalanchas, los atascamientos en descargas de silos, entre otras.
Como ejemplos de materia granular se encuentran los granos y semillas,
la nieve, la arena, etc.
Polvo
Polvo es un nombre genérico para las partículas sólidas con un diámetro
menor a los 500 micrometros (alternativamente, ver arena o gránulos) y, en
forma más general, materia fina. En la Tierra, el polvo que se encuentra en
la atmósfera terrestre proviene de varias fuentes, por ejemplo: polvo
del suelo levantado por el viento,erupciones volcánicas, incendios y polución.
El polvo disperso en el aire es considerado un aerosol y puede tener efectos
sobre las propiedades y comportamiento de la atmósfera frente a la radiación
solar y efectos significativos en el clima.
Nanomateriales
Los nanomateriales son materiales con propiedades morfológicas más

pequeñas que un micrómetro en al menos una dimensión.1 A pesar del hecho de
que no hay consenso sobre el tamaño mínimo o máximo de un nanomaterial,
algunos autores restringen su tamaño de 1 a 100 nm, una definición lógica
situaría la nanoescala entre la microescala (1 micrómetro) y la escala
atómica/molecular (alrededor de 0.2 nanómetros).
Básicamente casi todos los nanomateriales serán alguna especie de coloide.

Clasificación de los
nanomateriales
Los nanomateriales pueden ser clasificados por su dimensionalida:
Dimensionalidad cero: puntos y cúmulos.
Dimensionaldad uno: nano fibras, nanoesferas, filamentos, alambres y

varillas. (wiskers).
Dimensionalidad dos: películas, superficies, plaquetas, laminas, redes.
Dimensionalidad tres: nanomateriales 3D (composites).
Dimensionalidad compleja: dendrimeros y zeolitas.

Dimensionalidad cero: puntos y cúmulos.
Dimensionalidad uno: varillas, alambres, esferas.
Dimensionalidad
dos: películas,
redes, laminas.
Dimensionalidad tres: Nanocompositos
Dimensionalidad compleja:
zeolitas
Nano-helecho
Nano-cebolla
Muy importante
Debemos considerar los constituyentes

del nanomaterial a todo aquello que
afecta a sus propiedades.
Practica #1: síntesis de
nanomateriales.
Todos los materiales pueden en principio ser descritos a la nanoescala. Los

nanomateriales pueden ser de origen natural o artificial
Naturales. – Tiene una nanoestructura inherente, sin

ser procesados, modificados o producidos por el
hombre
nanomateriales
Artificiales. – Adquieren nanoestructura debido al

procesamientos dados por el hombre
Sin importar su origen, los nanomateriales poseen propiedades que dependen del
confinamiento espacial (están limitados por su dimensionalidad).
Objetivo de la practica: El estudiante deberá comprender que la
naturaleza es la principal aliada en la síntesis y producción de
nanomateriales.
Estructura y
Composicion
Se tratara de sintetizar distintos nanomateriales por medio de activación térmica por

radiación de microondas. El método lo expondrá el profesor.
Se observaran los posibles nanomateriales por microscopio óptico y electrónico.
Como se hará el reporte?
El estudiante deberá investigar cuales fueron las causas del éxito y fracaso en la
producción de los distintos nanomateriales. El reporte se enfocara en la discusión de su
investigación.
Tarea: Leer y traducir al español el siguiente texto.

http://nanoyou.eu/attachments/188_Module-1-chapter-2-proofread.pdf
El texto será discutido en horario de clase.

Naturales. – Tiene una nanoestructura inherente, sin

ser procesados, modificados o producidos por el
hombre
nanomateriales

El procesamiento
Estructura y
Composicion
Todo proceso químico conducido en cualquier escala puede descomponerse en una

serie ordenada de lo que pudieran Ilamarse OPERACIONES UNITARIAS, como
pulverización, secado, cristalización, filtración, evaporación, destilación... El número de
estas operaciones básicas no es muy grande, y generalmente sólo unas cuantas de ellas
intervienen en un proceso determinado.
De este modo para la clasificación de las operaciones unitarias se atiende a la propiedad
que predomina en una transformación. En base a ello la clasificación se hace en dos
grandes grupos:
• Operaciones unitarias físicas.

 De transferencia de materia.
 De transferencia de energía.
 De transferencia simultánea de materia y energía.
 De transferencia de cantidad de movimiento.-
 Complementarias.
• Operaciones unitarias químicas.

 Tiene por objetivo distribuir de una forma distinta los átomos de una molécula
para dar otra, es decir, el paso de los reactivos a los productos.
Manipulación de sólidos
Las características de manipulación de los sólidos son relevantes en muchísimos procesos industriales,
especialmente en los que intervienen:
• Polvos
• Pellets
• Cristales
• Agregados
Manipulaciones más comunes:
• Tamizado
• Estibamiento
• Mezcla a doble cono
• Pesado
• Separación ciclónica
• Molienda a bolas
Tamizado
Tamizar es separar una materia granulosa según el tamaño del grano para lo cual una
superficie perforada (tamiz, trama con luz definida) permite el paso de los componentes
finos y se lo impide a los más bastos. Al tamizar se obtiene una separación del material
en tamizado y residuo. Pueden obtenerse diferentes fracciones delimitadas
por el tamaño de partícula. Pueden definirse también el tamizado como la clasificación
en diferentes fracciones de tamaño de partícula con ayuda de tamices. Los tamices
tienen una malla cuadrada y en la mayor parte delos casos son metálicos. En el tamizado
suele descuidarse el considerar la importancia de la forma de las partículas. La sustancia
o mezcla posee después de haber pasado completamente un tamiz de la malla precisa,
un grado de trituración determinado. Este grado se designara según la luz de la malla del
tamiz.
Mezclado
El mezclado es una de lasoperaciones unitarias de la ingeniería química más difíciles de
someter a un análisis científico. Hasta el presente no se ha desarrollado ninguna
fórmula o ecuación aplicable al cálculo de grado del realización al que se verifica la
mezcla, o la velocidad con que se realiza, en determinadas condiciones. Se dice a veces
que solo el consumo de energía eléctrica de un mezclador proporciona una medida
real del grado en que se ha completado una mezcla, porque se necesita una cantidad
definida de trabajo para mezclar las partículas del material dentro del recipiente que lo
contiene. Con todo, esto nunca es verdad en la práctica, debido a las interferencias
imposibles de evaluar, tales como corrientes transversales, corrientes parásitas, que se
establecen, (incluso en las mezcla de plásticos y sólidos) dentro del recipiente.
Diagrama de proceso
http://www.scribd.com/doc/18417412/2-
OPERACIONES-UNITARIAS
Curso: Ingeniería de Nanomateriales.

Naturales. – Tiene una nanoestructura inherente,

sin ser procesados, modificados o producidos por el
hombre
[nano]materiales

El procesamiento

pulverización, secado, cristalización, filtración, evaporación, destilación... El número
de estas operaciones básicas no es muy grande, y generalmente sólo unas cuantas
de ellas intervienen en un proceso determinado.
El procesamiento es el causante, o la raíz de las propiedades, y

por lo tanto del desempeño.
De este modo para la clasificación de las operaciones unitarias se atiende a la
propiedad que predomina en una transformación. La ingeniería química clasifica en
dos grandes grupos:
• Operaciones unitarias físicas.
✓ De transferencia de materia.
✓ De transferencia de energía.
✓ De transferencia simultánea de materia y energía.
✓ De transferencia de cantidad de movimiento.-
✓ Complementarias.
• Operaciones unitarias químicas.
✓ Tiene por objetivo distribuir de una forma distinta los átomos de una
molécula para dar otra, es decir, el paso de los reactivos a los productos.
• Operaciones unitarias biológicas (clasificación no existente en la ingeniería
química).
✓ Dadas a partir de la de la intervención de organismos vivientes en la
transformación (por ejemplo, la síntesis por la intervención de bacterias).
El procesamiento puede ser dividido en operaciones
unitarias
Operación Unitaria #1A
Operación Unitaria #3 Operación Unitaria #4
Operación Unitaria #2B

Operación Unitaria #5
Resultado
#1
(Nano)Materiales naturales vs artificiales
Ciertos elementos Ciertos elementos

químicos químicos
Procesamiento natural Procesamiento artificial
(Nano)materiales (Nano)materiales
naturales sintéticos o artificiales
Propiedades Propiedades
Aplicaciones en la Aplicaciones en la
naturaleza tecnología
Nano-materiales naturales
Amosita o amianto blanco
Casi todos los minerales tienen características morfológicas por debajo de los 10 nm.
La naturaleza es la experta en nanotecnología
Se incluyo una ligera
variación en el
procesamiento de un
nanomaterial (un gen).
Casi todas la “operaciones
unitarias” permanecen
invariantes entre los
mutantes de una especie.
La mutación da ventajas?
Si la respuesta es si, entonces el
organismo se reproduce y
predomina sobre tu antecesor.
La selectividad que imponen los ambientes adversos es la clave de

la diversidad!
La naturaleza es la teacher!
Aprendiendo de la naturaleza!
hombre
nanomateriales

Casuales ( o no intencionales).- Dados por una

determinada secuencia de operaciones
Nanomateriales unitarias que resultan en un nanomaterial.
Artificiales
Intencionales.- se tiene control sobre las
operaciones unitarias.
Un nanomaterial casual dejará de serlo cuando tengamos control

sobre las operaciones unitarias que lo generan!
La clave es entonces tomar control
sobre el procesamiento!
Procesamiento sin control Nanomaterial casual
Procesamiento con Nanomaterial real

control
Regla de oro para modificar (nano)materiales, copiada de la
naturaleza: modificar a un tiempo solo una de las operaciones
unitarias.
Operación Unitaria #2ª (modificada)

Resultado
#2
Comparamos las propiedades.
resultado# Diseñamos el dispositivo
1 con el material #2
S
i
Tiene mejores Son las

propiedades el propiedades
S
resultado# material #2 las adecuadas
que el
i
2 para la
material#1? aplicación?
No No
Continuamos
modificamos
el procesamiento
Moraleja: la naturaleza es quien hace
la síntesis, debemos “jugar” con sus
reglas si queremos ser exitosos.
Tomado de: National Nanotechnology
Initiative
Los nueve grandes retos para la nanotecnologia:
1. Materiales nanoestructurados hechos a la medida.
2. Manufactura a nanoescala.
3. Detección y protección a sustancias químicas, biológicas
y explosivos.
4. Instrumentación y metrología a nanoescala.
5. Nano-electrónica, -fotónica y –magnetismo
6. Salud: terapia y diagnóstico.
7. Conversión eficiente y almacenamiento de energía.
8. Microvehículos y robótica.
9. Protección del ambiente.
M.C. Roco 4/01/04
Como producir nano-materiales?
Top-Down (desde arriba).
Reducir lo grande hasta hacerlo

pequeño.
Bottom-up (desde abajo).
Construir desde lo pequeño hacia lo

grande
Top-Down vs Bottom-
up
•Las técnicas de top-down toman un material

en bulto, este se maquina o modifica hasta
llevarlo a las dimensiones y forma requeridas
.
•Las técnicas bottom-up construyen creciendo

algo desde formas mas básicas, como átomos
y moléculas.
El método Top-Down en
semiconductores
El método de litografía
Limitado por la resolución de la

luz utilizada.
http://pages.unibas.ch/phys-meso/Education/Projektstudien/Lithographie/Litho-M1-Lithography.html
Que es lo que constituye un
proceso top-down?
• Producir una película
delgada sobre un
sustrato y después
reformar su superficie
por medio de foto-
litografía.
www.nanoscience.at/ aboutnano_en.html
Estado del arte en la tecnología
Top-down.
193 nm ArF excimer laser
• El uso de láseres
avanzados (λ =193 nm)
con mascarillas de fase
para producir
características de 65 nm.
•
• Requiere de óptica
http://www.lrsm.upenn.edu/~frenchrh/lithography.htm
avanzada.
Problemas con el método Top-
Down
•El costo de la tecnología crece
exponencialmente con el tamaño
requerido.
•Los limites físicos de la litografía son

un gran inconveniente.
•La densidad de energía y la disipación

de calor son un factor cuando se trata de
dimensiones pequeñas.
http://www.cit.gu.edu.au/~s55086/qucomp/gifs/intro.moore1.gif
El método bottom-up
•Es opuesto al método top-down.
•En lugar de selectivamente remover material,

el método bottom-up selectivamente agrega
material (átomos y moléculas) para crear
estructuras.
http://idol.union.edu/~malekis/ESC2
4/KoskywebModules/sa_topd.htm
Los fundamentos del bottom-
up
La naturaleza usa el esquema bottom-up para construir:
✓Cristales
✓Células
✓Humanos
✓La biología y la química pueden ser utilizados para

ensamblar, dirigir y construir el crecimiento de estructuras
complejas
Porque se requiere un método
bottom-up?
•Permite geometrías mas pequeñas y complejas que la litografía.
•Algunas estructuras son crecidas naturalmente por este método. Por

ejemplo los nanotubos de carbono.
•Las tecnologías de semiconductores orgánicos están basadas en

bottom-up.
•La formación de películas y estructuras es mas fácil
•Es mas económico que el método top-down.

Top-down Versus Bottom-up
Proceso Top Down Proceso Bottom Up
Inicia con el sustrato virgen Inicia con un sustrato virgen
Aplicar una capa de resina Alterar el área del sustrato

foto sensitiva donde la estructura será creada
agregando un polímero, un
defecto u otra técnica.
Exponer por medio de una

mascarilla con luz
ultravioleta y revelar la
zona expuesta. Crecer o ensamblar la
estructura determinada por
el paso anterior
(autoensamble)
Grabar el sustrato con el
patrón deseado
Los resultados obtenidos por medio de los procesos bottom-up and top-down pueden ser equivalentes
Breve listado de las técnicas más comunes para
producir nano-materiales:
•Condensación fase gas
•Depósito en vacio y vaporización (PVD)
•Depósito de vapores químicos (CVD)
•Depósito atómico por capas
•Implantación iónica
•Desbaste mecánico
•Desbastado por haces iónicos y láseres
•Método Sol-Gel
•Hidrolisis
•Electrodeposición
•Aglomeración
•Bio-métodos
•Autoensamblado selectivo
Autoensamble
•El autoensamble es la acción coordinada de entidades

independientes para producir estructuras ordenadas, con
forma definida y de mayor tamaño.
•Usado por la naturaleza.
•Se inicia a escala atómica.
•Es el fundamento del método bottom-up.

Proceso de Fabricación de
Nanodots (Nano-puntos)
1. Aplicar una capa templete de polímero para
producir nanodots
autoensamblada de
polímero.
2. Crecer una capa del
material deseado
para crear los
NanoDots.
65 000 000 000 nanodots por cm2

http://news.bbc.co.uk/1/hi/sci/tech/33010241.stm
Nanodots
Cada nanodot
podría almacenar
un bit de
información.
13 nm alto
65 000 000 000 80 nm
nanodots por cm2 ancho
Nanodots autoensamblados
http://physics.nist.gov/Divisions/Div841/Gp3/Projects/Atom/atom_dots_proj.h
tml
Materiales Nano escalados
Nanoalambre y Nanotubos
• Dimensión lateral: 1 – 100 nm
• Exhiben propiedades físicas
novedosas debido a:
– El confinamiento cuántico de dos dimensiones
– La estructura uno-dimensional
– La muy alta superficie especifica (Relación
Superficie/Volumen)
• Aplicaciones potenciales en muchos
dispositivos y sistemas
– Sensores y actuadores nanométricos
– Dispositivos fotovoltaicos - celdas solares - Celda solar de nanoalambres: La
superficie de los nanoalambres tienen
– Transistores, diodo, láseres mayor capacidad de absorber la luz
solar – McMaster Univ., 2008
nanotubos de carbono
Nanotubos de carbono
• Forma tubular de carbón con 1nm de diámetro.

(Equivalente a una lámina de grafito enrollada).
• Los nanotubos de carbono presentan propiedades
mecánicas extraordinarias. Módulo de Young > 1
Tera Pascal y resistencia a tensión ~ 200 GPa
• Los nanotubos podrían ser metálicos,
semiconductores o compuestos.
Sección de un nanotubo de carbono
Nanotechnology. A gentle introduction to the next big idea.

Mark Ratner, Daniel Ratner. Prentice Hall.
estructura de un nanotubo de pared simple
http://www.oviedo.es/personales/carbon/ind
ex.htm
Nanotubo compuesto
http://www.oviedo.es/personales/carbon/ind
ex.htm
Estructuras con nanotubos
Imagen de PVC irradiado con electrones de 2
MeV
a una dosis de 2000 Mrad
PVC-irradiado a 2000 Mrad
0.33nm
PVC irradiado a 1700 Mrads
Estructura cristalina con simetría hexagonal
de PVC irradiado a1700 Mrad
0.12 nm
Aplicaciones de nanotubos de carbono
• Interconexiones con alambres cuánticos

• Electrónica molecular basada en nanotubos
• Sensores: fuerza, presión, ambiente químico
• Como puntas de AFM para nanomanipulación
• Nanomotores
• Almacenamiento de Hidrógeno o Lítio
• Puntas para emisión de campo (pantallas TV)
• Cables de alta resistencia y bajo peso
• Materiales multifuncionales
• Lo que se les ocurra............
Los problemas fundamentales
• Nuevos fenómenos cuánticos propios de las
nanoestructuras.
• Los arreglos atómicos en la superficie de nanocristales.
¿Qué tan diferentes son de las estructuras macro?
• ¿Se podrán sintetizar nanotubos de determinada longitud y
helicidad? ¿Se podrán sintetizar heterouniones en 1-D?
• ¿Qué nuevos conocimientos podrán ser obtenidos del
estudio de sistemas poliméricos y biológicos, derivados de
la capacidad de estudiar propiedades de moléculas
individuales?
Compuesto Nanotubo de Carbono-
polímero
http://www.ipt.arc.nasa.gov/cntpolymer.html
Materiales Nano escalados
Proteina
Bionanomateriales
1) Materiales biológicos utilizados en la
nanotecnología
- Proteínas, enzimas, DNA, RNA, péptidos
1) Materiales sintéticos usados en
Enzimas entrecruzadas
aplicaciones biomédicas usadas como catalizador – Univ.
of Connecticut, Storrs , 2007
- Polímeros, silicio poroso, nanotubos de
carbón
Enzimas
usadas en
catálisis de Célula de hueso en silicio
Silicio poroso (PSi) oxidación poroso – Univ. of Rochester, 2007
Célula humana en PSi
Que es una nanoparticula?
• Una partícula sub-micrométrica cuyas dimensiones

son medidas en nanómetros.
Como se forma una nano-partícula?
action takes place Critical concentrantion, nucleation begins Aggregation happens due to i
Particles grow and consume all the solute
Subsequent growth of the nuclei lowers the solute concentration
Best time to synthesize nanoparticles
Img by deMello, J. & deMello, A. Microscale reactors: nanoscale products. Lab Chip 4, 11N–15N(2004).
Aplicaciones
Nanoelectrónica y computación
• Biomimética.........copiando a la naturaleza
– El cerebro humano contiene 1014 interconexiones y
opera 1016 ops/s, consumiendo muy baja potencia y con
elementos de computación muy imprecisos.
– El sistema inmunológico humano se auto-repara.
• Computadoras con el don de ubicuidad

– Elementos computacionales implantados en el cuerpo
humano, utensilios, herramientas y artefactos de todo
tipo.
“Existe igual distancia por recorrer ( en escala logarítmica) a

partir del presente, que la ya recorrida desde la ENIAC. El final
de la miniaturización de dispositivos CMOS representa, al mismo
tiempo, un peligro y una oportunidad.” -Stan
Williams HP.
• La física permitiría integrar 109 dispositivos en base a una
disipación de 1 watt y 1018 ops/s !NO SE SABE COMO!
– ¿Autómatas celulares cuánticos?
– ¿Nanoelectrónica molecular?
– ¿Circuitos sintetizados químicamente?
• La nanoelectrónica del futuro demanda procesos de
autoensamble y arquitecturas tolerantes a defectos.
Transistor de nanoalambre supera a
MOSFET’s
24 de mayo 2006
El anuncio lo hicieron investigadores de la Universidad
de Harvard. El dispositivo consiste de una coraza de
Ge rodeada de una capa de Si formando un transistor
de efecto de campo, con dieléctrico de alta-κ y
compuerta metálica.
Ge/Si nanowire heterostructures as high-

performance field-effect transistors
Nature 441, 489-493 (25 May 2006)
Jie Xiang, Wei Lu, Yongjie Hu, Yue Wu, Hao
Yan and Charles M. Lieber
Imagen por microscopía electrónica de transmisión de la sección
trasversal del dispositivo. El corte trasversal es en la región de la
fuente y los electrodos de drenaje.
Espín + Electrónica
Espintrónica: campo emergente en la investigación básica y
aplicada que sustenta el desarrollo de dispositivos electrónicos
que utilizan el espín electrónico para una nueva y particular
función. Sus aplicaciones en electrónica digital “convencional”
incluyen: memorias no-volátiles de ultra-alta densidad y baja
potencia, con ventajas en su rendimiento sobre las basadas en
tecnología del silicio. Las aplicaciones en el procesado de
información no-convencional incluyen: computación cuántica.
En biotecnología se abren nuevas rutas de investigación.
Retos técnicos: inyección eficiente de los espines. Transporte,

control y detección de la polarización del espín y de las
corrientes con espín polarizado.
Spintronics : cutting edge Physics
“Magnetricidad, observada por primera
vez”
Oct., 14, 2009
El Centro de Londres para la Nanotecnología (LCN) reportó que una carga

magnética se puede comportar como una carga eléctrica en algunos
materiales.
Los resultados de la investigación probaron la existencia de cargas magnéticas
de tamaño atómico, denominadas “monopolos magnéticos” que se comportan
e interaccionan como las más familiares cargas eléctricas. Se demuestra, al
mismo tiempo, una simetría perfecta entre la electricidad y el magnetismo –
fenómeno denominado magnetricidad - por los autores del LCN y del Consejo
para la Ciencia y la Tecnología que maneja las unidades ISSIS con fuentes de
neutrones y de muones.
Para probar experimentalmente la existencia de una corriente magnética, el
equipo de investigadores mapeó, de acuerdo con la teoría de Onsager de 1934,
el movimiento de iones en agua, como el movimiento de corrientes magnéticas
en un material denominado hielo-espín. Probaron la teoría aplicando campos
magnéticos a una muestra del hielo-espín, a muy bajas temperaturas, y
observaron el proceso de relajamiento de muones en el ISIS, técnica que utiliza
un super-microscopio que permite observaciones con resolución atómica.
Spin filtering in a parallel double quantum dot
Parallel quantum dot defined in 2DEG

Source
Drain
[F.M., F.R., E.C., (to be published)]

Dot 1
Dot 2
Medico-biológicas
Espectativas en medicina
y la salud
• Mejorar la capacidad de caracterización genética mediante

la aplicación de nanodispositivos para secuenciar más
eficientemente.
• Desarrollo de dispositivos remotos e “in vivo” para
tratamientos médicos y control de la salud.
• Utilización óptima de fármacos y los mecanismos de
aplicación “in situ”. Nuevas rutas de aplicación.
• Diseño y construcción de nuevos tejidos y órganos
artificiales para implantes, más durables y resistentes al
rechazo.
• Sensores para detección temprana y prevención
Diseño de fármacos a nivel molecular
• Macromoléculas biológicas vacunas

• Moléculas individuales y su interacción con el ADN
u otra proteínas.
• Enfoque mecanístico: anti-inflamatorios, anti-
depresivos, definir en detalles su acción específica
en el tiempo y en el espacio.
• La actividad del fármaco deberá conocerse en
función de mecanismos específicos evitando al
máximo los “efectos secundarios”.
Nanoterapias
Nuevas formas de destruir tumores.
Utilizando nanocápsulas de oro que se
implantan en el tumor y al calentarse
con radiación infra-roja, lo destruye
Nanopartículas de oro con segmentos cortos

de ADN permiten identificar la presencia de
una secuencia específica de ADN en una
Muestra dada.
Interfaces neuro-electrónicas
• Etapa visionaria, pero “Robocop” se podría volver

realidad.
• Implican la conexión mediante nano-dispositivos,
de sistemas computacionales con el sistema
nervioso.
• El sistema nervioso transmite señales eléctricas, via
el movimiento de iones de K y Na
• El objetivo de las interfaces neuro-electrónicas es
registrar, interpretar y eventualmente controlar
dichas señales y las respuestas
LOS PUNTOS CUÁNTICOS ( Q-dots) de
selenuro de cadmio (CdSe) producen
fluorescencia de diferentes colores
dependiendo del tamaño del punto
cuántico. Se trata de nanopartículas
semiconductoras y fluorescentes. El color
de la luz varía con el tamaño del punto y se
corre hacia la zona azul del espectro
visible, en la medida en que el punto se va
haciendo más pequeño. Las aplicaciones
potenciales de los puntos cuánticos
incluyen: láseres, pantallas a color y bio-
imágenes. El desarrollo de su potencial
comercial, sin embargo, ha sido lento ya
que los puntos cuánticos resultan muy
Fluorescencencia inducida por exposición a caros, generalmente del orden de 2,000
dls., por gramo, debido al alto costo de
luz ultravioleta en tubos de ensayo que
reactivos y solventes utilizados en el
contienen puntos cuánticos de selenuro de proceso de manufactura.
cadmio (CdSe) de diferentes tamaños. Sci.
Am. 5/12/2005
El efecto cuántico del tamaño
Motores moleculares
• Las estructuras biológicas se mueven o

tienen partes en movimiento.
• Los motores moleculares son
nanoestructuras complejas que ha
evolucionado con los seres vivos. i.e.,
quinesina, prestina,
Nanorotor
nanotovera
Algunos ejemplos de aplicaciones recientes:
• Materiales cristalinos utilizados en catalizadores; 3x10 9 dls/año

• Materiales mesoporosos ordenados para eliminar
contaminantes ultra-finos en aceites.
• Polímeros reforzados con nanopartículas para sustituir metales
en los automóviles y reducir el consumo de gasolina
Conclusiones
• Los próximos 10 - 15 años serán testigos de una
verdadera revolución científica y tecnológica,
derivada de la capacidad para ordenar,
organizar y manipular la materia, en la escala
nanométrica, en forma sistemática.
• Es indispensable ordenarnos y organizarnos
para participar en esta revolución en forma
sistemática y efectiva.
¡HAY MUCHA Y EXCITANTE FISICA, QUÍMICA Y BIOLOGÍA
EN LOS TIEMPOS POR VENIR !
Aplicaciones de la nanotecnología
Tecnologías de la información Energía

• Tecnologías mas eficientes
• Computadoras mas
en el consumo, manejo y
pequeñas, mas
producción de energía.
rápidas, mas eficientes
− celdas solares
y potentes. Impacto en − celdas de combustible
los medios de − Baterías
comunicación − catalizadores para producción
de combustibles
Medicina Productos de consumo
• Alimentos y bebidas
• Tratamiento de cáncer
−Mejores sistemas de empaque
• Reparación de hueso −Control de calidad de alimentos
• Terapias in-situ. −Nuevas fibras para textiles y
• Nuevos medicamentos mobiliario
• Herramientas medicas −Pinturas y barnices
• Diagnostico medico −Electrodomésticos y
• Técnicas de cosméticos
− Pinturas auto limpiables y
procesamiento de
resistentes.
imágenes. −Etc.
Nanotechnology Health and
Environmental Concerns
− Human and the environment come under
exposure to nanomaterials at different stages
of the product cycle
− Nanomaterials have large surface to volume
ratio and novel physical as well as chemical
properties which may cause them to pose
hazards to humans and the environment
− Health and the environmental impacts
associated with the exposure to many of the
engineered nanomaterials are still uncertain
− The environmental fate and associated risk of Exposure of human and the environment to
waste nanomaterials should be assessed – e.g. nanomaterials at different stages of product
toxic transformation, and interactions with life cycle – US environmental protection agency, 2007 (epc.gov)
organic and inorganic materials
Nanoscale Devices and Integrated
Nanosystems
Nanophotonic Systems
− Nanophotonic systems work with light signals
vs. electrical signals in electronic systems
− Enable parallel processing that means higher
A silicon processor featuring on-chip
computing capability in a smaller chip nanophotonic network – IBM Corp., 2008
− Enable realization of optical systems on
semiconductor chip
Fuel Cells
− Fuel cells use hydrogen and air as fuels
and produce water as by product
− The technology uses a nanomaterial 500 W fuel cell –
Schematic of a fuel cell
membrane to produce electricity – Energy solution center Inc. H2economy.com
Nanoscale Devices and Integrated
Nanosystems
Lab on Chip
− A lab on chip integrates one or more laboratory
operation on a single chip
− Provides fast result and easy operation
− Applications: Biochemical analysis (DNA/protein/cell
analysis) and bio-defense Lab on chip gene analysis
device – IBN Singapore, 2008
Drug Delivery Systems
Impact of nanotechnology on drug delivery systems:
− Targeted drug delivery
− Improved delivery of poorly water soluble drugs
− Co-delivery of two or more drugs
− Imaging of drug delivery sites using imaging
modalities Targeted drug delivery
– ACS Nano 2009, DOI: 10.1021/nn900002m
Medical Nanotechnology or
Nanomedicine
Nanomedicine is the application of nanotechnology in
medicine, including to cure diseases and repair
damaged tissues such as bone, muscle, and nerve
Key Goals for Nanomedicine

− To develop cure for traditionally incurable diseases (e.g. cancer) through the
utilization of nanotechnology
− To provide more effective cure with fewer side effects by means of targeted
drug delivery systems
Nanotechnology in Health Care
• Thermal ablation of
cancer cells
− Nanoshells have metallic
outer layer and silica core
− Selectively attracted to cancer
shells either through a
phenomena called enhanced
permeation retention or due
to some molecules coated on
the shells
Thermal ablation of cancer cells assisted
− The nanoshells are heated by nanoshells coated with metallic layer
with an external energy and an external energy source – National Cancer
Institute
source killing the cancer cells

Nanotechnology in Health Care
Treatment
• Targeted drug delivery
− Nanoparticles containing
drugs are coated with
targeting agents (e.g.
conjugated antibodies)
− The nanoparticles
circulate through the
Targeted drug delivery –
blood vessels and reach Targeted drug delivery using a
the target cells multicomponent nanoparticle
containing therapeutic as well
− Drugs are released as biological surface modifying
agents – Mauro Ferrari, Univ. of Cal. Berkley
directly into the targeted
cells
Benefits: Today & Tomorrow
Medicine Information Energy Materials Food, Water Instruments

and Technology Production Science and the
Health / Storage Environment
Drug GMR Hard Hydrogen Lightweight Remediation, Tunneling

delivery Disk Fuel Cells and strong Protection microscopy
EPA Interest
Consumer Products
▪ Self-cleaning glass, ceramics, and metals

▪ Stain-free clothing and mattresses
▪ Lighter weight, stronger materials
▪ Automobile bumpers, tennis racquets
▪ More efficient, cheaper catalytic converters on cars
▪ Longer lasting tires and tennis balls
▪ Improved dental-bonding/filling materials
▪ New types of burn and wound dressings
▪ Impermeable materials for food packaging
Nanomaterials –
Applications & Implications
The Good… The Bad…
• Cross blood-brain barrier – • Cross blood-brain barrier –

drug delivery impair health
• Placed in subsurface areas - • Placed in subsurface areas –
remediation impair ecosystem
• Small, real-time sensors – • Small, real-time sensors –
detection & protection privacy concerns
• Same compound, different • Same compound, different
properties – novel uses properties – reg. concerns
• Different disciplines – • Different disciplines –
increased collaboration limited understanding
Benefits of Nanotechnology
• In the computer world,

nanotechnology is important to
the development of small
computer circuits that can
reduced the size of computers.
Disadvantages of Nanotechnology
• Safety hazards with nanomaterials

• Some studies detected possible cancer-
causing properties of carbon nanotubes
• Some nanomaterials bounded with other
materials or components
Risk Assessment –
Life-Cycle Perspective
General Population Exposure
Manufacturing Consumer
Use or Misuse End of Life
Process
Recycle Disposal
Industrial Emissions Abrasion Pollution

Releases/Discharges Direct Contact Secondary Use
Risk Assessment –
Life-Cycle Perspective
Ecosystem Exposure
Manufacturing Consumer
Use or Misuse End of Life
Process
Recycle Disposal
Industrial Emissions Abrasion Land, Air, Water Pollution

Releases/Discharges Env. Application Incidental Env Debris
Curso: Ingeniería de Nanomateriales.
Quinta clase

hombre
[nano]materiales

El procesamiento

pulverización, secado, cristalización, filtración, evaporación, destilación... El número
de estas operaciones básicas no es muy grande, y generalmente sólo unas cuantas
de ellas intervienen en un proceso determinado.
El procesamiento es el causante, o la raíz de las propiedades, y

por lo tanto del desempeño.
El procesamiento puede ser dividido en operaciones
unitarias

Resultado
#1
(Nano)Materiales naturales vs artificiales
Ciertos elementos Ciertos elementos

químicos químicos
Procesamiento natural Procesamiento artificial
(Nano)materiales (Nano)materiales
naturales sintéticos o artificiales
Propiedades Propiedades
Aplicaciones en la Aplicaciones en la
naturaleza tecnología
La naturaleza es la experta en nanotecnología
Se incluyo una ligera
variación en el
procesamiento de un
nanomaterial (un gen).
Casi todas la “operaciones
unitarias” permanecen
invariantes entre los
mutantes de una especie.
La mutación da ventajas?
Si la respuesta es si, entonces el
organismo se reproduce y
predomina sobre tu antecesor.
La selectividad que imponen los ambientes adversos es la clave de

la diversidad!
La naturaleza es la teacher!
Aprendiendo de la naturaleza!
hombre
nanomateriales

Casuales ( o no intencionales).- Dados por una

determinada secuencia de operaciones
Nanomateriales unitarias que resultan en un nanomaterial.
Artificiales
Intencionales.- se tiene control sobre las
operaciones unitarias.
Un nanomaterial casual dejará de serlo cuando tengamos control

sobre las operaciones unitarias que lo generan!
La clave es entonces tomar control
sobre el procesamiento!
Procesamiento sin control Nanomaterial casual
Procesamiento con Nanomaterial real

control
Regla de oro para modificar (nano)materiales, copiada de la
naturaleza: modificar a un tiempo solo una de las operaciones
unitarias.
Operación Unitaria #2ª (modificada)

Resultado
#2
Comparamos las propiedades.
resultado# Diseñamos el dispositivo
1 con el material #2
S
i
Tiene mejores Son las

propiedades el propiedades
S
resultado# material #2 las adecuadas
que el
i
2 para la
material#1? aplicación?
No No
Continuamos
modificamos
el procesamiento
Moraleja: la naturaleza es quien hace
la síntesis, debemos “jugar” con sus
reglas si queremos ser exitosos.
Tomando el control
Temperatur
a
Presión
Concentració Procesamiento Nanomaterial

n
Fluj
o
Etc
Composició Catalizado
n r
Algunas variables físicas están relacionadas. Por ejemplo, la
presión con la concentración en un gas.
Rango de vacío Presión en Moléculas Camino libre
Torr por cm3 medio
Presión 760 2 X 1019 68 nm (68 X 10-9m)

atmosférica
Vacío bajo (low) 200 a 1 1019 a 1016 .1 a 100 µm
Vacío medio 1 a 10-3 1016 a 1013 .1 a 100 mm
Alto vacío 10-3 a 10-7 1013 a 109 10 cm a 1 km
Ultra alto vacío 10-7 a 10-12 109 a 104 1 a 105 km
Vacío < 10-12 < 104 > 105 km

extremadamente
alto
a 10-7 torr hay 1,000 millones de partículas
Presión en Moléculas/
Torr cm3
1 cm
760 2X 1019
200 a 1 1019 a 1016
1 a 10-3 1016 a 1013

1 cm
10-3 a 10-7 1013 a 109
10-7 a 10-12 109 a 104
< 10-12 < 104

1 cm = 10mm
a 10-12 torr hay 10,000 partículas
a presión atmosférica, 760 torr, hay 20,000,000,000,000,000,000 partículas

A presión atmosférica y a temperatura ambiente,
aproximadamente 8x1023 moléculas pegan en una superficie de
un centímetro cuadrado por segundo.
Esto significa que a una atmósfera, ~ 760 Torr a nivel del mar,
cada molécula de la superficie es golpeada 200 millones de
veces por segundo, o una vez cada 5 nanosegundos.
Si comparamos ese tiempo con el tiempo que normalmente se

necesita para hacer un experimento, por ejemplo, 20 minutos.
Durante nuestro experimento no queremos que un importante
número de moléculas de golpeen la superficie ya que pueden
adherirse o producir otros cambios.
El vacío es uno de los principales
aliados para producir
nanomateriales, porque?
Un
Unpoco
pocode
dehistoria
historia
Tecnología la clave para hacer cada vez
nanomateriales con mejor control!!!!!
Cuando pensamos en hacer síntesis -con

control a nivel atómico- pensamos que gran
parte del espacio está vacío.
Pero cuando analizamos el vacío nos damos
cuenta que ¡¡¡hay partículas por todas
partes!!!!
Dado que las partículas de la
atmosfera es un parámetro sin
control, para lograr nanomateriales
artificiales “no-casuales” debemos
controlar la atmosfera que rodea la
síntesis.
1. Conceptos básicos de vacío
1.1. Introducción
Iniciemos poniéndonos de acuerdo:
Definiciones: ¿de qué hablamos?
American Vacuum Society = AVS

AVS: el término vacío se refiere a cierto espacio lleno con gases a
una presión total menor que la presión atmosférica.
La atmósfera en la tierra tiene una presión media de

1013.25 hectopascales
al nivel del mar, medido en latitud 45º
La medida de presión del Sistema Internacional de Unidades

(SI) es el newton por metro cuadrado (N/m²) o Pascal (Pa).
La presión atmosférica a nivel del mar en unidades
internacionales es 101325 N/m² ó Pa que son exactamente
760 mm de mercurio
CNyN-UNAM Fundamentos de vacío http://www.cnyn.unam.mx/

!El aire pesa!
Además, la presión atmosférica varía de
lugar a lugar.
¿Porqué?
!En lugares altos tenemos menos aire
encima!
Ejemplos:
Ensenada, Acapulco, Los Cabos, Miami
1 atmósfera de presión = 760 mm
de mercurio
= 760 torr
Cd. De México 585 mm Hg
= 585 torr
“la presión disminuye 1 torr por cada 11
metros que nos
elevamos…..aproximadamente”
Dif. de presiones 760-580 = 175 torr
175 torr X 11m/1torr = 1925 m

EFECTOS INMEDIATOS:
el agua hierve en Ensenada a 100 ºC
en el DF a unos 93 ºC
Allá se gasta más gas…..y ¡las recetas de cocina fallan!
¡Sin embargo, podemos hacer hervir el agua a
temperatura ambiente!
(¡por demostrarse!)
¿cómo explicamos esto del agua hirviendo a diferentes
temperaturas?
¡pendiente por explicar!
IMPORTANTE
760 mm de mercurio son iguales a 760
torr
¿De dónde vienen esos 760 mm de Hg?

Un poco de historia
Según Aristóteles “la naturaleza le tenía miedo al vacío” por eso si se
intentaba vaciar algo el aire se apresuraba a llenarlo. La idea de que
vacío es falta de conocimiento también se debe al pensamiento
aristoteleano.
El desarrollo de la tecnología fue muy lento….la idea de no experimentar
mas que con la mente, una enseñanza que provenía del pensamiento
aristotélico, fue solo uno de los factores que pesó mucho en la edad
media para que no se desarrollara la tecnología...también hubo
algunos quemados….
Los antecedentes de la tecnología del vacío los encontramos en los
metalurgistas de Egipto, el Cáucaso y China al inventar los fuelles y
los pistones, con los que absorbían el aire y después lo comprimían al
presionar el fuelle para así activar el fuego para producir las altas
temperaturas necesarias para fundir el bronce y el hierro.
Podemos empezar la historia moderna del vacío con varios experimentos
que se realizaron a principios del siglo 17, por ahí alrededor de 1640…
Veamos que pasaba en Italia en esa época en la ciudad de Florencia:
En 1643, el físico
italiano
EvangelistaTorricelli
ideó un
procedimiento para
medir la presión
atmosférica.

¿Qué hizo Torricelli?

h = 76 cm
= 760 mm
Florencia está a nivel del mar!!!!
esta altura se usa como medida de

presión
1 atm = 760 mm de Hg
y en honor a su inventor:
h es decir,
= 760 torr
1 torr = 1 mm de Hg
Mercurio Por ejemplo, la Cd. de México tiene una
presión atmosférica de 585 torr
Hg

La presión en un lugar cambia
de acuerdo a las condiciones
climáticas:
En inglés: millibar la unidad

inglesa de presión es
1 lb/in2 = 1 psi
1 pound per square inch
1 atm = 760 torr = 1,013 milibares = 1.013 x 105 Pascales

1 milibar es un poquito mayor que 1 torr 1 milibar = 1.33 torr
Pa = Pascales se usa mas para presiones positivas como en prensas y en
llantas (tarea: ver sus llantas a cuantos Pa se deben inflar)
Tabla de equivalencias
Las unidades de presión más comunes

Otto Von Guericke desarrolló una bomba de vacío con la que alrededor de
1650 realizó varios experimentos
Experimento de los hemisferios de Magdeburgo

¡¡¡16 caballos no lograron separar los hemisferios!!!

Tomás Alva Edison haciendo vacío con un aparato a base de mercurio
en 1880

Año Autor Descubrimiento
Mejoras a la bomba de Von
Siglo XVIII Hauskbee y Nollet
Guericke
1850 Geissler y Toepler Bomba de columna de Hg
1865 Sprengel Bomba de gota de Hg
1905 Wolfgang Gaede Bomba de vacío o rotatoria
1913 Wolfgang Gaede Bomba molecular de vacío
1915 Wolfgang Gaede Bomba de difusión
1916 Irving Langmuir Condensación-difusión
1923 F. Holweck Bomba molecular
1935 Wolfgang Gaede Bomba de balastra o paleta
1936 Kenneth Hickman Bomba de difusión de aceite
1953 Schwartz y Herb Bomba iónica
Bomba criogénica
EL VACIO Y SUS APLICACIONES Laura Talavera y Mario Farías
1.2. Regímenes de vacío
régimen = rango
RANGOS DE VACIO
BAJO Y MEDIO ALTO ULTRAALTO

760 a 10-3 torr 10-3 a 10-7 torr 10-7 a 10-12 torr

Regímenes de vacío
régimen = rango
RANGOS DE VACIO
BAJO Y MEDIO ALTO ULTRAALTO

760 a 10-3 torr 10-3 a 10-7 torr 10-7 a 10-12 torr
Presión en torr Camino libre medio molecules por cm3
Aspiradora casera 600 70 nm 1019
Secado al vacío 1 a 0.1 100μm 1016
Bomba mecánica 1 a 10−3 100μm a10 cm 1016 a 1013
Foco incandescente 0.1 a 0.01 1 mm a1 cm 1014
Termo 10−2 a 10−4 1cm a 1m 1012
Termósfera terrestre 10−3 a 10−10 1cm a 1000 km 1014 a 106
Bulbo 10−7 a 10−10
Cámara de un equipo de MBE

10−9 a 10−11 1.105 km 109 a 104
(criobomba)
Presión en la luna 10−11 4 X 105
Espacio interplanetario 10
Espacio interestelar 1
Espacio intergaláctico 10-6

1.3 Conceptos básicos de gases
Gas:
- conjunto de átomos (moléculas) que no están ligados entres sí: LIBRES;
- llenan el recipiente que los contiene (los líquidos también? los sólidos?
-nos imaginamos pelotitas (partículas) que andan viajando en el recipiente
y chocan entre ellas y las paredes de ese recipiente
Presión: se produce por el choque de las partículas sobre las paredes del
recipiente
es decir, las partículas al chocar con las paredes ejercen una fuerza sobre
esa pared:
-entre más partículas mayor fuerza
-entre más gordas (masivas) mayor fuerza ---
-entre más rápidas mayor fuerza
-entre más “de frente” mayor fuerza
--entre más fuerza mas presión

--pero si todas estas mismas partículas pegan en una
área mayor la presión disminuye
P = F unidades lbs/pulgada cuadrada
A
La presión nos dice como se distribuye la fuerza
aplicada sobre un cuerpo:
P2 = 100 lbs
F F F = 100 lbs 10 inch2
P1 = 100 lbs
1 inch2
P2= 10 psi
P1 = 100 psi
A1 = 1 inch2 A = 10 inch2
2
La presión aumenta con la temperatura!
Recuerden una olla exprés, llega a explotar
demostración
Ley de los gases PV = nRT
P presión, V volumen, R constante, n número de moles (pensemos

en numero de moléculas) y
T temperatura en Kelvin.
Si P está en torr, V en litros y T en Kelvin (??)

entonces R = 62.4
Kelvin es la escala absoluta de temperatura:
0 °C = 273 K 27 °C = 300 K 0 K = -273 0 °C
Hagamos un calculito, Cuanto vale P si:
V = 22.4 lt, n = 1 mole y T =300 K
P X 22.4 = 1 X 62.4 X 273 ? Dividamos entre 22.4
P X 22.4 = P = 1 X 62.4 X 273 = 760 torr!

22.4 22.4
Camino libre medio:
es la distancia promedio que recorre una molécula entre
choque y choque
El camino libre medio es menor

que las dimensiones del
contenedor
Rango de vacío Presión en Moléculas/ Camino libre medio

Torr cm3
Presión 760 2 X 1019 68 nm (68 X 10-9m)
atmosférica
Vacío bajo (low) 200 a 1 1019 a 1016 .1 a 100 µm
Vacío medio 1 a 10-3 1016 a 1013 .1 a 100 mm

El camino libre medio es
mayor que las dimensiones
del contenedor
Rango de vacío Presión en Moléculas/ Camino

Torr cm3 libre medio
Ultra alto vacío 10-7 a 10-12 109 a 104 1 a 105 km
Vacío extremadamente alto < 10-12 < 104 > 105 km
Para vacíos cercanos a 10-3 torr el camino libre medio puede o no

ser mayor que las dimensiones del contenedor
Alto vacío 10-3 a 10-7 1013 a 109 10 cm a 1 km
.1m a 1000m
a 10-3 torr el camino libre medio es de 10 cm = .1m

a 10-3 torr el camino libre medio es de 1 metro
PRESIÓN DE VAPOR
AISLAMIENTO
= no entra ni
sale calor VAPOR VAPOR SATURADO (a una T)
Presión de vapor
al inicio un poco más tarde en equilibrio

salen más partículas de las que entran no. q´sale =no. qéntra
La presión de vapor depende de la temperatura. Ejemplo: una olla presto,

nitrógeno hierve a -296 °C (77K)
Los líquidos hierven a una temperatura fija cuando están en equilibrio con
la presión atmosférica: a esa temperatura su presión de vapor es 760 torr
Presiones de vapor de materiales seleccionados
Presión de Temperatura
Material vapor (°C)
(torr)
Agua 32 30
Aceite para 10-5 “
bombas
Grasa de 10-9 – 10-10 “
vacío
Apiezon L
Cemento 10-3 – 10-4 “
epóxico
Cobre (Cu) 10-11 500
Plomo (Pb) 5 x 10-5 500
Zinc (Zn) 2 500
Cadmio (Cd) 300 500
Material Temperatura Presión de
(°C) vapor
(torr)
Agua 100 760
93 585
0 4.5 Aceite 10-5 25 °C
para Torr
– 15 1.4 bombas
20 17.5 10-2 -10-3 “
Grasa
Torr
Mercurio 20 1 x 10-3 humana
360 760
Cuidado con tocar dentro de la cámara de vacío sin guantes:

huella digital = grasa + sudor = grasa + agua
grasa ….. peor que el agua porque tiene una presión de vapor menor,
alrededor de 10-3 torr (tarda mucho más en desaparecer….¡¡¡ semanas,
meses ¡¡¡)
Presiones de vapor para varios gases
Temperaturas P =760 torr

de ebullición
Presión (torr)
0 K = -273 °C Temperatura en
Kelvin
77 K = -196 °C
Con nitrógeno líquido no van a
Restar 273 para obtener °C condensar neón, hidrógeno ni helio
Presiones de vapor para varios metales
Temperaturas P =760 torr

de ebullición
Presión (torr)
No usar cadmio ni zinc 100 300400 500

700 1200
17003000
40006000
ni plomo Temperaturas en Kelvin

La presión total es la de la suma de las presiones parciales de sus
componentes.
Presión parcial de una mezcla de gases como el AIRE
Suma = 761 torr

Otra manera mas práctica de verlo es con la rapidez o tasa de desgasificación: a
que presión se evapora un litro cada segundo por cada cm2 de superficie del
material
Material Exposición al vacío
METALES 1 hora en vacío Más de 24 hs en
vacío
rapidez promedio Latón 2 X 10-6 1 X 10-7
de desgasificación Berilio 1 X 10-6 1 X 10-9
en
Aluminio 8 X 10-7 1 X 10-10
torr-litros/seg- (arosellos +)
cm2 Plomo 1 X 10-7 4 X 10-8
Cobre 1 X 10-7 1 X 10-10
Cobre (OFHC) 8 X 10-9 3 X 10-11
(arosellos +)
Hierro dulce 2 X 10-6 3 X 10-8
Acero 1018 2 X 10-6 1 X 10-8
(niquelado)
Hoja de oro 8 X 10-8 5 X 10-9
Titanio 1 X 10-9 5 X 10-10
Acero Inoxidable 5 X 10-8 1 X 10-10
rapidez promedio de desgasificación en
torr-litros/seg-cm2
Material Exposición al vacío

VARIOS 1 hora en vacío Más de 24 hs en vacío
Epoxy 2 X 10-5 < 1 X 10-6
Buna N 8 X 10-6 8 X 10-7

(arosellos)
Neopreno (arosellos) 3 X 10-6 4 X 10-8
Viton (arosellos) 8 X 10-7 2 X 10-8
Mylar 8 X 10-7 7 X 10-9
Acrílico 2 X 10-6 5 X 10-7
Nylon 5 X 10-6 4 X 10-8
Lexan (policarbonato) 7 X 10-7 6 X 10-8
PVC 5 X 10-7 1 X 10-7
Esteatita (cerámica) 5 X 10-8 7 X 10-9
Pyrex (7740) 1 X 10-7 5 X 10-9

Fuentes de gases en una cámara
Hablemos de fuentes que producen gases que queremos eliminar parar
lograr un buen vacío.
a) DEGASIFICACIÓN: término que involucra la natural evolución de
especies absorbida y adsorbidas que contribuyen a la carga de gas por
evacuar = contaminantes…todos los materiales “huelen”
i) sublimación: sólido a gas sin pasar por el estado líquido
zinc, cadmio, plomo, etc. Solución: escoger bien los materiales
ii) desorpción: fenómeno superficial como y desabsorción y desorbción de
agua, hidrógeno de metales, gases de arosellos (grasa o
contaminantes) Solución: limpieza y sentido común
adsorción difusón
La absorción es un fenómeno superficial

iii) permeación: paso de átomos o moléculas a través de paredes porsosas;
por difusión de átomos muy pequeños
como hidrógeno, el helio pasa a través del vidrio (máxime en estado
superfluído) Solución: escoger mejores materiales para las paredes,
paredes más gruesas,
adsorción
permeación absorción
b) RETROFLUJO: el aceite de las bombas de difusión “trepa”
por las paredes, el de las bombas mecánicas se mueve hacia la
cámara después de tiempos largos de bombeo. Los aceites
pueden contaminarse facilmente por agua, vapores orgánicos
(acetona, tricloroetileno, y otros solventes) Solución:
trampas frías y sentido común: mantener tapados las botellas
de aceites, no bombear por periodos excesivamente largos ,
etc.
c) FUGAS: (externas) a través de soldaduras, uniones mal
selladas (arosellos sucios, mal montados) Solución:
soldaduras profesionales y probadas, no usar sellos metálicos
(de cobre ó aluminio) dos veces!! Y SENTIDO COMÚN
fugas virtuales: “fugas” internas

venteo lateral venteo por arriba
venteo por abajo

sólo si ambos
lados son
evacuados
Como agujerear para ventear correctamente piezas maquinadas
tornillo: venteo por el centro
Tornillo: venteo con ranura

Rondana con venteo
Fuga virtual y
soluciones ranura de
venteo
Hacer
ambos lados
Suponiendo que se eliminan todas las fuentes de gases mencionada, el
vacío llegará a la presión última – el mejor vacío que este tipo de bomba
puede lograr en condiciones ideales.
Espectro típico de gases residuales en una cámara de vacío de acero inox

(sin calentar)
1.4 Unidades utilizadas
Rango de vacío Presión en torr
Presión Presión en torr

Presión 760
atmosférica
1 torr = 1
Vacío bajo 200 a 1
(low, rough, fore) 1 Pascal 7.5 X 10-3
1 atmósfera 760
Vacío medio 1 a 10-3
1 milibar 0.75
Alto vacío 10-3 a 10-7 1 lib/pulgada2 = psi 51.7
Ultra alto vacío 10-7 a 10-12

1mbar = 100 Pascal
Vacío < 10-12
extremadamente
alto
torr
Bibliografía.
J. M. Lafferti (Editor), Foundations of Vacuum Science and Technology, Ed.

John Wiley & Sons (1998). Completo, relativamente actualizado, tablas,
autores de la academia y la industria; contiene una lista de libros de vacío muy
útil.
G. L. Weissler and R.W. Carlson (Editores), Vacuum Physics and Technology, de

la serie “Methods of Experimental Physics” Vol. 14, Ed. Academic Press Inc.
(1979). Orientado científicamente, incluye técnicas de depósito de películas
delgadas.
A. Berman, Vacuum Engineering Calculations, Formulas, and Solved Exercises,

Ed. Academic Press Inc. (1992). Orientado hacia el diseño y construcción de
equipo de vacío.
American Vacuum Society Monograph series:

H. G. Tompkins - An Introduction to the fundamentals of
vacuum technology (1984)
- Pumps Used in Vacuum Technology (1991)
American Institute of Physics, Inc.
Muy sencillo, ameno y realmente fundamental.
CONCRETO
Es un material formado por materiales minerales calcáreos como la piedra caliza y

materiales arcillosos con contenido de alúmina y sílice. Este material “reacciona
químicamente con el agua, por tal razón posee la propiedad de fraguar y endurecer en
presencia de ella, además tiene propiedades de adhesión y cohesión que le permiten
aglutinar todos los agregados para conformar el concreto
Agregados
Son aquellos materiales inertes que poseen una resistencia propia
suficiente, que no perturban ni afectan el proceso de
endurecimiento del cemento y que garantizan una adherencia con la
pasta de cemento endurecida.
Son considerados material de relleno dentro del concreto, debido a

que éstos constituyen mayor volumen dentro de la mezcla,
haciéndola más económica.
El material puede variar en la
mineralogía de sus componentes o
las condiciones físicas de sus
partículas, de forma tal que la
distribución del tamaño, la forma y
la textura son factores que tienen
un efecto en el comportamiento
del concreto.
Son inertes, tienen una resistencia propia suficiente que no altera

ni afecta el proceso de endurecimiento del cemento y que garantiza
una adherencia con la pasta de cemento endurecida. Pueden ser
naturales o artificiales, dependiendo de su origen.
Agregado Grueso
Es considerado como agregado grueso aquel material retenido en el tamiz de

4.76 mm (No. 4), este material puede estar compuesto por gravilla, grava,
piedra y piedra rajón, dependiendo de los tamaños comprendidos, ésta es la
materia prima para fabricar el concreto. El tamaño del agregado grueso para
concreto depende del sistema de colocación, del refuerzo que lleve la
estructura y de la resistencia para la cual se diseñe, por tal motivo los
agregados a ser utilizados en las mezclas de concreto deberán ser de buena
densidad, para adquirir mejores resistencias.
El agregado fino es aquel material que pasa por el tamiz de 4.76 mm (No. 4), es
denominado arena y su función en el concreto es como lubricante sobre el cual
pueden rodar los agregados gruesos, para darle una manejabilidad adecuada al
concreto. La cantidad de este material es de sumo cuidado debido a que afecta la
demanda de agua y el exceso de éste hace que la muestra sea más cohesiva y produzca
un asentamiento menor incrementando el consumo de cemento
Agua
Es de importancia en el concreto, en razón a que ella hace que el cemento se hidrate y

reaccione químicamente formando un gel que sirve como aglutinante de las partículas
constituyentes del concreto lubrica la mezcla con un volumen aproximadamente del 15%
del volumen total del concreto, en donde sólo el 5% es la cantidad necesaria para
hidratar el cemento y la cantidad restante sirve para proveer a la mezcla de
manejabilidad además constituye el agua evaporable. Una cantidad excesiva de agua
incrementaría la manejabilidad de la mezcla en estado fresco pero podría llegar a
ocasionar disminución en la resistencia del mismo. (Sanchez de Guzman, 1987)
Aditivos
Son adicionados a la mezcla inmediatamente antes o durante su mezclado, son usados para modificar las propiedades
del concreto con el fin de que sea más adecuada a las condiciones de trabajo o para lograrlo en forma más económica.
Acelerantes
Cuya función es reducir el tiempo de fraguado y acelerar el desarrollo temprano de resistencia. Las ventajas al usar este
tipo de aditivo es que se reducen los tiempos de desencofrado, permitiendo el uso pronto de estructuras nuevas. El
acelerante más conocido es el de cloruro de calcio
Plastificantes
Permiten reducir el agua de amasado y acelera las resistencias iniciales y finales del concreto, modificando levemente el
tiempo de fraguado. Además facilita la colocación del concreto debido a que incrementa su manejabilidad
Retardantes
Además de retardar el tiempo de fraguado en el concreto reduce al agua y trabaja como plastificante al mismo tiempo.
Estos son de gran utilidad cuando se fabrica concreto en clima caliente evitando así la formación de juntas fría
Propiedades del concreto fresco
Esta es la etapa en la cual se puede manipular el concreto, en ella se realizan actividades tales como mezclado de los
materiales para la conformación del mismo, transporte, colocación de la mezcla dentro de la formaleta adecuada y vibrado
de la misma (Asocreto, 2000), a fin de evitar hormigueros y de eliminar el aire atrapado por las partículas durante el
proceso. Con el fin de realizar un buen control de calidad en estado fresco al concreto y con el propósito de tomar
decisiones rápidas durante la colocación del mismo, se hace necesario realizar una serie de métodos de ensayos, que
permiten medir estas propiedades:
Manejabilidad Esta puede definirse como la cantidad de trabajo interno útil necesario para producir la compactación total,
entendiéndose como trabajo interno, a la energía requerida para vencer a la fricción interna entre las partículas en el
concreto (Neville & Brooks, 1987). Otros autores la definen como la capacidad que posee el concreto de ser colocado y
compactado apropiadamente
Inclusores de aire
Es un aditivo que origina aire en el concreto en pequeñas cantidades en forma de burbujas pequeñas durante el mezclado.
Es utilizado para aumentar la manejabilidad y la resistencia al congelamiento en el concreto.
Reductores de agua
Usado para reducir la cantidad de agua de mezclado requerida para producir un concreto con una consistencia
determinada o para incrementar el asentamiento de un concreto con un contenido dado de agua 5.7.6
Superplastificantes
Llamados también aditivos reductores de agua de alto rango. Son combinaciones de sustancias químicas, que al
adicionarse a un concreto normal, le dan una manejabilidad extrema o proporcionan una gran reducción de agua, que
excede los parámetros obtenidos con aditivos reductores de agua normales
Ensayo de asentamiento Uno de los ensayos que miden la manejabilidad del concreto fresco es el ensayo de
asentamiento, el cual se encuentra descrito en la norma NTC-396, el cual mide la consistencia del concreto o fluidez de
la misma, el cono de dimensiones prefijadas por Abrams es llenado en tres capas de igual volumen compactándolas con
25 golpes con una varilla de acero de dimensiones y peso prefijado en el ensayo, una vez se ha llenado completamente
el cono, éste es retirado sin girarlo, de ésta forma como la mezcla está fresca y se le ha retirado el soporte lateral que la
sostiene, la mezcla se asienta, se toma la diferencia de alturas entre la que tenía la mezcla antes de ser retirado el molde
y la que tomó una vez retirado y con esta se mide la manejabilidad de la mezcla, dando como resultado mezclas secas
(2.5 – 3.5 cm), semi-secas (3.5 – 5.0 cm), media (5-10 cm), húmeda (10.0 – 15.0 cm) y muy húmedas (mayor a 15.0 cm)
(Asocreto, 2000)
Ensayo de la bola de Kelly Descrito en la norma ASTM C360, es otro de los ensayos utilizados para medir la
manejabilidad, está basado en la resistencia a la penetración del concreto, consiste en un cilindro de masa constante
que tiene una punta esférica que se deja hundir bajo la acción de su propio peso, dependiendo de la profundidad que se
alcanza depende la manejabilidad del concreto. (Neville & Brooks, 1987)
Segregación Se define como la tendencia que poseen las partículas gruesas de separarse de la fase del mortero del
concreto y la deficiencia de esas partículas en el perímetro del concreto colocado. (Asocreto, 2000) La segregación se
presenta cuando se usan mezclas secas o pobres, en las cuales las partículas gruesas tienden a separarse y en mezclas
muy húmedas en las cuales se producen separación de una parte de los agregados.
Exudación o sangrado Se presenta cuando las partículas gruesas se sedimentan o se segregan y parte del agua del
mezclado tiende a elevarse a la superficie de la mezcla recién colocada, debido a que los materiales sólidos de la mezcla no
pueden retener toda el agua cuando se asientan durante el fraguado de la mezcla. Para determinar la exudación el método
descrito por la norma NTC 1294 lo determina, compactando un espécimen y apisonándolo sin perturbación y el otro
espécimen por vibración de forma intermitente durante el ensayo. (Asocreto, 2000)
Masa unitaria y rendimiento volumétrico Se mide según lo estipulado en la norma NTC- 1926, consistente en determinar
la masa requerida para llenar un molde de volumen conocido, compactándolo con 25 golpes con una varilla de 5/8” lisa. La
masa unitaria real del concreto se determina mediante el cociente de la masa neta del concreto y el volumen del
recipiente; valor que es utilizado para la determinación del rendimiento volumétrico, al dividir la masa total de los
materiales mezclados entre este valor.
Contenido de aire Para medir el contenido de aire en el concreto se encuentran diferentes métodos de ensayo, entre las
cuales se encuentran el ensayo de presión normal NTC 1028, el volumétrico NTC 1032 y el gravímetro NTC 1926. (Asocreto,
2000)
Método de presión Está basado en la Ley de Boyle, en donde se tiene en cuenta la relación entre la presión y el volumen.
Este equipo esta calibrado para realizar el contenido de aire directamente cuando se le aplica una presión predeterminada.
(Asocreto, 2000)
Método gravimétrico Se precisa la remoción del aire de volumen conocido de concreto agitándolo dentro de un exceso de
agua y finalmente en el método gravimétrico, es usado el mismo equipo para la determinación del rendimiento del concreto
en estado fresco realizando el mismo procedimiento y el contenido de aire se expresa en porcentaje con relación al volumen
total del concreto.
Contenido de agua Se hace importante medirla debido a que son base fundamental para determinar si la cantidad de agua
real presente en la mezcla es la estipulada en el diseño de mezcla. La norma NTC 3752 describe la forma de hallarla,
mediante la medición de la concentración de ión cloruro resultante de la reacción química de la mezcla del concreto, con
una solución de cloruro de volumen y características conocidas. (Asocreto, 2000).
Propiedades del concreto endurecido

El concreto es capaz de soportar grandes esfuerzos de compresión, dependiendo de las propiedades físicas, químicas,
mecánicas y de la interacción de cada uno de los componentes. (Asocreto, 2000).
Resistencia a la compresión La gran mayoría de estructuras se diseñan supuestamente para que resistan a éste tipo de
esfuerzos; razón por la cual este es un aspecto de gran relevancia, en razón a que sirve como criterio de calidad del
concreto El espécimen de concreto es cargado hasta su rotura, por medio de una prensa de características y
especificaciones definidas, con una velocidad controlada según lo establecido en la norma NTC-673 La resistencia a la
compresión se calcula dividiendo la carga máxima soportada por el espécimen por el área de la sección transversal del
mismo.
Propiedades del concreto endurecido
El concreto es capaz de soportar grandes esfuerzos de compresión, dependiendo de las propiedades físicas, químicas,
mecánicas y de la interacción de cada uno de los componentes. (Asocreto, 2000).
Resistencia a la compresión La gran mayoría de estructuras se diseñan supuestamente para que resistan a éste tipo de
esfuerzos; razón por la cual este es un aspecto de gran relevancia, en razón a que sirve como criterio de calidad del
concreto El espécimen de concreto es cargado hasta su rotura, por medio de una prensa de características y
especificaciones definidas, con una velocidad controlada según lo establecido en la norma NTC-673 La resistencia a la
compresión se calcula dividiendo la carga máxima soportada por el espécimen por el área de la sección transversal del
mismo.
Resistencia a la flexión Ensayo importante en las estructuras de concreto simple sometidos a éste tipo de esfuerzos, como
es el caso de las losas de los pavimentos Para éste ensayo se elaboran vigas de concreto de 0.15 m por 0.15 m de sección
por una longitud de 0.60 m, las cuales son cargadas en su tercio medio hasta la rotura. La resistencia a la flexión se mide
por medio del módulo de rotura, dependiendo del lugar donde ocurra la falla. (Asocreto, 2000). 5.9.3 Resistencia a tracción
Conocido como el método brasilero NTC-722, este parámetro se relaciona con el agrietamiento que el concreto presenta a
causa de la contracción inducida por los cambios de temperatura. Este valor es muy pequeño razón por la cual no es tenido
en cuenta para efectos de diseño. (Asocreto, 2000). El ensayo consiste en cargar un cilindro de dimensiones convencionales
a lo largo de dos líneas axiales diametralmente opuestas a través de listones de longitud igual a la del cilindro hasta llevarlo
a su máxima carga
Módulo de elasticidad dinámico del concreto El módulo de elasticidad dinámico del concreto puede ser determinado
no destructivamente usando la prueba de resonancia (Malaikah y otros, 2004) descrita en la norma ASTM C-215,
utilizando el pulso ultrasónico y midiendo la velocidad que tarda la onda en atravesar la muestra de concreto. Nótese
que al utilizar fórmula para la determinación de la velocidad longitudinal del pulso ultrasónico se deduce el módulo de
elasticidad dinámico. (Asocreto, 2000).
Módulo de elasticidad estático del concreto y coeficiente de Poisson El módulo de elasticidad estático secante
es la relación que existe entre el esfuerzo y la deformación unitaria axial, al estar sometido el concreto a esfuerzos de
compresión dentro del comportamiento elástico. Es la pendiente de la secante definida por dos puntos de la curva del
esfuerzo- deformación, dentro de esta zona elástica. Estos puntos son definidos como 0 y el 40% de la resistencia
máxima del concreto. (Asocreto, 2000). El coeficiente de Poisson es la relación entre las deformaciones transversal y
longitudinal, al estar sometido el concreto a esfuerzos de compresión dentro del comportamiento elástico. Las normas
NTC 4025 (NTC, 2008). Y la ASTM C 469 (ASTM, 2009), describen el proceso para su determinación. En la cual se
utilizan cilindros de los mismos que se utilizan en la prueba de resistencia a la compresión del concreto, a estos
especímenes se les adapta un dispositivo llamado extensómetro, consistente en dos anillos, uno unido de manera
rígida y el otro atado a dos puntos opuestos de forma diametral, que permiten rotar. Este dispositivo posee dos
deformímetros para realizar lecturas de deformación no solo longitudinal sino también transversal, a fin de permitir la
medición de las mismas.
Pruebas físico-mecánicas de los agregados
En cuanto a las propiedades físicas que son significativas en el comportamiento mecánico del concreto (NTC, 2008) se
encuentran: la granulometría, densidad, porosidad, masa unitaria y la forma y textura de los agregados.
Pruebas Físicas
Granulometría Es la distribución del tamaño de las partículas de una masa de agregado. El análisis granulométrico
consiste en hacer pasar una masa conocida de material a través de una serie de tamices o mallas que poseen aberturas
cuadradas ubicadas de forma tal que los tamaños más grandes se encuentren ubicados de mayor a menor abertura y
pesando el material que queda retenido en cada uno de ellos. En el caso de agregados para concretos éste ensayo
permite además de mostrar la distribución de los tamaños de los agregados, calcular los tamaños de los mismos como
son el tamaño máximo ( TM ), el tamaño máximo nominal ( TMN ) y el módulo de finura ( MF ), parámetros básicos
para diseño de concretos
Textura La textura es un parámetro importante en lo referente a la influencia que el agregado posee en cuanto a la
adherencia de éste con la pasta de cemento fraguada, de igual forma para la densidad y las resistencias a tanto a
compresión como a flexión.
Densidad Esta depende directamente de las propiedades de la roca madre (Asocreto, 2000), la densidad aparente es
importante para el diseño de las mezclas de concreto, para la determinación de las cantidades de los agregados por peso
para un volumen unitario de concreto
Porosidad y absorción La porosidad de una agregado se mide por medio del % de absorción de agua u otro líquido
(Sanchez de Guzman, 1987) que este material posea, vale la pena anotar que entre más % de absorción posea un
agregado más poroso será, menos denso y por consiguiente el concreto será menos resistente, deduciéndose de esta
manera que un agregado de mejor calidad será aquel que posea menor absorción
Masa Unitaria Es la relación entre la cantidad de material en un recipiente determinado y el volumen que esta ocupa. Se
pueden determinar las masas unitarias sueltas y las masas unitarias compactas. Para la determinación de la masa
unitaria suelta se procede a llenar un molde de peso y volumen conocido por gravedad desde una cierta altura de caída y
la masa unitaria compacta se determina llenando el molde en tres capas compactadas con 25 golpes. El procedimiento
de ensayo se encuentra descrito en la norma NTC-92.
Propiedades Mecánicas
Dureza Se determina por medio del ensayo de desgaste en la máquina de los Ángeles referidos en la norma NTC-93 y 98,
esta propiedad depende de la constitución mineralógica y de la procedencia del agregado. Esta propiedad es usada como
indicador de la calidad inherente de varias fuentes de agregados (Sanchez de Guzman, 1987).
Sanidad La sanidad de los agregados es un parámetro medido en el ensayo descrito por la norma NTC-126, en relación a
que los agregados pueden en ocasiones estar contaminados con contenidos de sulfato y cloruros adheridos a su
superficie, además, el ataque de los cloruros también puede presentarse cuando los agregados se encuentran expuestos
a un ambiente agresivo. Estas reacciones que no son observables a simple vista deben estudiarse mediante ensayos de
laboratorio a fin de medir la peligrosidad de éstas en el concreto.
Contenido de Materia orgánica La materia orgánica consiste en productos de descomposición de material en forma de
humus o marga orgánica, que suelen estar presente en las arenas(Neville & Brooks, 1987) . Sus efectos perjudiciales se
pueden comprobar mediante la prueba colorimétrica descrita en la norma NTC-127
T R A N S P O R TAT I O N R E S E A R C H
Number E-C170 December 2012
Nanotechnology in
Concrete Materials
A Synopsis
TRANSPORTATION RESEARCH BOARD
2012 EXECUTIVE COMMITTEE OFFICERS
Chair: Sandra Rosenbloom, Director, Innovation in Infrastructure, The Urban Institute, Washington,
D.C.
Vice Chair: Deborah H. Butler, Executive Vice President, Planning, and CIO, Norfolk Southern
Corporation, Norfolk, Virginia
Division Chair for NRC Oversight: C. Michael Walton, Ernest H. Cockrell Centennial Chair in
Engineering, University of Texas, Austin
Executive Director: Robert E. Skinner, Jr., Transportation Research Board

2012–2013 TECHNICAL ACTIVITIES COUNCIL
Chair: Katherine F. Turnbull, Executive Associate Director, Texas A&M Transportation Institute,
Texas A&M University System, College Station
Technical Activities Director: Mark R. Norman, Transportation Research Board
Paul Carlson, Research Engineer, Texas A&M Transportation Institute, Texas A&M University System,
College Station, Operations and Maintenance Group Chair
Thomas J. Kazmierowski, Manager, Materials Engineering and Research Office, Ontario Ministry of
Transportation, Toronto, Canada, Design and Construction Group Chair
Ronald R. Knipling, Principal, safetyforthelonghaul.com, Arlington, Virginia, System Users Group
Chair
Mark S. Kross, Consultant, Jefferson City, Missouri, Planning and Environment Group Chair
Peter B. Mandle, Director, LeighFisher, Inc., Burlingame, California, Aviation Group Chair
Harold R. (Skip) Paul, Director, Louisiana Transportation Research Center, Louisiana Department of
Transportation and Development, Baton Rouge, State DOT Representative
Anthony D. Perl, Professor of Political Science and Urban Studies and Director, Urban Studies Program,
Simon Fraser University, Vancouver, British Columbia, Canada, Rail Group Chair
Steven Silkunas, Director of Business Development, Southeastern Pennsylvania Transportation
Authority, Philadelphia, Pennsylvania, Public Transportation Group Chair
Peter F. Swan, Associate Professor of Logistics and Operations Management, Pennsylvania State,
Harrisburg, Middletown, Pennsylvania, Freight Systems Group Chair
James S. Thiel, General Counsel, Wisconsin Department of Transportation, Legal Resources Group
Chair
Thomas H. Wakeman, Research Professor, Stevens Institute of Technology, Hoboken, New Jersey,
Marine Group Chair
Johanna P. Zmud, Director, Transportation, Space, and Technology Program, RAND Corporation,
Arlington, Virginia, Policy and Organization Group Chair
Transportation Research Circular E-C170
Nanotechnology in Concrete Materials

A Synopsis
Prepared by
Bjorn Birgisson
Anal K. Mukhopadhyay
Georgene Geary
Mohammad Khan
Konstantin Sobolev
for the
Task Force on Nanotechnology-Based Concrete Materials

Transportation Research Board

500 Fifth Street, NW
Washington, D.C.
www.TRB.org
TRANSPORTATION RESEARCH CIRCULAR E-C170
ISSN 097-8515
The Transportation Research Board is one of six major divisions of the National Research Council, which serves
as an independent advisor to the federal government and others on scientific and technical questions of national
importance. The National Research Council is jointly administered by the National Academy of Sciences, the
National Academy of Engineering, and the Institute of Medicine. The mission of the Transportation Research Board
is to provide leadership in transportation innovation and progress through research and information exchange,
conducted within a setting that is objective, interdisciplinary, and multimodal.
The Transportation Research Board is distributing this Circular to make the information contained herein
available for use by individual practitioners in state and local transportation agencies, researchers in academic
institutions, and other members of the transportation research community. The information in this circular was taken
directly from the submission of the authors. This document is not a report of the National Research Council or the
National Academy of Sciences.
Design and Construction Group

Thomas J. Kazmierowski, Chair
Concrete Materials Section

Mohammad S. Khan, Chair
Task Force on Nanotechnology-Based Concrete Materials

Bjorn Birgisson, Chair
Neal S. Berke Steven H. Kosmatka Roger C. Schmitt, Sr.

Mark E. Felag Richard A. Livingston Rathinam Panneer Selvam
Edward J. Garboczi Anal K. Mukhopadhyay Surendra P. Shah
Georgene M. Geary Jan Olek Konstantin Sobolev
James D. Grove Claudia P. Ostertag Wynand Jacobus van der Merwe Steyn
Wouter Gulden H. Celik Ozyildirim Donald A. Streeter
Karin M. E. Habermehl-Cwirzen Laila Raki Thomas J. Van Dam
Mohammad Shamim Khan Florence Sanchez Suneel N. Vanikar
TRB Staff
Frederick D. Hejl, Associate Division Director, Engineer of Materials and Construction
Michael DeCarmine, Program Officer
Michael Nabinett, Senior Program Assistant

Washington, D.C.
www.TRB.org
Javy Awan, Production Editor; Jennifer Correro, Layout and Proofreading

Preface
T he mechanical behavior of concrete materials depends to a great extent on structural

elements and phenomena which are effective on a micro- and nanoscale. The ability to target
material modification at the nanostructural level promises to deliver the optimization of material
behavior and performance needed to improve significantly the mechanical performance, volume
change properties, durability, and sustainability of concrete.
This synopsis is written to assist in the identification of promising new research and
innovations in concrete materials using nanotechnology that can result in improved mechanical
properties, volume change properties, durability, and sustainability. This publication was
developed both for the practitioner who wants a general knowledge of how nanotechnology can
shape—and is shaping—the future and for the academician who is interested in a compilation of
the latest research including detailed references related to nanotechnology in concrete.
Parts 1, 3, and 4 are on a level that can be comprehended by a reader who has no
background in nanotechnology. Part 1 is a general overview for practitioner and academician
alike. Part 3 highlights some of the current implementation case studies, and Part 4 identifies
some of the challenges and sets a course for future direction.
In Part 2, at the front of each of the main sections is a general description for the
practitioner. The body of the section details the state of the art in research and technology in
nanotechnology. This synergy of practical needs and future vision will change the future of
concrete construction in the transportation industry.
—Bjorn Birgisson
Chair, Task Force on Nanotechnology-Based Concrete Materials
iii
Contents
Part 1: Nanotechnology for Concrete: Overview ........................................................................1
Part 2: Nanotechnology-Based Research in Concrete to Date...................................................4

High-Performance Cement and Concrete Materials .....................................................................4
Mechanical Properties................................................................................................................4
Formation of Dense Microstructure and More Efficient Cement Hydration ..........................4
Higher Compressive Strength Concrete..................................................................................7
Higher Tensile Strength, Ductile, and Tougher Concrete.......................................................8
Improved Aggregate–Paste Bond Strength .............................................................................9
Improved Concrete Performance Using Nanoporous Thin Film Technology ......................10
Self-Healing of Microcracks Through Use of Chemistry and Microbes ..............................10
Nanomaterials for Electrical Conductivity and Stress-Sensing Concrete.............................10
Durability Properties ................................................................................................................11
Reduced Permeability ...........................................................................................................11
Improved Shrinkage Properties.............................................................................................12
Sustainable and Safe Concrete Materials and Structures .........................................................12
Sustainable Cements .............................................................................................................12
Degradation of Pollutants and Self-Cleaning Concrete ........................................................13
Concrete with Nonconventional Aggregates ........................................................................13
Reactive Powder Concrete for Optimized Design ...................................................................14
Multiscale Characterization and Modeling of Concrete .............................................................15
Nanoindentation and Atomic Force Microscopes for Characterization of Concrete ...............15
Characterization of the Hydration Process ..............................................................................17
Nanoscale Model of Portland Cement Concrete ......................................................................19
Intelligent Concrete Materials Through Integration of
Nanotechnology-Based Sensing Technologies ........................................................................20
Self-Sensing and Self-Powered Materials ...............................................................................20
Nanotechnology-Based Devices ..............................................................................................21
Enhanced Concrete Pavement Design and Construction ............................................................21
Part 3: Implementation Case Studies.........................................................................................22

Photocatalytic Concrete ..............................................................................................................22
Nanomodified Concrete for Self-Compacting Concrete and Improved Slipform Paving ..........23
Ultra-High-Performance Bridge Elements .................................................................................24
Part 4: Future Challenges and Directions .................................................................................25
References .....................................................................................................................................27
v
PART 1
Nanotechnology for Concrete

Overview
N anotechnology is an emerging field of science related to the understanding and control of

matter at the nanoscale, i.e., at dimensions between approximately 1 and 100 nm
(www.nano.gov). At the nanoscale, unique phenomena enable novel applications.
Nanotechnology encompasses nanoscale science, engineering, and technology that involve
imaging, measuring, modeling, and manipulating matter at this length scale.
Just how small is “nano”? In the serviceability index system of units, the prefix “nano”
means 1-billionth or 10–9. Therefore 1 nm is 1-billionth of a meter. It’s difficult to imagine just
how small that is, so here are some examples (www.nano.gov):
• A sheet of paper is about 100,000-nm thick.

• A strand of human DNA is 2.5 nm in diameter.
• There are 25,400,000 nm in 1 in.
• A human hair is approximately 80,000 nm wide.
• On a comparative scale, if the diameter of a marble was 1 nm, then diameter of the
Earth would be about 1 m.
Nanoscale particles are not new in either nature or science. Recent developments in
visualization and measurement systems for characterizing and testing materials at the nanoscale
have led to an explosion in nanotechnology-based materials in areas such as polymers, plastics,
electronics, car manufacturing, and medicine.
Matter can exhibit unusual physical, chemical, and biological properties at the nanoscale,
differing in important ways from the properties of bulk materials and single atoms or molecules.
Some nanostructured materials are stronger or have different magnetic properties compared to
other forms or sizes of the same material. Others are better at conducting heat or electricity. They
may become more chemically reactive or reflect light better or change color as their size or
structure is altered.
Nanotechnology is not simply working at ever-smaller dimensions; rather, working at the
nanoscale enables scientists to utilize the unique physical, chemical, mechanical, and optical
properties of materials that naturally occur at that scale.
Of particular relevance for concrete is the greatly increased surface area of particles at the
nanoscale. As the surface area per mass of a material increases, a greater amount of the material
can come into contact with surrounding materials, thus affecting reactivity.
Nanotechnology considers two main approaches: (a) the ‘‘top down” approach in which
larger structures are reduced in size to the nanoscale while maintaining their original properties
without atomic-level control (e.g., miniaturization in the domain of electronics) or deconstructed
from larger structures into their smaller composite parts and (b) the ‘‘bottom-up” approach, also
called ‘‘molecular nanotechnology” or ‘‘molecular manufacturing” (example: www.nano.gov) in
which materials are engineered from atoms or molecular components through a process of
assembly or self-assembly (Figure 1).
1
2 Transportation Research Circular E-C170: Nanotechnology in Concrete Materials
FIGURE 1 The top-down and bottom-up approaches

in nanotechnology (1) (Sanchez and Sobolev, 2010).
Thus the basic concept behind nanomodification of materials is that of bottom-up

engineering, starting with engineered modifications to the molecular structure with an aim to
affect the bulk properties of the material. Conceptually, this is simply an imitation of nature. In
practice, the introduction of nanotechnology represents a revolution that is allowing for the
development of high-performance and long-lasting products and processes within an ideal
context of sustainable development.
The 2000 Presidential Commission on Nanotechnology likened the potential impact of
nanotechnology on society to that of the Industrial Revolution. The report (www.nano.gov) by
the commission identified economic and safe transportation as one of the nine grand challenges
where nanotechnology had the greatest potential for pay-off. Concrete-based materials are
considered by the National Nano Initiative as examples where nanotechnology may have a
particularly large impact in the future.
Part 1: Nanotechnology for Concrete 3
Concrete, the most ubiquitous material in the world, is a nanostructured, multiphase,

composite material that ages over time (Sanchez and Sobolev, 2010). It is composed of an
amorphous phase, nanometer- to micrometer-size crystals, and bound water. The properties of
concrete exist in, and the degradation mechanisms occur across, multiple length scales (nano to
micro to macro) where the properties of each scale derive from those of the next smaller scale
(Figure 2, page 5). Nanoengineering of concrete can take place in one or more of the three
locations such as (a) in the solid phases, (b) in the liquid phases, or (c) at the interfaces between
liquid–solid and solid–solid (Garboczi, 2009).
The mechanical behavior of concrete materials depends to a great extent on structural
elements and phenomena that are effective on a micro- and nanoscale. The size of the calcium
silicate hydrate (C-S-H) phase, the primary component responsible for strength and other
properties in cementitious systems, lies in the few nanometers range (Taylor, 1997). The
structure of C-S-H is much like clay, with thin layers of solids separated by gel pores filled with
interlayer and adsorbed water (Mehta, 1986). This has significant impact on the performance of
concrete because the structure is sensitive to moisture movement, at times resulting in shrinkage
and consequent cracking if accommodations in element sizes are not made (Jennings et al.,
2007). Hence, nanotechnology may have the potential to engineer concrete with superior
properties through the optimization of material behavior and performance needed to significantly
improve mechanical performance, durability, and sustainability.
The development of nanotechnology-based concrete materials requires a
multidisciplinary approach, consisting of teams of concrete materials experts: civil engineers,
chemists, physicists, and materials scientists. Porro et al. (2010) presented an overview of how
nanotechnology could be applied to concrete technology, emphasizing the multidisciplinary
approach needed for successful breakthroughs leading to ultra high-performance materials and
new multiscale models that enable the prediction of bulk material properties from composition
and processing parameters. Grove et al. (2010) identified opportunities for nanotechnology
leading to new concrete products and materials, and also for improving the sustainability and
reducing the environmental footprint of concrete-based materials in the future. Finally, Birgisson
et al. (2010) identified the following key breakthroughs in concrete technology that are most
likely to result from the use of nanotechnology:
• Development of high-performance cement and concrete materials as measured by

their mechanical and durability properties;
• Development of sustainable concrete materials and structures through engineering for
different adverse environments, reducing energy consumption during cement production, and
enhancing safety;
• Development of intelligent concrete materials through the integration of
nanotechnology-based self-sensing and self-powered materials and cyber infrastructure
technologies;
• Development of novel concrete materials through nanotechnology-based innovative
processing of cement and cement paste; and
• Development of fundamental multiscale model(s) for concrete through advanced
characterization and modeling of concrete at the nano-, micro-, meso-, and macroscales.
PART 2
Nanotechnology-Based Research in Concrete to Date
HIGH-PERFORMANCE CEMENT AND CONCRETE MATERIALS
T he addition of nanofine particles can improve the properties of concrete due to the effect
increased surface area has on reactivity and through filling the nanopores of the cement
paste. Nanosilica and nanotitanium dioxide are probably the most reported additives used in
nanomodified concrete. Nanomaterials can improve the compressive strength and ductility of
concrete. Carbon nanotubes or nanofibers (CNT-CNF) have also been used to modify
strength, modulus and ductility of concretes. CNFs can act as bridges across voids and cracks
that ensure load transfer in tension. Ultra high-performance concretes (UHPC) used in
current practice and found in the research literature have mainly been developed using some
type of nanomodification or the use of an admixture developed using nanotechnology
methods. Some of the ways nanotechnology can be used to affect concrete include modifying
the cement properties through nanomodification, modifying the cement paste itself through
admixtures, or affecting the concrete mixture using nanoporous thin film (NPTF) coatings for
the aggregates themselves.
Durability of concretes can also be improved through reduced permeability and
improved shrinkage properties. These effects can be accomplished through nanomodified
cements or the use of nanodeveloped additives to the paste.
Mechanical Properties
Incorporation of nanomaterials into the matrix to improve concrete mechanical properties has
emerged as a promising research field. Nanoscale particles are characterized by a high surface
area-to-volume ratio and many are highly reactive (Figure 2). Most of the concrete-related research
to date has been conducted with nanosilica (nano-SiO2) (Bjornstrom et al., 2004; Flores, 2010; Ji,
2005; Jo, 2007; Li, 2004, 2006, 2007; Qing, 2007; Lin KL, 2008; Lin DF, 2008; Sobolev, 2005,
2009; Sanchez, 2010; Qing, 2008; Kuo, 2006) and nanotitanium oxide (nano-TiO2) (Li, 2006,
2007). A few studies on incorporation of nanoiron (nano-Fe2O3) (Li, 2004), nanoalumina (nano-
Al2O3) (Li, 2006), and nanoclay particles (Chang, 2007; Kuo, 2006) have also been reported.
Manufacture of nanosized cement particles and the development of nanobinders (Lee, 2005;
Sobolev, 2005) is another area where limited numbers of investigations have been carried out
(Figure 3).
Formation of Dense Microstructure and More Efficient Cement Hydration
Scanning electron microscopy (SEM) microstructural studies of mortar specimens with and without
nanoparticles have revealed the mechanisms for improved performance with nano-SiO2 (Figure 3).
When a small quantity of nanoparticles is uniformly dispersed in a cement paste, the hydrated
products of cement deposit on the nanoparticles due to their higher surface energy, i.e., act as
4
Part 2: Nanotechnology-Based Research in Concrete to Date 5
Nan -Engineered Concrete

High -Strength /High -Performance Concrete
Conventional Concrete
1 ,000 ,000
Nanosilic
Specific Surface Area, m2/kg
Precipitated Silica Fume

10,000 Silica
Metakaolin
Finely Ground
Mineral Additives Portland Cement
100 Fly Ash Aggregate Fines
Natural Sand
1
Coarse
Aggregates
0.01
1 10 100 1,000 10,000 10 ,000 1,000,000 10,00 ,000 100,000,000
Particle Size, nm
FIGURE 2 Particle size and specific surface area related

to concrete materials (adapted from Sobolev, 2005).
nucleation sites. Nucleation of hydration products on nanoparticles further promotes and accelerates
cement hydration (Bjornstrom et al., 2004; Lin, 2008). The addition of colloidal silica resulted
acceleration of C3S dissolution and rapid formation of C-S-H phase in cement paste (Bjornstrom et
al., 2004).
The other mechanisms of improved performance are that: (a) nanoparticles fill the nanosize
pores of the cement paste, and (b) nano-SiO2 reacts with Ca(OH)2 (i.e., pozzolanic reaction) and
generates additional C-S-H (Sobolev, 2005; Jo, 2007). Both processes are influenced by the particle
size and the proper dispersion of the nanoparticles within the cement paste, with colloidal dispersions
being more effective than the powder (Gaitero et al., 2010). A reduction in Ca(OH)2 content and
increase in C-S-H content in cement mortar as a result of nano-SiO2 addition was noticed through
DTA and XRD testing (Tang et al., 2003). With the addition of 3% (by weight) of nano-SiO2,
significant improvement of early-age interfacial transition zone (ITZ) structure with respect to
reduction in content, crystal orientation degree, and crystal size of portlandite crystals was reported
by (Qing et al., 2003). An increase of chemically combined water content and heat of hydration and a
decrease of CH content in presence of nanometer-sized SiO2 powder was reported by Lu et al.
(2006). The microstructural studies by NMR, BET, and MIP indicated that portland cement
composites with nanosilica produce more solid, dense, and stable bonding framework (Shih et al.,
2006). In another study (Dolado et al., 2005), it is reported that the improvement in strength due to
nanosilica addition was not related to pozzolanic reaction, but due to the formation of denser
microstructures through growth of silica chains in C-S-H.
The addition of silica nanoparticles has important implications for the hydration kinetics and
the microstructure of the paste such as (a) an increase in the initial hydration rate, (b) an increase of
the amount of C-S-H gel in the paste through pozzolanic reaction, (c) reduction of porosity, (d)
improvement in the mechanical properties of the C-S-H gel itself (e.g., greater alumina-content,
longer silicate chains) (Gaitero et al., 2010). Sum of these factors resulted in pastes with 30% more
compressive strength. Nanoindentation studies have shown that the volume fraction of the high
stiffness C-S-H gel increased significantly with addition of nanosilica (Mondal et al., 2010), which
significantly improves concrete durability. Samples with nanosilica showed almost twice the amount
of high-stiffness C-S-H as the sample with silica fume. The addition of nanosilica particles (5 to 70
nm, synthesized by using sol-gel method) along with superplasticizing admixture in portland cement
mortar resulted compressive strength to reach up to 63.9 MPa and 95.9 MPa at the ages of 1 day and
28 days, respectively (Flores et al., 2010) and flexural strength of 23.5 MPa at 28 days. Silica
nanoparticles modify the ITZ of cement mortar in four different ways, i.e., (a) acting as nucleation
site, (b) generating more C-S-H through pozzolanic reaction that is also more dispersed through a
nucleation effect, (c) controlling crystallization, and (d) improving the microfilling effect (Hosseini et
al., 2010). The effect of nanoparticles at early ages (especially in the first 3 days) is more noticeable
than with other curing ages. The ultra high reactivity of nanosilica particles contributes to the
promotion of hydration reaction and also expedites the pozzolanic reaction.
A combined effect of the above mechanisms produces a uniform dense microstructure with
improvement not only in the cement paste but also in the ITZ.
A few studies have shown that nano-TiO2 can accelerate the early-age hydration of portland
cement (Jayapalan et al., 2010), improve compressive and flexural strengths (Li H et al., 2007).
Conduction calorimeter based test results (Sato and Diallo, 2010) indicated that the addition
of nano-CaCO3 significantly accelerated the rate of heat development and shortened the induction
period of C3S hydration. It was proposed that nano-CaCO3 either broke down the protective layer on
C3S grains during hydration to shorten the induction period, or accelerated C-S-H nucleation (i.e.,
seeding effect).
FIGURE 3 Spherical nano-SiO2 particles of uniform distribution

observed using TEM (Sanchez and Sobolev, 2010).
Higher Compressive Strength Concrete
Research showed that the compressive and flexural strengths of cement mortars containing
SiO2 and Fe2O3 nanoparticles were both higher than those of plain cement mortar (Li et al.,
2004; L. Hui, 2004). The experimental results show that the compressive strengths of mortars
with nanosilica (NS) were all higher than those of mortars containing silica fume at 7 and 28
days. An addition of 10% nano-SiO2 with dispersing agents resulted in a 26% increase of 28-
day compressive strength whereas the increase was 10% with 15% silica fume (H. Li et al.,
2004) without dispersing agents. Other research showed that the addition of small amounts of
NS (i.e., 0.25%) caused 10% increase of compressive strength and 25% increase of flexural
strength at 28 days (Sobolev et al., 2009). Nanofume, a new ultrafine, powder admixture of
amorphous SiO2 produced from fly ash, was used to prepare high-strength concrete based on
normal portland cement. Compressive strength of the concrete increased with increasing
specific surface area of nanofume (20 m2/g to 130 m2/g). Nanofume with a specific surface
area between 30 m2/g to and 50 m2/g was recommended for the preparation of a concrete with
compressive strength of 120 MPa.
NanoAl2O3 was found to be very effective in increasing the modulus of elasticity of
cement mortar. With 5% of nanoAl2O3 (approximately 150 nm average particle size), the
elastic modulus increased by 143% at 28 days, whereas the increase of compressive strength
was not very obvious (Zhenhua et al., 2006). A proper mixing procedure was selected in order
to ensure adherence of nanoAl2O3 particles on the sand surfaces. It is believed that during
cement hydration, these nanoalumina particles were available to fill the pores at the sand–paste
interfaces and created a dense ITZ with less porosity. With an increase in nanoAl2O3 content,
the elastic modulus of mortars increases when nanoAl2O3 content is less than 5%. At higher
replacement level (e.g., >5%), agglomeration of nanoparticles caused ineffective densification
of ITZ and as a result, the elastic modulus of mortars decreases.
The effect of synthetic nano-ZrO2 powder addition in cement on the strength
development of portland cement paste was studied by Fan et al. (2004). Reduction in porosity
and permeability, enhancement in compressive strength, and improvement in microstructure of
cement paste were observed due to the addition of nano-ZrO2 powder in cement. Both pore
filling and bridging action were identified as possible mechanisms for improvement.
The effect of incorporating nanometer-sized franklinite (ZnFe2O4) particles obtained
from electric–arc–furnace dust (EAFD) on strength properties of portland cement paste was
studied by Balderas et al. (2001). The powder obtained after acid treatment of the EAFD
consisted basically of nanometer-sized particles of franklinite. Incorporation of the EAFD in a
portland cement paste caused a retardation in the setting time. Nevertheless, after 7 days, the
compressive strength of the portland cement–EAFD pastes was superior to portland cement
alone, and, after 28 days, the extent of hydration of the portland cement–EAFD paste was
equivalent to portland cement alone. A compressive strength of 72 MPa was attained after 42
days for OPC doped with 10 wt% EAFD.
Improvement in flexural strength in mortar and concrete due to the addition of calcium
carbonate particles with surface area ≥ 10 m2/g was observed by Cervellati et al. (2006).
The organo-modified montmorillonites (OMMT) particles are hydrophobic and thus
can be utilized to improve the strength and permeability of cement mortar and concrete. The
compressive and flexural strengths of cement mortars can be increased up to 40% and 10%,
respectively, by the addition of OMMT particles.
Higher Tensile Strength, Ductile, and Tougher Concrete
CNTs-CNFs are potential candidates for use as nanoreinforcements in cement-based materials.

CNTs-CNFs exhibit extraordinary strength with moduli of elasticity of the order of TPa and
tensile strength in the range of GPa, and they have unique electronic and chemical properties
(Ajayan, 1999;, Salvetat et al., 1999; Srivastava et al., 2003). Cementitious materials (e.g.,
concrete) typically behave as brittle materials with low tensile strength and are prone to
cracking. Incorporation of fibers into cementitious materials is a common practice to increase
tensile strength and ductility and improve durability. The interfacial interactions between
CNTs and cement hydrates produce high bond strength. CNTs act as bridges across cracks and
voids, which ensures load-transfer in tension (Makar, 2005; G. Li et al., 2005).
Research has shown that flexural strength and stiffness of cementitious materials can be
increased by adding low concentration (e.g., 0.025% by weight of cement) of homogeneously
dispersed multiwall CNTs (MWCNTs). It is reported that adding small amounts of CNTs (1%)
by weight could increase both compressive and flexural strength (Mann, 2006).
Research has revealed that incorporation of macrofibers and microfibers in
cementitious system can control cracking through bridging and load transfer across cracks and
pores (Makar 2005). Although, microfibers delay the propagation of microcracks, they do not
stop their initiation. CNFs are able to bridge nanocracks and pores and achieve good bonding
with the cement hydration products. In one study incorporation of an optimal amount of CNFs
(close to 0.048 wt%) was shown to improve flexural strength of the cementitious matrix
significantly (Metaxa et al., 2010). To develop high-performance nanofiber–cement
nanocomposites, a homogeneous distribution of the nanofibers in cementitious matrices must
be achieved. Segregation of CNF in cement paste due to improper distribution of CNF fibers is
a common concern.
The effect of CNTs in cement mortar at different types and dosage rates of multiwall
nanotubes was studied by Manzur and Yazdani (2010). The initial results are encouraging but
depend largely on the mixing techniques and workability issues. A sonication technique was
adapted to ensure uniform dispersion of CNTs. MWCNT was added in sequence and was
sonicated for 5 min for each addition. An increase in mean strength is observed up to 0.5 wt%
MWNT addition compared with the control sample of both types of MWNT; addition of 0.3
wt% MWNT provided the highest mean compressive strengths. A smaller-sized MWNT results
higher compressive strength as small MWNTs are distributed at a much finer scale and
therefore fill the nanopore space more effectively. Some of the challenges are (a) achieving
proper dispersion; (b) high water demand to achieve satisfactory workability in nanotube-
reinforced cement composites; and (c) reduction in strength due to formation of large voids.
Strong attraction among nanoscale fibers (CNFs-CNTs) due to van der Waals forces
makes uniform distribution of fibers in the matrix difficult. With the use of superplasticizer,
CNFs can be uniformly dispersed in water by ultrasonic processing. But mixing a water-
superplasticizer-CNF dispersion with cement doesn’t ensure uniform distribution of CNFs in
cement paste. To achieve better fiber dispersion in paste, either functionalized or highly
dispersible CNFs should be used. The CNFs can be implanted or grown on cement particles
(Nasibulina et al., 2010). An investigation on the relationship between cement particle size and
the dispersion of CNFs-CNTs in paste revealed that large cement particles prevent a uniform
distribution, when fibers are very small or used in high dosages. It is advisable to use fresh
cement with minimal amount of large grains and clumps for making CNF-CNT reinforced
cementitious composites (Yazdanbakhsh et al., 2010).
Time-consuming steps are required in purifying and functionalizing the carbon
nanomaterials in order to obtain a good dispersion. A novel cement-hybrid material (CHM)
was synthesized in which CNTs and CNFs are attached to the cement particles by two different
methods: screw feeder and fluidized bed reactors (Nasibulina et al., 2010). CHM has been
proved to increase the compressive strength by two times and the electrical conductivity of the
hardened paste by 40 times.
Micro- and nanoscale characterization of ITZ of UHPC revealed that an enhanced fiber-
matrix interfacial region, created by thermal treatment, contributes significantly to the
reductions in tensile-creep deformation measured for UHPC subjected to early curing at 90°C
and 60°C. The results suggest that a more moderate but longer period of thermal curing may be
appropriate and may offer a practical alternative for the curing of prestressed UHPC elements.
This has relevance to the development of guidelines for optimizing practical curing regimes for
fiber-reinforced UHPC and demonstrates the necessity to perform tensile-creep tests in cases in
which satisfactory long-term tensile performance is desired (Garas et al., 2010).
Similarly, the reinforcement of combined nanocellulose and microcellulose fibers in
reactive powder concrete (RPC) was found to be effective in increasing the toughness of an
otherwise brittle material. Preliminary results show that the addition of up to 3% micro- and
nanofibers in combination increased the fracture energy by more than 50% relative to the
unreinforced material (Peters et al., 2010).
Use of polycarboxylate-based HRWR proved successful in disaggregating the CNFs in
solution and improved the dispersion of CNFs in the cement paste at the individual fiber level
but inhomogeneous distribution (i.e., areas of high and low CNF density) of the fibers cannot
be avoided. Addition of 0.2 wt% CNF resulted in increased splitting tensile strength of 22% in
portland cement composites. Migration of CNFs along the bleed water (depending on the
water-binder ratio used) sometimes creates a porous layer of agglomerated CNFs intermixed
with cement paste at the upper surface of the composite (Gay and Sanchez, 2010).
Improved Aggregate–Paste Bond Strength
With the addition of 3% of nano-SiO2, significant improvement of early age ITZ structure with
respect to reduction in content, crystal orientation degree, and crystal size of portlandite
crystals was reported by Qing et al. (2003). It is believed that during cement hydration, the
nanoalumina particles fill the pores at the aggregate–paste interfaces and created a dense ITZ
with less porosity, which was mainly responsible for significant increase of elastic modulus of
mortars (Z. Li et al., 2006).
Improved Concrete Performance Using Nanoporous Thin Film Technology
As discussed above, most nanotechnology research has focused on characterizing concrete

when nanosilica particles are dispersed in the cement paste. Nanoparticles added during mixing
affect only the microstructure of the paste without making any significant improvement in the
strength of the interfacial transition zones (ITZ). The addition of nanoparticles as NPTF on
aggregate surface before concrete mixing was found to be an effective way to improve the ITZ
and thereby the performance of concrete (Munoz and Meininger 2010). Water suspended
nanoparticles (i.e., colloidal suspension) are used to coat aggregates through dip- or spray-
coating methods. The technology necessary to apply NPTF on aggregates is already available
in the market. This is a cost-effective method as small quantify of nanoparticulate additives is
needed to obtain significant results as opposed to conventional powder addition method.
Improvements in compressive, tensile, and flexural strengths and reduction in drying shrinkage
have been observed through the incorporation of NPTFs in mortar and concrete. The overall
modulus of elasticity increase in mortars with nanosilica coated aggregates is believed to be
due to the improvements in the ITZ. Meininger and Munoz (2010) showed how the addition of
NPTFs resulted in 8% to 22% reduction in relative porosity in the ITZ. This improvement in
performance can ameliorate longitudinal and transverse cracking, corner breaks, punchouts,
and D-cracking in concrete pavement. Research on NPTF additions in concrete is in an early
stage. Further work is needed to understand the mechanisms and the full-scale impact of this
technology.
The addition of nano-SiO2 into concrete as thin films on aggregate surfaces has a high
potential for improving the overall performances of concrete. Mortar made with a nano-SiO2-
cement ratio of 0.0032 deposited as a surface coating of just one-third of the total fine
aggregates showed an average 35% improvement in compressive strength, flexural strength,
and tensile strength at early ages along with a reduction in chloride permeability (Sanfilippo et
al., 2010).
Self-Healing of Microcracks Through Use of Chemistry and Microbes
Self-healing polymers, which include a microencapsulated healing agent and a catalytic

chemical trigger (Kuennen 2004), could be especially applicable to fix the microcracking in
bridge piers and columns. When the microcapsules are broken by a crack, the healing agent is
released into the crack along with a catalyst. Subsequent polymerization bonds the crack faces.
Preliminary work on assessing the self-healing performance of cementitious composite
using microcapsules (PSMs) with oil core and silica gel shell (Yang et al., 2010) is very
promising. The microcapsules were dispersed in fresh cement mortar along with carbon
nanofibers and silica fume. EIS (electrochemical analyses) was used to characterize
microstructural properties and self-healing effect of the fiber-reinforced cement mortars. The
EIS data suggested that the inclusion of PSMs enabled the mortar composite to heal at least
part of the artificially induced microcracks (Yang et al., 2010).
Nanomaterials for Electrical Conductivity and Stress-Sensing of Concrete
The addition of CNTs treated with a mixed solution of H2SO4 and HNO3 or untreated CNTs to
cement paste results in a considerable decrease in electrical resistivity and a distinct
enhancement in compressive strength. The cement paste with treated CNT reinforcement
showed higher mechanical strength, higher compressive sensitivity and lower electrical
conductivity than those with untreated CNT (G. Li et al., 2007).
Concrete with nano-Fe2O3 can have self-diagnostic ability of stress as well as
improvement of compressive and flexural strengths (Li et al., 2004; Xiao and Ou, 2004). It was
observed that the volume electric resistance of cement mortar changes with the applied load in
presence of nano-Fe2O3 (30-nm particle size). On the other hand the plain cement mortar is
poor in monitoring its stress. The resistance linearly decreased with the increase of the
compressive loading for mortars with nano-Fe2O3 more sharply with 5% nano-Fe2O3. Based on
this observation, it is logical to postulate that concrete with nanoFe2O3 should be capable to
sense its own compressive stress. This property can be used for structural health monitoring in
real time without the use of any embedded or attached sensors, which can be considered as a
potential application in constructing smart structures.
Han et al. (2004) studied change of specific resistance under compression for cement
paste containing two types of nano-TiO2 particles (i.e., anatase and rutile based) and
nanocarbon fiber. They observed that the cement paste containing anatase TiO2 shows
pressure-sensitivity property whereas paste containing rutile-based nano-TiO2 does not show
that property. Cement paste containing carbon fiber shows the best pressure-sensing property
with lowest specific resistance. The rate of reduction of specific resistance for paste with
anatase nano-TiO2 was 7% to 10% whereas it was 17% to 35% for paste with carbon fiber.
Durability Properties
Reduced Permeability
It is expected that permeability (with respect to gas, liquid, ionic movement) of concrete with
nano-SiO2 should be low enough to increase its durability and service life (Sobolev, 2005).
Incorporation of 1.5% of nanosilica with average particle size of 15 nm has caused a
decrease in water penetration depth, gas permeability, and diffusion depth (Wagner et al.,
1994). The water permeability test showed that the nano-SiO2 concrete has lower water
permeability than the normal concrete (Tao Ji, 2005).
Reactive nanoparticles can be electro-kinetically transported to reduce the
permeability of hardened cement paste (Cardenas et al., 2006) through some kind of
chemical reactions. Nanosilica (20-nm size) and nanoalumina (2-nm size) particles dispersed
in simulated pore fluids were used to make colloidal nanoparticles. It was observed that 5-
min treatment using 5 V of potential applied over a span of 0.15 m is sufficient to drive
nanoparticles into the pore system. The coefficients of permeability for each paste were
reduced by 1 to 3 orders of magnitude.
Use of calcium carbonate particles with surface area ≥10 m2/g in mortar and concrete
to improve hardened properties such as high permeability to water vapor but low
permeability to liquid water was observed (Cervellati et al., 2006).
Nanoclay particles have shown promise in enhancing the mechanical performance, the
resistance to chloride penetration, and the self-compacting properties of concrete and in
reducing permeability (Chang et al., 2007; Kuo et al., 2006; Morsy et al., 2009; He and Shi,
2008). OMMT, which have been widely used in polymer–clay nanocomposites (PCN), are
employed as fillers and reinforcements in cement mortars (Kuo et al., 2006). The hydrophilic
montmorillonite (MMT) nanoparticles cannot be directly used as reinforcements in cement
and concrete because (a) water absorbed in the interlayer regions between silicate sheets will
cause detrimental expansion and (b) the interlayer alkali cations of MMT nanoparticles are
harmful to the durability of cement mortar and concrete. The OMMT nanoparticles modified
by a cationic-exchange reaction become hydrophobic and thus can be utilized to improve the
strength and permeability of cement mortar and concrete. The coefficients of permeability of
cement mortars could be 100 times lower if an optimal dosage (less than 1%) of OMMT
nanoparticles is added. The OMMT nanoparticles around capillary pores can obstruct the
diffusion of pore solution and aggressive chemicals and thus reduce the permeability of
cement mortar and concrete. MIP results showed that the accessible pore volume is
significantly reduced due to the obstruction of OMMT micro-particles around capillary
pores. The optimal dosage of OMMT nanoparticles approximately increases with the water-
to-cement (w/c) ratio in a mix design. Clusters of OMMT micro-particles were observed
from SEM micrographs when the dosage of OMMT micro-particles is larger than 1%.
Addition of nanoMMT composite (liquid form with planar diameter of about 100 nm) in
cement paste (0.4 and 0.6 wt%) causes increase of compressive strength (~ 13.24%) and
decrease of permeability coefficient (~ 49.95%) with more dense solid materials and stable
bonding framework in the microstructure (Chang et al., 2007). Additionally, nonmodified,
nanosized smectite clays were observed to act as nucleation agents for C–S–H and to modify
the structure of C–S–H (Lindgreen et al., 2008; Kroyer et al., 2003).
Improved Shrinkage Properties
Nanoclay particles have shown promise in reducing shrinkage of concrete (Chang et al.,
2007; Kuo et al., 2006; Morsy et al., 2009; He and Shi, 2008).
The moisture and drying resistance of a novel cement-based nanocomposite, polymer
intercalated–exfoliated (PIE) cement, has been studied by Qiao et al. (2006). The effects of
the post-processing treatment procedure and the nanofiller content are discussed in this
study. The experimental results indicate that the flexure strength of the PIE cement is higher
than that of ordinary portland cements by more than an order of magnitude and is quite
insensitive to the humidity level.
Alkali–aggregate reactions have been studied at nanoscale (Bernabeu et al., 2005). In-
situ and ex-situ experiments on the alkali dissolution of mica have been carried out with an
atomic force microscope (AFM). The cleavage properties of mica make it extremely suitable
for nanoscale surface evolution studies. Crystal growth on the basal [001] surface of
muscovite has been quantitatively monitored in order to gain insights on the kinetics and
mechanisms of silicate dissolution and precipitation reactions in an alkali environment.
The nanoindentation study showed that the volume fraction of the high-stiffness C–S–
H gel increased significantly with addition of nanosilica (Mandal et al., 2010). Volume
fractions of high-stiffness C-S-H were 38% and 50% for samples with 6% and 18%
nanosilica, respectively. This has significance to the durability of concrete. Gaitero et al.
(2008) reported that high stiffness C-S-H is more resistant to calcium leaching. Using 29Si
magic-angle spinning–nuclear magnetic resonance (MAS-NMR) spectroscopy of cement
paste with nanosilica showed that nanosilica increases the average chain length of C-S-H gel.
Sustainable and Safe Concrete Materials and Structures
Sustainable Cements
Belite cement is an environment friendly (reduced CO2 emissions) and energy-efficient

cement and offers superior durability. Although, long-term strength gain of belite cement can
be either comparable or even better than ordinary portland cement, low early strength due to
slow hydration rate is a limitation for its widespread use. Addition of nanoparticles to
accelerate belite hydration at early ages was studied by different researchers (Dolado et al.,
2007; Campillo et al., 2007). Different nanoparticles were added to belite cement and both
the early-age mechanical properties and microstructure modification were studied. The
results showed that the addition of nanoparticles can overcome the drawback of this type of
eco-friendly cements, which will enable them to be competitive to OPC.
Nano-SiO2 could significantly increase the early-age compressive strength of high-
volume fly ash concrete, which has early age strength gain characteristics similar to that of
belite cement concrete (Li, 2004). Significant increase (i.e., 81%) of 3 days compressive
strength was observed in nano-SiO2 added high-volume fly ash concrete (HVFC) in
comparison with HVFC without any nano addition. The addition of fly ash alone leads to
higher porosity at early ages, while nano-SiO2 actually lowers the concrete porosity through
pore size refinement at early ages. The enhancement of pozzolanic activity of the fly ashes
due to the presence of nano-SiO2 was observed from heat of hydration test data. The
maximum temperature due to heat of hydration was 61°C for the concrete with 50% fly ash
incorporating 4% nano-SiO2 whereas it was 65°C for plain portland cement concrete (PCC)
and 51°C for HVFC. The benefits of using HVFC in terms of better durability and long-term
mechanical properties had already been established but low early-age strength of HVFC is a
drawback. The addition of nano-SiO2 has a great potential to overcome this drawback of
HVFC. The composite addition of nano-SiO2, fly ash, and silica fume was found to be very
effective way to achieve good performance and an economic way to use nano-SiO2 (Feng et
al., 2004).
Degradation of Pollutants and Self-Cleaning Concrete
Concrete containing nano-TiO2 has proven to be very effective for the self-cleaning of
concrete as well as converting some pollutants to innocuous forms. Nano-TiO2 triggers a
photocatalytic degradation of pollutants (e.g., NOx, carbon monoxide, volatile organic
compounds, chlorophenols, and aldehydes from vehicle and industrial emissions) (Vallee et
al., 2004; Murata et al., 1999; Chen, 2009). Photocatalytic concrete pavement blocks were
found to be very effective in removing NOx through photocatalytic reaction of TiO2
(Kamitani et al., 1998; Murata et al., 2002). The surface reactions have been explored using
X-ray photoelectron and Raman spectroscopy (Dalton et al., 2002). In Europe and Japan,
nano-TiO2–based “self-cleaning” concrete products are commercially available for use in the
building facades and in concrete paving materials. The performance is confirmed in
laboratory settings under an ultraviolet light with intensity similar to natural levels, however,
long-term performance under outdoor exposure condition is yet to be established.
Pollution-reducing photocatalytic performance of a series of premix products
containing nano-TiO2 mineral pigments was evaluated by Enea and Guerrini (2010). The
tested products are hydraulic binders (natural hydraulic lime and cement) and pigments
(inorganic) with a wide range of color selection. These materials seemed to be particularly
interesting as finishing coatings for new buildings or for the renovation of historic buildings,
which can guarantee better maintenance of building surfaces and provide a valid contribution
to the reduction of pollution in urban environments.
Concrete with Nonconventional Aggregates
The possibility of using incinerator bottom ash as a substitute for natural aggregates was
investigated (Park et al., 2007). The rough, porous surfaces typical of bottom ash particles,
which diminishes the strength of solidified products, was modified by the introduction of
colloidal silica, resulting in a significant increase of mechanical strength was accomplished
by a slight amount of silica (<1 wt% to total). Moreover, a pozzolanic reaction was induced
during initial cement hydration due to the nanoparticle size of about 20 nm in colloidal silica
solution. Cylindrical specimens and bricks were prepared from bottom ash added to a
colloidal silica (SiO2) solution and cement, and then their compressive strengths were
evaluated. Cylindrical specimens showed an increase of approximately 60% in compressive
strength when a colloidal solution containing 4 wt% silica particles was sprayed onto the
bottom ash. The strength of bricks containing colloidal silica was in excess of 20 MPa, which
is suitable for a wide range of applications. Results of leaching tests based on toxicity
characteristic leaching procedure (TCLP) proved that the solidified bottom ash possessed
good chemical stability.
Reactive Powder Concrete for Optimized Design
A process for synthesis of cement with nanoscale particle sizes has recently been developed.
These nanocements can be tailored with varying phase compositions. Addition of
nanocement in RPC systems has the potential to further enhance the properties of an already
optimized system. The replacement of a small fraction of the conventional cement with these
nanocements causes faster cement hydration reaction and reduces the induction period
(Dham et al., 2010). The additional benefit of use of nanocement is creating denser
microstructure which causes higher compressive and tensile strength. A reduction in
permeability through the improvement of ITZ is expected to be a potential merit of
nanocement additions in RPC. The improvement in strength was not accompanied by an
increase of elastic modulus. Further research is needed to analyze the effect of nanocement
additions on the long-term durability of the RPC systems.
The leaching of calcium from a hydrated cement matrix is of vital importance for
structures like water containers, dams, bridges, etc., which have to be in contact with water
during their lifetime. Characterization techniques such as 29Si MAS NMR, X-ray diffraction,
mercury intrusion porosimetry, and EDX–microanalysis have been used to evaluate the effect
of the nanoparticles in the cement matrix nanostructure and their impact on the evolution of
the Ca leaching throughout time (Gaitero et al., 2005). Subsequent analysis of the results
indicates that silica nanoparticles can reduce Ca leaching by decreasing the amount of
portlandite in the matrix and reducing the degradation rate of the C-S-H gel.
Building construction takes time, in part because the binding process of cement is
based on the slow recrystallization and precipitation of calcium silicate species. Since the
material reactivity is controlled by surface area, a reduction in particle size of portland
cements has been used to prepare faster binding formulations. The present work investigates
a new and direct, one-step preparation of calcium silicate-based nanoparticles of a typical
portland cement composition by flame spray synthesis. Isothermal calorimetry revealed that
the hardening of this new nanocement corroborated a more than tenfold increase of initial
reactivity with different reaction kinetics if compared to conventionally prepared cements. At
present, the unfavorably high porosity of nanocements, however, underlines the need for
additional improvements of chemical composition and formulation to make these highly
reactive materials applicable to modern construction work, where load-bearing strength is of
importance (Halim et al., 2007).
MULTISCALE CHARACTERIZATION AND MODELING OF CONCRETE
N anoindentation is a method where the mechanical properties of a material are measured

at nano level. A nanosize needle is inserted into a material and load-displacement
curves are developed based on the resulting force and movement of the needle. The slope of
the curve and the maximum load is used to characterize the material at a nanoscale. SEMs
(scanning electron microscope) are high-magnification micropscopes that are used in
nanoindentation to identify the movement and also to identify the spatial relation of particles
to each other, which is important at a nano level.
Modeling of the C-S-H gel is done through nano indention type methods, and using
these type methods two distinct C-S-H forms have been identified. The amount and type of
C-S-H in a mix can be used to predict the resulting properties of the cement pastes. It is
difficult to investigate the nanostructure of C-S-H with typical methods. Nanotechnology
tools can also be used to monitor the progress of the cement hydration reaction, which can be
useful in evaluating admixtures or processes such as thermal degradation and enhance the
knowledge of developmental properties of concrete. Being able to see the cement reaction
over time also has the potential to provide for the development of new materials for
controlled delivery of admixtures in concrete.
Nanoindentation and Atomic Force Microscopes for Characterizing Concrete
Nanoindentation includes a variety of indentation hardness tests applied to small volumes.

Indentation is perhaps the most commonly applied means of testing the mechanical properties of
materials. Small loads and tip sizes are used, so the indentation area may only be a few square
micrometers or even nanometers. Typically, an indenter with a geometry known to high
precision is used. During the course of the indentation process, a record of the depth of
penetration is made, and then the area of the indent is determined using the known geometry of
the indentation tip. While indenting, various parameters such as load and depth of penetration
can be measured. A record of these values can be used to extract mechanical properties of the
material (e.g., Poon et al., 2008).
The ability to conduct nanoindentation studies with nanometer depth, and sub-
nanonewton force resolution is also possible using a standard AFM setup. AFM is a type of
scanning probe microscopy where the sample is scanned under the probe by a piezoelectric
translator in order to get information on surface properties. The probe has a very sharp tip, often
less than 50Å; when the tip is approached to the sample surface, interaction forces between the
tip and the surface cause a deflection of the cantilever. This deflection is detected by an optical
lever technique. The AFM allows for nanomechanical studies to be conducted alongside
topographic analyses, without the use of dedicated instruments. Load-displacement curves can be
collected similarly for a variety of materials, and mechanical properties can be directly calculated
from these curves (e.g., Kurland et al., 2011).
Measuring of mechanical properties of cementitious materials at the nanoscale is still an
emerging science. Considering the sizes of ITZ and capillary pores, a spatial resolution of about
1 µm, which was thought to be the minimum for nanoindentation, is required (Kim et al., 2010).
Ultrasonic AFM (AFAM) was used to characterize the cement paste in order to achieve this
resolution. AFAM gives a more concentrated probability of the modulus than nanoindentation.
Considering the contact and indent sizes, AFAM is a more promising means of measuring
mechanical properties at the nanoscale.
The influence of internal curing by water filled lightweight aggregates (LWAs) on the
microstructure of mortars was studied by scanning AFM and SEM (Peled et al., 2010). The
differences and similarities that exist at both the microscale and nanoscale of conventionally
cured mortars and internally cured mortars were studied. It was found that LWAs can be used for
internal curing to provide a greater degree of hydration in a small region around the aggregate
interface, which results in a microstructure that is denser and more homogeneous and that
contains less CH.
TEM and SEM studies have revealed the presence of nanosized hydration products
embedded in a cross-linked polymer matrix (Bortzmeyer et al., 1995). The nanoscale composite
structure of the cement is thought to play an important part in the mechanical properties.
TEM studies of C-S-H gels in portland cement indicated large fluctuations in the local
calcium–silicon ratio (Viehland et al., 1996). Lattice imaging studies have revealed the presence
of nanocrystalline regions within an amorphous matrix. The local composition within the
nanocrystalline regions is believed to be homogeneous. Optical diffractograms taken from
individual nanocrystalline regions demonstrated the coexistence of both jennite and 1.4-nm
tobermorite structural elements, supporting the essential features of the Taylor nanophasic model
(Taylor, 1993).
NMR spectroscopy [cross-polarization (CP) technique in combination with MAS] was
used to investigate the hydration of alkali-activated slag (Wang and Scrivener, 2003). The NMR
study provides information on the polymerization of silicates, the role of aluminates in cement
hydration and the nanostructure of C-S-H gel.
Recent progress in experimental and theoretical nanomechanics opens new venues in
materials science for the nanoengineering of cement-based composites. Some recent results
obtained by nanoindentation technique have been reviewed (Constantinides, Ulm, and Van Vliet,
2003), which reveal that the C-S-H gel exists in two different forms: a low-density form and a
high-density form. These two C-H-H types have different mean stiffness and hardness values and
different volume fractions. While the volume fractions of the two phases depend on mix
proportions, the mean stiffness and hardness values do not change from one cement-based
material to another; instead they are intrinsic properties of the C-S-H gel.
It has long been recognized, in cement chemistry, that two types of C-S-H exist in
cement-based materials, but less is known about how the two types of C-S-H affect the
mechanical properties. By means of nanoindentation tests on nondegraded and calcium-leached
cement paste, the existence of two types of C-S-H was confirmed and the distinct role played by
the two phases on the elastic properties of cement-based materials was investigated
(Constantinides and Ulm, 2004). It was found that (a) high-density C-S-H is less affected by
calcium leaching than low density C-S-H and (b) the volume fractions of the two phases in the
C-S-H is not affected by calcium leaching. The nanoindentation results also suggest that the
elastic properties of the C-S-H phase are intrinsic material properties that do not depend on mix
proportions of cement-based materials. The material properties and volume fractions are used in
a novel two-step homogenization model that predicts the macroscopic elastic properties of
cement pastes with high accuracy. In particular, from an application of the model to decalcified
cement pastes, it is shown that that the decalcification of the C-S-H phase is the primary source
of the macroscopic elastic modulus degradation that dominates over the effect of the dissolution
of portlandite in cement-based material systems.

Nanoindentation was employed (1 µm resolution) for the characterization of N-A-S-H gel
in alkali (Na-silicate solution) activated low-calcium fly ash (AAFA) cured both at ambient and
elevated temperatures (Nemecek et al., 2010). The intrinsic Young’s modulus of the N-A-S-H
gel was found to be around 17.7 GPa, irrespective of the curing procedure. N-A-S-H gel can be
considered mechanically similar to low-density C-S-H gels in cement paste. Therefore, AAFA
binder can be successfully used as an alternative binder for partial replacement of portland
cement.
In the presence of high concentrations of NaOH, fresh C-S-H gels deteriorated in short
reaction times. High alkaline contents led to polymerization with a rise in the mean chain length
in the original gel. The inclusion of soluble silica, in addition to aluminum (the situation alkali-
activated SCM) and alkalis, in the C-S-H gels favored the precipitation of a silicon-rich gel, with
aluminum and calcium in its composition. This was a product of the direct reaction between the
portlandite and the soluble Si and Al added. The soluble Si and Al in the medium, taken up by
the original C-S-H gel, modified gel structure and chemical composition (Garcia-Loderio et al.,
2010).
Characterization of the Hydration Process
The poorly crystalline C-S-H phases that form near room temperature have a broad similarity to
the crystalline minerals tobermorite and jennite, but are characterized by extensive imperfections
and structural variations at the nanometer scale. Both new and previously published data show
that these phases generate a family of solubility curves in the CaO-SiO2-H2O system at room
temperature. As demonstrated by 29Si MAS NMR data and by charge balance calculations, the
observed solubility differences arise from systematic variations in Ca-Si ratio, silicate structure,
and Ca(OH)2 content. Based on this evidence, the solubility curves are interpreted as
representing a spectrum of metastable phases whose structures range from purely tobermorite-
like to largely jennite-like. These findings give an improved understanding of the structure of
these phases and reconcile some of the discrepancies in the literature regarding the structure of
C-S-H at high Ca-Si ratios (Chen, Thomas, Taylor, Jennings, and Hamlin, 2004). Similarly, a
new technique has been proposed to rationally assess the nanomechanical behavior of C-S-H
based on a statistical analysis of hundreds of nanoindentation tests. Two structurally distinct but
compositionally similar C-S-H phases, i.e., low density (LD) C-S-H and high-density (HD)
C-S-H, or outer and inner products, have been identified. Both the phases exhibit a unique
nanogranular behavior which is driven by particle-to-particle contact forces rather than by
mineral properties (Constantinides and Ulm, 2007).
Early hydration (1, 7, 14, and 28 days) of five ordinary portland cement pastes with
different w/c ratios (0.3, 0.4, 0.5, 0.6, and 1.0 wt.) was investigated through positron annihilation
lifetime spectroscopy and compared with the results obtained from thermogravimetric analyses
(Consolati, Dotelli, and Quasso, 1999). This technique allows to separate gel pores from the
capillary pores which facilitates to monitor the evolution of pores with aging time. It is found
that the concentration of gel pores increases with aging time and w/c ratio. However, the pore
sizes do not show any significant variations with aging time or w/c.
It is difficult to investigate nanostructure of C-S-H with conventional instrumental
methods. Neutron scattering methods possess unique capabilities to characterize cementitious
materials. Quasi-elastic neutron scattering is used to monitor the progress of the cement
hydration reaction and to determine the distribution of the water content among the various
states, i.e., free, chemically bound, or physically trapped water in the gel network. Small-angle
neutron scattering (SANS) proves to be well suited to determine the surface and volume fractal
dimensions of the gel as a function of time and as a function of additives such as fly ash or silica
fume (Livingston et al., 1995).
The mechanism of deterioration of mechanical properties (stiffness, strength) due to
thermal degradation of C-S-H is still an enigma. A new experimental technique was introduced
that allows one to rationally assess the evolution of the nanomechanical behavior of cement paste
at elevated temperatures. Specifically, the thermal degradation of the two distinct C-S-H phases,
i.e., LD C-S-H and HD C-S-H is assessed based on a statistical analysis of hundreds of
nanoindentation tests. From a combination of nanoindentation, thermogravimetry and
micromechanical modeling, a new mechanism has been identified (DeJong and Ulm, 2007). The
thermally induced change of the packing density of the two C-S-H phases is the dominant
mechanism that drives the thermal degradation of cementitious materials. The loosening of the
packing density was explained due to the shrinkage of C-S-H nanoparticles that occurs at high
temperatures, most probably due to the loss of chemically bound water.
The addition of TiO2 nanoparticles can be used to increase the rate of hydration and
potentially the rate of strength development of cement pastes but the addition of nano-TiO2
particles increases the shrinkage in cement paste (increase of shrinkage is proportional to the
replacement level). Hence, an optimum dosage or particle size distribution of nanoparticles could
be used to avoid or reduce the undesirable effects. Thus, it is proposed that the setting behavior,
strength development, and permeability of photocatalytic and other portland cement mixes can
be optimized by controlling compositional variables and particles size (Jayapalan et al., 2010).
In situ studies of the microstructures of fresh cement paste can greatly enhance
knowledge of the development properties of concrete at an early age (e.g., setting and hydration),
which can be helpful for improvement of the quality of concrete (Venkiteela et al., 2010). The
use of quantomix capsuling system in conventional SEM can be very effective for observing the
evolution of the actual microstructure of the cement paste. There was no significant development
of dynamic shear modulus (GWR) before the initial setting. Furthermore, the same shear modulus
level was observed at the time of initial setting irrespective of w/c ratios. GWR increases
significantly after the initial setting time and a better correlation between the solid phase and its
corresponding elastic modulus was possible from 6- to 8-h age.
The complex rheological behavior of cement paste is basically related to the interactions
at the molecular level, which, unfortunately are poorly understood. The rheological behavior of
cement-based materials is directly linked to the aggregation, deaggregation, reaggregation, and
dispersion of the solid particles. Characterization of the internal structure of fresh cement paste
has been obtained through in situ particle chord length distribution measurements. The chord size
evolution depends on the rate of aggregation of particles forming flocs and the rate of floc
breakage from shear-induced forces. The results showed that mixtures designed with the same
initial slump flow can have significantly different internal structures and that these internal
structures are highly sensitive to the shearing conditions. The strength and the stability of the
internal structure decrease as the average size of the flocs increases (Ferron and Shah, 2010).
An extremely small amount of C-S-H nuclei (0.3%) significantly increases the degree of
hydration by promoting the growth of C-S-H clusters into the pore solution instead of around the
C3S or cement grains. Although, the early growth occurs in the pore solution, the mechanical
properties of the cement pastes are preserved and use of seeding consequently accelerates the
strength developments of mortars (Nicoleau, 2010).
Studying the structural and chemical composition of C-S-H after carbonation is critical
for determining the durability and serviceability of concrete. Recent studies showed that the
mechanical properties are likely to be enhanced when mineral admixture and polymer are
introduced but no molecular-level studies have been conducted on carbonated C-S-H yet.
Scanning transmission X-ray microscopy (STXM) was used to study C-S-H modified by two
organic polymers (HDTMA and PEG 200) and exposed to different reaction times with CO2 (Ha
et al., 2010). No calcite formed in the presence of HDTMA, even though the C-S-H sample
reacted with an intense concentration of CO2. It seems polymers interfere with CO2 penetration
into the C-S-H layer structure and hinder the formation of CaCO3. The CO2 reaction strongly
depends on the types of organic polymers incorporated within the C-S-H structure as the mineral
phase formed within the C-S-H varies with the types of polymers used. Further work in terms of
more experiments and careful analysis is needed in order to make recommendation on practical
use of polymers as additives to arrest carbonation.
Nanoscale Model of Portland Cement Concrete
The innovations in concrete technology which are currently being applied in the field such as
high and ultra high performance (strength), and self-consolidating concrete have been discussed
(Scrivener et al., 2007). They discussed the factors which have enabled these developments and
ongoing needs in these areas. The importance of sustainability as the major driver for future
innovations and prospects for development of new cementitious materials with lower
environmental impact is briefly discussed. Finally the importance of innovation in research is
examined. The dramatic development in experimental and computational techniques over recent
years opens up wide-ranging possibilities for understanding the micro- and nanoscale chemical
and physical processes which underlie performance at a macroscopic level. The example of
computational approaches at the atomic and molecular scale is presented in detail. In order to
take advantage of the opportunities presented by such new techniques, there needs to be greater
efforts to structure interdisciplinary, multi-group research.
The measurement of elastic properties at the nanoscale is a prerequisite to building a
foundation for nanomechanics applications. Nanoindentation is widely used to measure the
properties of elasticity (Kim et al., 2010). It is supposed that a low modulus (10 to 20 GPa)
corresponds to C-S-Hs and that a high modulus (40 to 50 GPa) corresponds to CH. AFAM more
effectively demonstrates the differentiation of nanoparticles than nanoindentation. The
nanoindentation results give an effective (average) modulus for the indented area of about 1 µm
whereas AFAM can measures modulus of a small contact area with a diameter of about 30 nm.
AFAM is expected to differentiate two types of C-S-H at the nanoscale effectively because of its
improved resolution. AFAM measures the modulus directly at the nanoscale whereas
nanoindentation evaluates the modulus of each nanocomposite by applying an inversion
technique on the measured effective moduli.
The discrete element method (DEM) was used to model nanoindentation of C-S-H
(Chandler et al., 2010). It is assumed that the particles are spherical with diameters of ~ 5 nm.
Both modulus and hardness, calculated from the DEM, were much smaller than the results from
nanoindentation experiments. The effects of interparticle forces on the elastic modulus and
hardness were studied to explore possible reasons for the differences. The DEM simulations give
insight into the morphology of C-S-H nanoparticles and the interparticle forces between C-S-H
nanoparticles. The nature of the interparticle forces and their effects on the bulk properties of C-
S-H were explored to assess the plausibility of various mechanisms contributing to C-S-H
behavior.
It is known that increasing the tensile strength in cement paste can minimize the
shrinkage cracking potential of concrete. To enhance macroscopic mechanical properties (e.g.,
tensile strength), it is necessary to understand the structure and behavior of C-S-H gel at the
atomic level. Derivation of tensile and compressive strengths of C-S-H structure by using
molecular dynamics simulations from uniaxial stress-strain data was conducted by Murray et al.
(2010). A plausible atomic structure of C-S-H gel is proposed. The results showed that the
maximum strengths (compressive and tensile) for the proposed C-S-H structures are three orders
of magnitude higher than the strength at the macrolevel. The young’s modulus values of the C-S-
H unit with dimer silicate chains and the C-S-H unit with continuous silicate chains in the b
direction were found to be 70 and 96 GPa, respectively. However, the strength of the proposed
C-S-H gel is 23% of the compressive strength. This research also concludes that elastrostatic
forces and bond forces in the silicate chains are the main contributors to cement strength at the
atomic level and that breakage in silicate chains leads to low tensile strength in C-S-H gel.
INTELLIGENT CONCRETE MATERIALS THROUGH INTEGRATION OF

NANOTECHNOLOGY-BASED SENSING TECHNOLOGIES
N anoelectronic mechanical systems (NEMS) combine electrical and mechanical materials

together at the nanoscale. NEMS are being developed in the health care arena to
develop drug delivery systems that deliver the drugs right to the source of the infection or
cancer. NEMS in transportation has the capability of providing for measurement of hydration
in the plastic state while also providing the future stress strain properties of the hardened
concrete. NEMS can be designed to be used as part of quality assurance for construction
materials. They can be designed to measure material properties of the concrete during
hydration. These sensors can also be designed to provide for measurement of long-term
degradation by continuous monitoring of the stress and strains in the final structure. This
information can be used to maintain performance models for structures or pavements, or it
can have safety implications to prevent unforeseen failures by sending out a warning when
stress levels are excessive.
Self-Sensing and Self-Powered Materials
Concrete can be transformed into a self-sensing device by properly embedding a network of

CNTs. By measuring changes in the electrical resistance of this network of CNTs wirelessly, the
initiation and propagation of damage in concrete structures can be detected and monitored. In a
proof of concept study, Saafi (2009) embedded wireless cement–CNT sensors in concrete beams,
and then subjected the beams to monotonic and cyclic loading. These sensors were responsive to
loading induced damages, and capable of detecting damages at early stages of loading.
Calcium carbonate particles with surface area ≥ 10 m2/g were used to improve the sound
absorption of mortar and concrete (Cervellati et al., 2006).
Nanotechnology-Based Devices
NEMS can be used for better quality control of concrete, which indirectly helps to improve its
durability. NEMS are wireless nanomachines designed to measure (a) density and viscosity of
green concrete during mixing and pumping, (b) strength development, (c) shrinkage stress, and
(d) parameters affecting concrete durability such as temperature, moisture, chloride, pH, and
carbon dioxide (McCoy et al., 2005).
Researchers at Alabama A&M University’s Center for Transportation Infrastructure
Safety and Security (TIS2) have explored the use of nanotechnology-based devices for in-place
measurement of concrete density and viscosity. A wireless densitometer–viscometer, which was
originally developed by Sandia National Laboratories to measure the density and viscosity of oil,
was miniaturized and modified for use in fresh concrete. The device consisted of smooth and
textured nanoresonators, a microresistance temperature detector, and a power source-free radio
frequency communication system. It was envisioned that with proper packaging and sealing, the
device could be mixed with fresh concrete, allowing in-place workability measurements
remotely and online (Saafi and Romine, 2005).
Microelectromechanical systems (MEMS) has been used to measure temperature and
internal relative humidity of concrete by utilizing microcantilever beams and moisture-sensitive
thin polymer (Norris et al., 2008). MEMS were found to be (a) effective and sensitive in
measuring concrete temperature and moisture and (b) durable under corrosive environment and
internal–external stresses. Monitoring temperature and moisture is very important in order to (a)
monitor setting and hardening characteristics of concrete and (b) predict the possibility of
occurrence of concrete chemical distresses such as corrosion of steel reinforcement, freeze–thaw
distress, carbonation, and alkali-aggregate reaction. The areas that need further investigation are
(a) long-term behavior and repeatability of MEMS embedded into concrete and (b) wireless
interrogation such as signal processing, powering, communication, location, orientation, data
storage, and computation capabilities.
ENHANCED CONCRETE PAVEMENT DESIGN AND CONSTRUCTION
The abrasion resistance of concrete containing nanoparticles (both nano-TiO2 and nano-SiO2) for
pavement is experimentally studied (H. Li et al., 2006). The abrasion resistance of concrete
containing nano-TiO2 is better than that containing the same amount of nano-SiO2. The
effectiveness of nano-TiO2 (NT) in enhancing abrasion resistance increases in the order: 5% NT
< 3% NT < 1% NT (with the decrease on NT content).
The flexural fatigue performance of concretes containing nanoparticles is significantly
improved and the sensitivity of their fatigue lives to the change of stress is also increased. The
concrete containing nano-TiO2 (1 wt%) showed the best flexural fatigue performance (better than
concrete containing polypropylene fibers), which has been extensively used in paving concrete
(H. Li et al., 2007).
PART 3
Implementation Case Studies
I f nanoparticles are integrated with traditional building materials, the new materials would
possess outstanding properties for the construction of super high-rise, long-span or intelligent
civil infrastructure systems (Li, 2004). However, even though, in some ways, nanotechnology is
an integral part of every concrete mixture, in other ways it’s application is still limited. Calcium
silicate hydrate is fundamentally a nano system and work is continuing to develop tools to better
observe and model the material. In addition, modern chemical admixtures are designed and
prepared by manipulating the molecular structure of complex organic compounds, and such
materials are used in virtually every batch of concrete prepared in the United States.
On the other hand, usage of nanomaterials such as CNTs has yet to find acceptance for
everyday use. Products such as RPCs are commercially available and are aimed at improving
structural performance and have been used in bridge construction in several states. However, a
recent review of state departments of transportation (DOTs) in the United States showed that
none of the respondents reported using nanoproducts to date except for the use of TiO2 for
photocatalytic concrete. This dichotomy suggests that although nanotechnology materials may be
in use, they are not recognized as such by the practitioner.
PHOTOCATALYTIC CONCRETE
White cement containing TiO2 nanoparticles can have photocatalytic properties, which allow the
maintenance of the aesthetic characteristics of architectural and decorative concretes over time
(Cassar et al., 2003) along with removal of pollutants as an additional benefit. White cement
containing photocatalytic self-cleaning nanoparticles has been used in the construction of the
modernistic “Dives in Misericordia” church in Rome. TiO2 coatings (15 nm thick) have been
applied to glass windows to photocatalytically decompose dirt and smut particles that adhere to
the glass (Skarendahl et al., 2003). Other applications of nanotechnology in the building sector
include thin film solar cells, coatings with embedded nanoparticles to provide infrared and
ultraviolet screening on windows, tailored molecules to improve cement, colloidal silica (10 nm
particle size) for improving polymer-based floor coatings, improved insulation materials with a
porosity of the order of 10 to 100 nm, nanofilters to purify water, improved paint coatings, and
asphalt blends with better oxidation resistance.
Currently, there are several trial photocatalytic pavements sections that have been either
built or are being planned. One such section using TiO2 is in St. Louis, MO. This pavement is a
new highway constructed in 2011. The nanomodification product used contains the anatase form
of TiO2 that acts as a very reactive catalyst that helps to break down NOx when exposed to UV
light. Trials in Europe have shown that the material helps to reduce smog in urban areas. The
trial in Missouri is in a semi-urban environment. The trial section will be monitored and
compared to similar data collected over a full year at an adjacent section of the roadway that
does not contain the compound. Air quality will be monitored at and near the highway at more
than one level. Another section of the roadway used TXActive in the pervious shoulders, and the
22
Part 3: Implementation Case Studies 23
quality of the water passing through it will be monitored to assess the effectiveness of the
compound in treating pollutants in the water.
Another example of the application of nanotechnology based photocatalytic concrete is in
Baton Rouge, Louisiana where an approximately ¼ mile of a concrete roadway was sprayed with
a photocatalytic coating, with an objective to demonstrate the ability of ultrafine TiO2 to trap and
degrade nitrogen oxides in the environment. The performance of the coated test section was
compared with untreated sections by measuring NOx in the air and the nitrates deposited on the
concrete pavement surface. The results of initial monitoring indicated that the coating was
effective in photocatalytic degradation of NOx. A number of factors were identified that affect
the performance of the photocatalytic coating. These include relative humidity, light intensity,
solar radiation, and wind speed and direction (Dylla et al., 2012).
NANOMODIFIED CONCRETE FOR SELF-COMPACTING

CONCRETE AND IMPROVED SLIPFORM PAVING
The dispersion–slurry of amorphous nanosilica was used to improve segregation resistance for
self-compacting concrete by Bigley and Greenwood (2003). Addition of nanoparticles such as
silica in concrete has been realized an effective way to develop high-performance and self-
compacting concrete with improved workability and strength.
Another near-implementation ready application of nanotechnology includes the use of
nanoclays for producing self-consolidating concrete for slip form paving. The key to slipform
paving is that the material must be workable enough to be consolidated, yet stiff enough to stand
without formwork after the paver moves on at the end of the processing. Therefore, concrete slip
form pavement construction typically uses dry stiff concrete with slump of less than 5 cm (2 in.).
A slipform paving machine processes the fresh concrete, including placement, leveling, casting,
consolidation, and finishing. Equally spaced vibrators in the paving machine introduce extensive
internal vibration to consolidate and compact the fresh concrete (pack the materials and remove
larger sized trapped air voids). These internal vibrators may cause overvibration of the stiff
concrete if the vibration frequency is set incorrectly or the paving machine moves too slowly.
Overvibration leads to segregation of aggregates and significant reduction of smaller-sized
entrained air in the concrete along the path of the vibrators. When such a pavement is subjected
to heavy traffic loading or freeze–thaw weather cycles during its service life, so-called vibrator
trails (surface defects indicating segregation of aggregates, leaving a cement-rich layer) can
occur, or longitudinal cracks can form.
To eliminate the need for internal vibration in the paving process, Shah et al. (2008) and
Tregger et al. (2010) collaborated with the National Concrete Pavement Technology Center at
Iowa State University to extend self-consolidating concrete technology to slipform pavement
applications. The challenge to develop SF-SCC is that the material must change from very fluid
to very stiff during the slipform process. The development of SF-SCC required changing the
microstructure by combining concepts from particle packing (how particles of different sizes are
arranged and how that affects compressive strength), admixture technology (the combination of
different mineral and chemical admixtures), and rheology (the study of how materials flow).
Specifically, the addition of a nanoclay consisting of highly purified magnesium aluminosilicate
in very small dosages (1 percent by weight of cement) and Class C fly ash to the composition
made it possible to maintain a balance between flowability during compaction and stability after
compaction. For this research, the Iowa State team developed a model minipaver that simulates
the slipform paving process without the application of internal or external vibration. At the end
of the process, concrete slabs of modified mix with fly ash and nanoclay showed much better
shape stability and surface smoothness than the slab with a standard sliporm concrete mix, as
well as the greatest increase in green strength and compressive yield stress of the paving
concrete.
ULTRA-HIGH-PERFORMANCE BRIDGE ELEMENTS
Reactive powder concretes or ultra-high-performance concretes (UHPC) are nano to

microstructure optimized materials that have already been used in several states for bridge
construction. The Iowa DOT and Wappelo County, Iowa built the first UHPC Bridge in North
America in Wappelo County, Iowa in 2006. It was a joint project between Wappelo County and
the DOT, with the IHRB (Iowa Highway Research Board) and FHWA a part of the funding and
the Bridge Engineering Center at Iowa State doing the research. This bridge used a standard I-
shaped girder section constructed using UHPC. Compressive strengths of 18,000 to 30,000 psi
have been achieved in the construction of UHPC bridge beams. Different types of structural
shapes are also being researched. Further research in Iowa developed a pi-shaped girder that
takes advantage of the improved ductility properties of UHPC. New York State and Virginia
have also built bridges with UHPC components. Other states are researching the use of these
materials in beams and in prestressed concrete piling. Both Iowa and Georgia have performed
research on UHPC substructure elements. A unique concrete h-pile shape was developed in Iowa
for IHRB Project TR-558 (Figure 4). The pile was driven and load tested along with a steel
H-pile for comparison. The weights of the piles were approximately equal but the axial and
vertical load capacity of the UHPC concrete pile was greater than the H-pile.
FIGURE 4 IHRB Project TR-558.

PART 4
Future Challenges and Directions
S ome of the potenial areas of applications of nano-based products as well as future direction
are listed below.
1. Engineered materials using nanotechnology that will allow maximum use of locally
available materials and avoid unnecessary transport. Design ductile, flexible, breathable,
permeable, or impermeable concrete properties on demand.
2. Design concrete mix that is resistance to freeze–thaw, corrsion, sulfate, ASR, and
other environmental attacks.
3. Develop speciality products such as products with blast resistance and conductive
properties as well as temperature-, moisture-, and stress-sensing abilities.
While nanotechlogy-based construction products provide many advantages to the design

and construction process as identified in the National Roadmap for Nanotechnology in Concrete
(Birgisson et al., 2010), the following can be considered as future challenges.
1. Production of nanomaterials may in some cases require relatively high energy. Given
the desire of the construction industry for their materials to be sustainable as well as cost- and-
energy effective, the use of nanotechnology may in certain cases create an environmental
challenge to the construction industry. For example, the production of nanosilicate materials by
grinding requires high energy, which runs counter to the construction industry’s continual efforts
to make their materials sustainable as well as cost and energy effective. However, Birgisson and
Dham (2011) described how nanosilicate platelets can be produced through chemical processing
of montmorillonite clays, with minimal use of energy. In summary, the net sustainability impact
should be investigated.
2. Developing a better procedure to ensure proper dispersion of nanomaterials in large-
scale field applications. Effective dispersion of nanoparticles is key to achieving the full benefits
of adding nanoparticles in cementitious system. Self aggregation, especially at high dosages of
nanoparticles, is a common concern (Ozyildirim and Zegetosky, 2010), which sometimes leads
to nonhomogeneous microstructure development and poor performance. The application of
superplasticizer and high-speed mixing were found to be effective in proper dispersion of
nanosilica particles (Flores et al., 2010). This is consistent with the observations by other
researchers that high-intensity, high-shear mixing with the use of a proper dispersant would be
helpful in thorough mixing with minimal clumping (Ozyildirim and Zegetosky, 2010).
3. With more research and practice efforts, smart design, and planning, construction
projects can be made sustainable and avoid damages to environment.
4. Lack of adequate research and development funding.
5. Slow adoption rates of new technologies.
6. Low level of collaboration for multidisciplinary problems.
7. Inadequacy of quality control technologies.
8. The imaging of cement-based materials need further enhancement.
25
Finally, any potential health safety concerns for nanomaterials are not completely
investigated, even though the typically small addition rates of nanoparticles in concrete may act
to reduce the likelihood of adverse negative health and environmental effects. Human exposure
to nanoparticles is inevitable as nanoparticles become more widely used and, as a result,
nanotoxicology research is now gaining attention. However, while the number of nanoparticle
types and applications continues to increase, studies to characterize any health effects are few in
comparison. In the medical field in particular, nanoparticles are being utilized in diagnostic and
therapeutic tools to better understand, detect, and treat human diseases. A review (Lewinski et
al., 2008) states that even though nanoparticles may not be inherently safe, it is premature to
state that they are inherently dangerous. This uncertainty is a significant factor influencing the
decisions of industry and government leaders, as exhibited in the amended version of the
national nanoinitiative in 2008, intended to strengthen research efforts on the environmental,
health and safety issues related to the use of nanotechnology.
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Hardened Cement Paste and Aggregate. Guisuanyan Xuebao, Vol. 31, No. 5, 2003, pp. 517–522 (in
Chinese).
Yohanis, Y. G., and B. Norton. Life-Cycle Operational and Embodied Energy for a Generic Single-Storey
Office Building in the U.K. Energy, Vol. 27, No. 1, 2002, pp. 77–92.
Zhi, G., and G. Zhili. Applications of Nanotechnology and Nanomaterials in Construction. First International
Conference on Construction in Developing Countries (ICCIDC–I): Advancing and Integrating
Construction Education, Research, and Practice, Karachi, Pakistan, Aug. 4–5, 2008.
The National Academy of Sciences is a private, nonprofit, self-perpetuating society of distinguished scholars
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their use for the general welfare. On the authority of the charter granted to it by the Congress in 1863, the
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Ralph J. Cicerone is president of the National Academy of Sciences.
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selection of its members, sharing with the National Academy of Sciences the responsibility for advising the
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Washington, DC 20001
Copyright © 2010 American Scientific Publishers Journal of
All rights reserved Nano Education
Printed in the United States of America Vol. 2, 13–26, 2010
RESEARCH ARTICLE
Introducing Nanotechnology to Mechanical and
Civil Engineering Students Through Materials
Science Courses
Marwan Al-Haik1 ∗ , Claudia Luhrs2 , Zayd Leseman3 , and Mahmoud Reda Taha4
1
Department of Engineering Science and Mechanics, Virginia Tech, Blacksburg, VA 24061, USA
2
Department of Mechanical and Aerospace Engineering, Naval Postgraduate School Monterey, CA 93943, USA
3
Department of Mechanical Engineering, University of New Mexico, Albuquerque, NM 87131, USA
4
Department of Civil Engineering, University of New Mexico, Albuquerque, NM 87131, USA
Four junior faculty members from Delivered

the Mechanical by Ingenta
and Civil to:
Engineering Departments at the Uni-
versity of New Mexico (UNM)Polytechnic
Virginia have developed new experiments
Institute and pedagogical methods that
& State University
introduce undergraduate students toIP the: field of nanotechnology.
128.173.163.164 Toward this effort, we introduced
“Nanotechnology Discovery Courses” that comprise two
Tue, 14 Jun 2011 23:11:51 interlocking undergraduate engineering
materials science core courses enriched with three nanotechnology modules and four hands-on
nanotechnology experiments. Using this framework ensured continuous flow of nanotechnology con-
cepts to a senior level technical elective course that equips students with hands-on experience in
constructing nano/micro systems and devices. Between the two leading departments of the project
153 undergraduate students were exposed to the nanotechnology discovery courses by their junior
year during the academic years 2008–2009. The developed nanomodules, while familiarizing UNM
students with nanotechnology, did not strain the outline of classical material science courses nor
did it financially burden the students (for example, there were no extra lab fees). Affirmative survey
indicated that more than 67% of the students strongly favored the newly implemented nanomod-
ules. Furthermore, 65% of the surveyed students preferred including nanotechnology in the core
courses rather than a standalone course. Students favored the hands on experiments that required
minimal calibration (Scanning electron microscopy) compared to experiments that required inten-
sive calibration and post analysis of data (for example, nanoindentation). Based on the success
of this pilot research, several undergraduate students participated in nanotechnology research at
UNM. The major finding of this investigation is that nanotechnology education can be introduced
to the engineering curricula by incorporating nanotechnology modules in core courses, mentor-
ing undergraduate students in nanotechnology research, and introducing a standalone senior-level
nanosytems course.
Keywords: Undergraduate Education, Microstructure, Nanomaterials, Carbon Nanotubes,
Ceramics Nanoparticles, Microelectromechanical Systems, Nanoindentation,
Nanomodules, Nanodevices.
1. INTRODUCTION fact probably an incomplete list but it makes the point.

How do you possibly teach all these areas to students in
The idea of introducing nanotechnology to the engineer- a four year honors degree?.” Alternatively, other investi-
ing curriculum is as old as the nanotechnology field itself. gators have proposed utilizing lower division courses as
One of the first standalone nanotechnology undergraduate a departure course to familiarize undergraduate students
degrees in the world was established at Flinders Univer- with the concepts of nanotechnology.
sity (Australia) in 2000. The pioneers at Flinders raised a
There has been several nanotechnology courses devel-
valuable concern: “The field (nanotechnology) is currently
oped at other universities as well. Loyola Marymount
in its infancy and is incredibly broad, spanning chemistry,
University developed a new course (Introduction to Nano-
physics, biology, mathematics, and engineering. This is in
technology) toward biological applications. Faculty in
Northwestern University’s Materials Science & Engineer-
∗
Author to whom correspondence should be addressed. ing Department introduced a new nanotechnology course
J. Nano Educ. 2010, Vol. 2, No. 1/2 1936-7449/2010/2/013/014 doi:10.1166/jne.2010.1008 13

Introducing Nanotechnology to Mechanical and Civil Engineering Students Through Materials Science Courses Al-Haik et al.
to senior undergraduate and junior graduate students and at the University of New Mexico (UNM). This was accom-
reported the experience as a successful practice. Instructors plished by adding new lecture components to two materials
RESEARCH ARTICLE
at the University of Nevada introduced five blocks to teach science core courses to introduce the students to particular
the core principals of nanotechnology to audiences with aspects of nanotechnology. Reinforcement on these top-
varying levels of understanding. All these successful pio- ics was planned by hands-on experiments that utilize the
neering experiences developed new undergraduate courses, UNM’s existing nanotechnology infrastructure. These dis-
but most offered these new courses only as optional or covery courses are prerequisites for an additional newly
technical electives. Additionally, most of these courses developed course on the theory, fabrication, and charac-
were developed by a single department, although offered terization of nanosystems/devices. This course also has a
to several other departments. laboratory component where students fabricate nanosys-
The authors of this article believe that in order for a tems/devices in the clean room. The rest of this article
nanotechnology program to flourish it must take root in a outlines the newly developed nanomodules and provides
curriculum’s core courses and be taught by a multidisci- some preliminary results together with proposed future
plinary group of instructors. A current successful exam- work to improve the ongoing nanotechnology education at
ple of a multidisciplinary effort is at Union College in the UNM.
Schenectady, New York. A National Science Foundation
(NSF) grant was awarded to this predominately liberal arts
campus of 2,000 students (15 percent of whom are engi- 2. GOALS, OBJECTIVES, AND INTENDED
neering students). With prerequisites of calculus, physics, EDUCATIONAL
Delivered by Ingenta to: OUTCOMES
and chemistry, the investigatorsVirginia
have developed Frontier
Polytechnic Institute & State University
of Nanotechnology and Nanomaterials that was IP offered to As future scientists and engineers, students should be
: 128.173.163.164
sophomore science and engineering majors. Tue, 14 Jun 2011 prepared to enter a workforce that requires knowledge of
23:11:51
All efforts to teach nanotechnology to undergradu- nanotechnology. Four junior faculty members from two
ates can be broken into two main types of approaches: engineering programs at the University of New Mexico,a
strictly virtual (i.e., simulated) and hands-on. Proponents Albuquerque, NM, have employed their collective knowl-
of the strictly virtual (hands-off) approach, argued that edge in nanotechnology to develop new experiments and
“ nanotechnology experiments are delicate, limited in pedagogical methods to help introduce undergraduate stu-
availability, and expensive to set up and maintain. The use dents to this field of cutting-edge research by no later
of a web-based approach circumvents these drawbacks and than their junior year. Our goal was to cultivate a cul-
enables the experiment to be run securely, safely, and on tural change in engineering undergraduate education at
a 24/7 basis.” Meanwhile, other investigators highlighted the UNM by tying the material science curriculum across
the importance of bringing hands-on experience to inte- the school of engineering (SOE) through a group of
grate nanotechnology into the undergraduate curriculum. integrated learning modules focused on nanoscience and
For example, a group at the University of Nevada-Reno nanotechnology.
has carried out an experiment to move nanotechnol- We envisioned creating a series of interlocking courses
ogy/microtechnology to the undergraduate and graduate for undergraduate nanoscience education. This develop-
classroom in related fields of scanning-probe micro- ment leveraged two programs at the UNM: Mechani-
scope (SPM) technology. Another example is Polla et al., cal Engineering and Civil Engineering. This investigation
who brought hands-on microelectromechanical systems developed and tuned Nanotechnology Discovery Courses
(MEMS) fabrication into the undergraduate curriculum. that comprised two interlocking undergraduate Engi-
Our own experiences, a published student’s opinion, neering Materials Science core courses (ME370/CE305)
and other engineering and science educators’ experiences enriched with three nanotechnology modules (Introduction
are all in favor of introducing hands-on experimental to Nanotechnology, Nanostructures and Nanosynthesis and
modules. Nanocharacterization) and two materials science labora-
Despite the difference in the methods and tools, most of tories (ME352/CE305) that employ four hands-on nano-
the cited literature and the current group of authors share technology experiments (e.g., use of electron microscopy,
the NSF view that “ Adding nanoscale perspectives in X-ray diffraction (XRD), and nanoindentation).
teaching leads to better fundamental understanding, shar- This approach carries the following novel aspects:
ing similar concepts and courses in various disciplines and • While familiarizing student with nanotechnology, it does
areas of relevance (combining the ‘depth’ of nanoscience not strain the general outline of classical materials science
with the ‘breath’ of all affected areas), and broader acces- course for being introduced as a set of separate modules.
sibility to science and technology.” Keeping this view
in focus, the subsequent sections detail a plan that was a
All four authors were at UNM at the time of the implementation of
carried out to integrate nanotechnology into existing core the nanotechnology modules (2008–2009), two of the authors moved to
courses in the Mechanical and Civil Engineering curricula other institutions in 2010–2011.
14 J. Nano Educ. 2, 13–26, 2010

Al-Haik et al. Introducing Nanotechnology to Mechanical and Civil Engineering Students Through Materials Science Courses
• Utilizing core course for the introduction of nanotech- maintained at a dedicated web page developed by the
nology into the curriculum will not financially burden authors.
RESEARCH ARTICLE
the students; for example, no extra lab fees will be The Department of Civil Engineering at the UNM cur-
necessary. rently offers an undergraduate civil engineering materials
• The proposed integration of nanotechnology into mate- class and laboratory (CE305). This 4-hour credit course
rials science core courses and interdepartmental technical includes two 90-minute lectures and one 3-hour weekly
electives will readily provide students with different back- experiment. This core course is required for all civil engi-
grounds from crosscutting programs (mechanical and civil neering students and is a prerequisite for all 400-level civil
engineering) with nanotechnology experience that is natu- engineering courses. CE305 provides the basis for material
rally interdisciplinary. science to civil engineering students as well as the funda-
• As an alternative to web-based computer interactive mental background on civil engineering materials, such as
modules, we use state-of-the-art facilities at the disposal the fundamentals of bonding of materials, phase diagrams,
of engineering students at UNM to introduce experimental and the behavior of materials under stress including frac-
modules that are robust, easy to grasp, and depict practical ture and fatigue. The course also covers basic construc-
applications. tion materials such as steel, Portland cement, aggregate,
concrete, masonry, wood, and asphalt. Lectures also intro-
duce the microstructure of major civil engineering mate-
rials such as concrete and cover how this microstructure
3. ENGINEERING MATERIAL SCIENCE
affects the
Delivered by Ingenta to:macroscale behavior. Lecture notes and solu-
UNDERGRADUATE CORE COURSES
tions to sample
Virginia Polytechnic Institute & State Universityproblems are available to students via the
Starting in the spring semester 2008, two exist- course
IP : 128.173.163.164 website as the course integrates a number of text-
ing UNM materials science courses wereTue, revised by books that
14 Jun 2011 23:11:51 cross the area between material science, civil
including mutual nanotechnology components/modules engineering materials behavior, and testing. CE305 is the
both theoretically and experimentally. The Mechanical first place where CE students realize the multi-scale link
Engineering Department at the UNM typically offers its between a material’s atomic structure, microstructure, and
upper-division undergraduate materials science (ME370 its macroscale behavior. On its classical form—prior to
Engineering Materials Science, 3 credit hours) and its lab the nanomodulus implementation—most laboratory exper-
course (ME352 Experiments in Materials Science, 1 credit iments focus on macroscale phenomena. The CE305 lab-
hour) in the format of one-semester themed modules. The oratory introduces to students the stress–strain curves for
former outline of the course covers the structure of mat- materials, determining the properties of concrete using
ter and its relation to mechanical properties: the mechani- destructive and non-destructive testing methods and the
cal behavior of structural materials—metals, ceramics, and behavior of wood and aluminum.
polymers. Its prerequisite is general chemistry. This course These two courses/laboratories are required for all
is typically taken by students during their junior year senior students majoring in Mechanical and Civil engineer-
and is required of all senior-level mechanical engineering ing and are offered twice a year. On average, 25–30 stu-
students. It is also a prerequisite for the upper-division dents take the ME370/352L course every semester. CE305
design course ME460. The course and the laboratory are is offered once annually and typically has a class size of
offered twice a year (during both the spring and fall 35–40 students.
semesters). The course is taught using two 90-minute lec-
tures every week. Lectures are typically delivered using 4. NEW EDUCATIONAL NANOTECHNOLOGY
Microsoft PowerPoint presentations; sample problems are MODULES
solved on a weekly basis. The textbook in use for this
class is the book by Callister. The Materials Laboratory We have integrated three nanotechnology modules into
(ME352L) course covers the effects of microstructure, the two materials science courses. The lecture portions
processing, composition, and thermal treatment on the of this class, ME370/CE305, were redesigned to include
physical and mechanical properties of engineering mate- three nanotechnology modules. While a sole instructor
rials. The laboratory is taught on a weekly basis, con- taught the classical parts of the courses, the newly devel-
sisting of three-hour sessions. The students are divided oped modules were co-taught concurrently by all the four
into teams of 3–4 students. The lab manual was written authors. The developed modules are:
by the authors and posted to the students via the lab-
oratory web page. The laboratory consisted of classical 4.1. Module 1: Introduction to Nanotechnology
modules dealing with topics such as grains-microstructure
(polishing and light microscopy), Brinell and Vickers hard- This module defines a framework in terms of the mate-
ness tests, the Charpy impact test, and the tension test. rials/dimensions considered for study and describes dif-
The class lectures, problem solutions, and handouts were ferent types of nanomaterials that have been synthesized
J. Nano Educ. 2, 13–26, 2010 15

for applications in nanotechnology (nanoparticles, nano-

tubes, and thin films). It further explains the superior prop-
RESEARCH ARTICLE
erties of nanomaterials as a result of the reduction of

dimensions (an almost defect-free structure). The module
also explains the size-dependent properties (mechanical,
optical, and electrical—ferroelectric and ferromagnetic).
The module concludes by describing the current and
future novel prospects of nanomaterials: mechanical and
structural—carbon nanotubes electronics (semiconductors)
and energy (photovoltaic, ceramic nanoparticles), among
others.
4.2. Module 2: Nanostructure and Nanosynthesis

In this module the structure of the materials is explained
using a “bottom-up” approach. While this is usually
the case for the classical treatment of the microstruc-
ture of metals (atom-crystal-grain), cement composites
(crystals-transition zones-composite), ceramics (molecule-
Delivered by Ingenta to:
crystal), and polymer (atom-mer-molecule-chain), the
Virginia Polytechnic
module explicitly introduces nanomaterials with useful Institute & State University
IP
structure/properties at the nanoscale, such as increased: 128.173.163.164
tensile strength, enhanced fracture toughness, Tue,
and 14 Jun 2011
fatigue
Fig.23:11:51
1. Some carbon allotropes that pure carbon can take: (a) diamond,
(b) graphite, (c) lonsdaleite, (d) C60 , (e) C540 , (f) C70 , (g) amorphous
life. The concept of nanoscale is bound to the currently carbon, and (h) carbon nanotube.
taught concepts of bond energy and principles of fracture
and the long-sought defect-free materials. The “top-down”
approach is also introduced although not explored in detail. background for some electron microscopy techniques
This module is divided into two parts: Part I: Carbon (scanning electron microscopy (SEM) and transmission
Nanostructures and Part II: Ceramics and Nanoparticles. electron microscopy (TEM)) is demonstrated and their
Part I discusses the nature of the carbon bond and inter- uses explained from the aspects of studies on size, mor-
atomic potentials. This part also introduces briefly some phology, internal structure, and chemical composition. The
carbon allotropes (different molecular configuration; atoms most commonly used method for mechanical characteri-
are bonded together in a different manner) that pure car- zation of materials at the nanoscale—nanoindentation—is
bon can take, including diamond, graphite, lonsdaleite, also described in one full lecture. Finally, a lecture on
C60 , C540 , C70 , amorphous carbon, and carbon nanotubes the electrical properties of nanomaterials is given in the
(CNTs) as shown in Figure 1. The module elaborates on prospect of materials of microelectromechanical systems
CNTs (chirality, single wall, and multiwall CNTs). The (MEMS) and devices, emphasizing the length scale effect
module also discuss different CNT fabrication methods on electrical properties, with special attention given to
and current applications: mechanical reinforcement, field CNTs.
emission, fuel cells, and chemical sensors. Module 3 is also divided into three parts: Part I is
Part II focuses on ceramics and nanoparticles where
focused on electron microscopy, Part II is dedicated to
the students get introduced to the generation process of
material characterization, and Part III examines electronic
novel ceramic nanoparticles and some of their applica-
properties. The students in a typical materials science class
tions as catalysts, coatings, sensors, and fuel cells. Systems
are fascinated and intrigued when they see (in the text-
such as SiO2 , TiO2 , Ce/Zr oxides, Al2 O3 , metal-ceramic
book or course notes) images produced by TEM and SEM,
composites, and complex oxides are reviewed. The newly
introduced nanosilica and nanoalumina particles and their such as famous images showing fault stacking or vacan-
influence on the strength and microstructure of cementi- cies, interstitial voids, and calcium hydroxide (CH) crys-
tious composites are also discussed. tals stacked at the transition zone. However, the students
usually are not taught how a TEM and SEM can produce
such images at a very small scale. The purpose of Part I in
4.3. Module 3: Nanomaterial’s Properties and
this module is to provide the student enough background
Characterization
about the principles of how TEM and SEM function. In
This module introduces undergraduate students to this module we provide a description of electrical lenses,
commonly used equipment and techniques for charac- electron beam generation, vacuum chamber, and so on.
terization of materials at the nanoscale. The theoretical The TEM and SEM are both located in user facilities at the
16 J. Nano Educ. 2, 13–26, 2010

UNM’s main campus, steps away from both the Mechan- were submitted individually and covered topics such as
ical and Civil Engineering Departments. ethics in nanotechnology, nanomaterials for energy, and
RESEARCH ARTICLE
Furthermore, in Part II the students are directed to biomedical applications of nanomaterials. Each student
examine methods of mechanical characterization using had to read at least five refereed scholarly articles in topics
nanotechnology. Since its inception in 1992, nanoinden- related to his or her term paper to be aware of the state of
tation has quickly become the workhorse for determin- the art.
ing nanomechanical properties. This method is commonly
used to find a material’s elastic modulus and hardness
values. The theory of nanoindentation for metals, poly- 5. INTEGRATING NANOTECHNOLOGY
mers, and ceramic is introduced with an emphasis on its MODULES TO THE MATERIALS SCIENCE
advantage over its macroscopic counterpart. For example, LABORATORIES
nanoindentation can be utilized to test materials that are
not necessarily precast or machined in a specific shape (for The laboratory component ME352 and the lab for CE305
example, mechanical testing of a human tooth (Al-Haik were modified to include four experimental nanotechnol-
et al., 2008)) such as the famous dog bone-shaped tensile ogy modules that were co-taught by the four authors.
test sample. Also nanoindentation can be used to test very While all four experimental nanotechnology modules were
thin materials or materials that are too brittle (for example, adopted in mechanical engineering ME352L, only three
testing the micro beams on a MEMS chip (Trinke et al., experimental nanomodules were adopted in the lab of civil
2009)). The methods of obtaining the Young’s engineering CE305. The choice of the modules adopted
modulusby Ingenta
Delivered to:
in the CE305 lab was governed by the parts adopted on
and hardness values, and reproducibility of data also are
Virginia Polytechnic Institute & State University
discussed. The challenges in linking these observations to the nanotechnology lecture modules in CE305 and the
IP : 128.173.163.164
specific needs for the CE305 laboratory to cover other
macroscale properties are explained. Tue, 14 Jun 2011 23:11:51
In Part III, students examine electronic properties. One specific experiments related to civil engineering materials.
lecture is planned to introduce fundamental concepts about The plan for the experiments adopted in both laboratories
the electrical properties of materials. Using these basic is shown in Table I. All laboratory work in both ME352L
concepts, the electrical properties of CNTs and their use and CE305 was arranged using laboratory teams with eth-
in field effect transistors are discussed. nic and gender diversity taken into account. We present
A schematic representation of how the three modules here two sample nanoexperiment modules for clarifying
and their parts are integrated in both ME370 and CE305 is the nature of the revised lab modules.
shown in Figure 2. The rationale in selecting the modules
to be incorporated in each course is to accommodate 5.1. Lab Module 1: Nanoindentation Experiment
specific discipline needs while emphasizing the multi-
disciplinary nature of the integrated materials. Students of Examining material properties using hardness tests has
both classes will be sharing these modules in both lectures been used as non-destructive tests for metals for the last
and the laboratory experience. 100 years. Indentation depends on pushing a hard indenter
Beside the in-class and hands-on nanomaterials mod- into the surface of the material and recording the load and
ules, students also were asked to prepare a term paper indentation depth. In traditional experiments students in
discussing a specific application of nanotechnology and/or ME370/CE305 learned about determining material hard-
nanomaterials and their role in society. The term papers ness, which is a measure of a material’s resistance to sur-
face penetration by two hardness tests: macro hardness
(using Rockwell and/or Brinell) and micro hardness (using
Vickers microindentation with a diamond pyramid). In the
newly developed experiments, the interest lies in determin-
ing nanoscale hardness. Researchers showed that material
nanoscale hardness could be related to material stiffness
(elastic modulus) and energy absorption (toughness and
resilience) (Oliver & Pharr, 1992).
The recent advances in hardware control and
load/displacement measurements at the nanoscale trans-
formed nanoindentation into a technology that is both
robust and reliable for materials mechanical characteriza-
tion. Nanoindentation experiments comprise loading the
specimen to a specific load (usually in the range of micro
Fig. 2. Nanoscience educational modules being used to integrate mate- to milli Newton (mN)), keeping the load constant for a few
rials science classes across the School of Engineering at UNM. seconds to realize materials creep (strain growth with time)
J. Nano Educ. 2, 13–26, 2010 17

Table I. Integrated nanotechnology—materials science laboratories (ME352L and CE305).
Week ME352 (the lab for ME370) NEU modules CE305 lab
RESEARCH ARTICLE
1 Labs tour and safety procedures Measurements and technical reports

2 Technical writing, measurements Compression and bending tests of wood
3 Metallography: Molding, grinding, Tension test of mild steel. Torsion test of
polishing, and light microscopy aluminum
4 Module 1: SEM dislocation in brass Module 1: Electron scan microscopy (SEM) Module 1: SEM of cement morphology
5 Hardness: Brinell, and Vickers Charpy v-notch impact test, Brinell and
Vickers hardness tests
6 Module 2: Nanoindentation of brass Module 2: Nanoindentation Module 2: Nanoindentation of cement
7 Charpy impact testing Aggregate gradation, unit weight and voids
in aggregate
8 Tensile testing: Elastic–plastic deformation Cement mortar, setting time, blain fineness
9 Heat treatment: Annealing and quenching Concrete batching and fresh concrete
testing
10 Module 3: Nanoindentation: Effect of heat treatment on steel modulus and hardness
11 Module 4 Module 4: Transmission electron microscopy Asphalt experiments: gyratory compaction,
(TEM) of alumina nanoparticles, carbon rice specific gravity, resilience modulus
nanotubes
12 Ductile to brittle transition in metals Delivered by Ingenta to: Concrete testing, Young’s modulus &
Virginia Polytechnic Institute & State UniversityPoisson’s ratio of PCC
IP : 128.173.163.164
Tue, 14 Jun 2011 23:11:51
and unloading the specimen leaving an indentation impres- used nanoindentation to test concrete as an inhomogeneous
sion. A picture and schematic representation of the nanoin- material with different phases.
denter (NanoTest® ) that was used for nanoindentation tests
are shown in Figure 3. The NanoTest system is capable 5.2. Lab Module 2: Scanning Electron
of measuring hardness, modulus, toughness, adhesion, and Microscopy (SEM)
many other properties of thin films and other surfaces. The
NanoTest is a fully modular system that allows users to In this module, students in each discipline are directed
configure the system to meet their individual needs. Alter- to use the SEM to investigate one material of interest.
native nanoindentation machines are available with differ- While the mechanical engineering students were mentored
ent working mechanisms, but all nanoindenters provide to use the SEM to identify carbon nanostructures, stu-
a time-dependent, load-indentation depth response of the dents in civil engineering utilized the SEM to identify
material and can also provide a three-dimensional image the nano- and microstructure of cementitious composites.
of the indentation impression using an atomic force micro- The SEM sessions for mechanical engineering students are
scope (AFM) or a high resolution digital camera typically devoted to the study of carbon-based nanomaterials: nano-
available with the indenter. tubes, nanofibers, and metal-carbon composites. Nanosized
In this experiment, students indented four samples using carbon tubes, fibers, and particulates are analyzed at var-
ious degrees: their shape, size, and composition are the
the nanoindentation: 4340 steel that was heat treated and
focus of the practices. Alignment operations of the micro-
left to cool at different cooling rates by changing the
scope and sample preparation techniques were demon-
medium (furnace, air, oil and water). Sample nanoinden-
strated. Students have the opportunity to introduce samples
tation curves of the heat-treated steel samples are shown
into a microscope chamber and perform basic functions to
in Figure 4. Students indent 5 samples at a 50-mN load acquire images under supervision.
and will find the nanoscale properties of the different sam- On the other hand, civil engineering students study
ples using the load versus nanoindentation depth curves. cement and its hydration under the SEM. Students examine
While the theory of nanoindentation was covered previ- the factors affecting the reactivity of cements. For exam-
ously in the lecture modules added to the materials science ple, high tricalcium silicate (Ca3 SiO5 ; also known as alite
courses, students learned how the Young’s modulus and or C3 S) content yields a high early strength gain, while
hardness values can be obtained using the Oliver–Pharr high gypsum content yields even higher early strengths;
method through a built-in Java template with the Nano- The microstructure of aggregates also plays a role in dic-
Test system. Finally, students also learned how tone can tating the mechanical properties of concrete. For exam-
use an instrumented AFM attached to the NanoTest sys- ple, finer aggregates lead to more exposed surfaces to
tem to locate the trace of indentation they performed on water contact, which in return facilitates a higher rate
the sample’s surface. Civil engineering students (CE305) reaction of cement leading to higher early strengths. This
18 J. Nano Educ. 2, 13–26, 2010

every week, each lab had 4 groups of students (3–4 stu-

dents) performing the same experiment. For civil engineer-
RESEARCH ARTICLE
ing students there were 2 lab sections every week and the
students were divided into 4 groups for every experiment.
Because we wanted the new nanoexperiments to be
hands-on we carried out specific arrangements to ensure
the students interactions with several instruments while
maintaining the instruments in operational mode. In the
SEM module, usually the instructor or a graduate student
places the samples inside the microscope chamber and
gets the machine to the running mode prior to the exper-
iment. The students usually were divided into groups of
4 each, and each group got the instrument for a halfhour
to capture an image. Given that the students had not used
the instruments before and the instruments are dual usage,
the students’ supervision was strict. For example students
were not allowed to change the hardware setup or vent
the chamber. We just focused on getting the students to
be able toto:
Delivered by Ingenta control the spot size; focus on a single feature;
and control
Virginia Polytechnic Institute & State theUniversity
contrast brightness fine-focus and stigmata;
then capture
IP : 128.173.163.164 an image. The TEM experiments were solely
run by
Tue, 14 Jun 2011 23:11:51 the instructors considering the level of sophisti-
cation needed to run the instruments. However, students
who participated in the investigator’s research group were
able to learn the full operation of the TEM and some of
them were successful in obtaining highquality images for
publications, presentations and posters.
For the nanoindentation experiments, the instruc-
tor/graduate students usually install the sample and cali-
brate the instrument (this might take 2 hours, so usually
the machine was kept running 6 hours prior to the exper-
iment). As the machine is fully computer-controlled, stu-
dents did not need to open the NanoTest enclosing cabinet.
And since the cabinet is made of plexiglass it was easy
for the students to observe the experiment: stage move-
ment, engaging and disengaging of the indenter tip and
the sample. For the nanoindentation students were allowed
®
Fig. 3. Layout and schematic of the NanoTest system used for the to use the sample stage controller/motor to bring the sam-
nanoindentation lab module. ple within 25 micron from the indenter tip. A pre-written
indentation test template was carried out—usually for less
module introduces different cements pastes to civil engi- than 5 minutes—and the students used the NanoTest analy-
neering students with the intention of studying the phase sis software to get the final results of interest: elastic mod-
present in the samples by SEM. Figure 5(a) shows an ulus and hardness. Simplified instructions to perform these
SEM micrograph of the calcium silicate hydrate (C–S–H), tasks were handed to students prior to the lab. After the
which is a colloidal gel that is a very complex, poorly crys- students performed one nanoindentation cycle and ana-
talline material. Figure 5(b) shows an SEM micrograph lyzed it they were handed data from 25 nanoindentation
of (monosulphoaluminate) Ettringite, which forms in the tests that were carried out by the instructor/teaching assis-
early stages and later converts to a plate-like microstruc- tant so they could perform statistical analysis.
ture when gypsum is used and water is available. Finally,
Figure 5(c) shows calcium hydroxide (CH) crystals, which 6. NEW COURSE DEVELOPMENT
take the form of a plate-like material and are responsi-
ble for the low strength and non-durable performance of We introduced a new course, ME461-E, on the the-
concrete and mortar. ory, fabrication, and characterization of nano/micro-
Regardless of whether the experiment was classical or a electromechanical systems (NEMS/MEMS). This course
new nanoexperiment, for ME352 there were 3 lab sections was offered twice in the fall semesters of 2008 and 2009.
J. Nano Educ. 2, 13–26, 2010 19

(a) (b)
RESEARCH ARTICLE
(c) (d)

IP : 128.173.163.164
Tue, 14 Jun 2011 23:11:51
Fig. 4. Nanoindentation curves (loading-unloading) for different samples of 4030 steel that were heat treated at different cooling rates: (a) slow
cooling in furnace, (b) cooling in air, (c) quenching in oil, and (d) quenching in water.
This course is a laboratory course on the physical the- laboratories, barring any unforeseen circumstances such as
ory, design, analysis, fabrication, and characterization happened in the first semester we attempted this module.
of nanoelectromechanical systems (NEMS) and micro- In addition to the CNT modules, students also performed
electromechanical systems (MEMS). The main objective experiments where they make nano-thickness membranes
of this course is the fabrication of important types of used as pressure sensors and MEMS actuators. A pic-
nano/microstructures used in NEMS/MEMS devices and ture of an MEMS actuator that was made in ME461-E is
systems by multi-disciplinary and multi-ethnicity teams. shown in Figure 7(a), and a photograph of students work-
Therefore, the emphasis was on techniques used in the ing on the fabrication experiment in the UNM clean room
synthesis and fabrication of NEMS/MEMS. Basic tech- is shown in Figure 7(b). For ME461-E there was one lab
niques were discussed separately and then sequenced in session every week with roughly 4 groups of students.
order to build up these commonly used processes. Exam-
ples of the fabrication techniques discussed are photo-
7. RESULTS FROM IMPLEMENTATION
lithography, nanolithography, deposition and growth of
OVER TWO YEARS
thin films and CNTs, dry and wet chemical etching, and
alignment and bonding techniques. The developed nanomodules were delivered at the UNM
With the funding from another NSF grant, we were in 2008 and 2009. The new modules contributed heavily
able to add classroom modules on using focused ion beam toward tailoring the mechanical and civil engineering cur-
(FIB) technology for nanolithography and nanopattern- ricula toward nanomaterials through a series of seven class
ing of substrates as well as new modules on CNTs. A lectures and four hands-on experimental modules together
chemical vapor deposition furnace for growth of CNTs with training through undergraduate research.
was designed, built, and operated by undergraduate stu- To accommodate the new modulus in the ME370/CE305
dents using support from the current grant. Figure 6 shows we modified the class curriculum by removing topics such
some of the CNTs that were grown. We envision that as diffusion, which is covered later in the senior year along
this experiment module will be a permanent part of future with courses such as heat transfer and thermodynamics.
20 J. Nano Educ. 2, 13–26, 2010

(a)
RESEARCH ARTICLE
(b)

IP : 128.173.163.164
Tue, 14 Jun 2011 23:11:51
Fig. 6. SEM and TEM images of single walled carbon nanotubes
(SWCNTs). (a) and (b) are SEM images of SWCNTs aligned to their
(100) Si substrate. (c) and (d) are TEM images of SWCNTs.
(c)
utilized nanoindentation to measure the hardness, modulus
and qualitative measure of toughness. Also we got rid of
a lab session that was a dedicated statistical analysis of
experimental data because the students are exposed to this
in the measurement course and as a standalone course in
statistics. However we kept the writeup for the statistical
analysis posted on the lab web page.
By the end of each semester, upon finishing the deliv-
ery of all the nanotechnology lectures and experiments, a
survey was conducted to probe students’ opinion and sug-
gestions regarding the nanomaterials modules. The survey
consistent of 17 questions asking the student to rank dif-
ferent aspects of the nanomodules (substance, relevance,
content, instructor, background preparation, etc.). Roughly,
110 students from Mechanical Engineering and 53 students
from Civil Engineering participated in the survey. The sur-
Fig. 5. SEM micrographs of cement components: (a) C–S–H com- vey was conducted anonymously, and students were pro-
pound, (b) ettringite, and (c) CH crystals.
vided extra space to provide additional comments as they
saw fit. The survey questions together with the accumu-
Also we removed the manufacturing aspects of materials lated results are shown in Table II.
as there was a dedicated course that covers the manufac- Based on feedback from the survey, the students’
turing processes offered by the department of Mechanical responses were very positive and encouraging in terms
Engineering. Finally we eliminated the materials selec- of continuing to improve the modules. Sample statistics
tion lectures, as the ME department introduced a dedicated on the response to three questions from the survey are
course for materials selection in design. shown in Figure 8. Overall the majority of the students
For the laboratory, we switched one of the (67%) ranked the nanotechnology experience gained by
macro/microscale hardness tests with the nanoindentation. the enriched materials courses as very good to excellent.
Also instead of utilizing the Charpy test to measure the About 8% of the students did not have a positive opinion
brittleness of steel as a result of different cooling rates we for the nanomodules. Unfortunately, students who gave a
J. Nano Educ. 2, 13–26, 2010 21

(a) (b)
RESEARCH ARTICLE
Fig. 7. (a) A MEMS actuator fabricated by students involved in the NUE program. (b) Students fabricating MEMS inside a University of New Mexico
clean room during the NEMS/MEMS class.
poor evaluation of the program did not provide any con- engineering materials class might have an impact on the
structive written feedback or suggestions to improve the results of that survey. Construction management students
program in the future. enroll in the civil engineering materials class to gain
The fact that students with construction manage- material science knowledge necessary for their degree
ment background represent about 30–40% Delivered
of the civil by Ingenta to: However, most of construction management
requirements.
Table II. Results of the survey conducted after the implementation of Nanomodules in ME370/ME352L and CE305.
IP : 128.173.163.164
1 What is your opinion of the ME340/CE305 course Tue, material14 Jun 2011
in general 23:11:51
(lectures, handouts, and lab experiments)?
Excellent (39%) V-Good (32%) Good (21%) Fair (8%) Poor (0%) No opinion (0%)
2 What is your opinion of the nanomaterials lectures?
3 What is your opinion of including the nanoexperiment; nanoindentation, SEM, TEM, and XRD?
4 On a scale of 5–1, were the learning objectives of the new nanomaterials modules clear to you?
(5) Perfectly clear (22%) 4 (31%) 3 (39%) 2 (5%) (1) Very unclear (0%) No opinion (3%)
5 On a scale of 5–2, did you have enough knowledge from earlier courses that you found to be useful for this course?
(5) Very much so (44%) 4 (26%) 3 (21%) 2 (9%) (1) Not at all (0%) No opinion (0%)
6 Did the nanomaterials modules provide enough knowledge of what nanomaterials are, their applications, and the impact of
nanotechnology on society?
Yes I think so (34%) Just enough knowledge (27%) Fair level of knowledge (31%) Very little knowledge (8%) Not at all (0%)
7 Do you believe the introduction of the nanomaterials to ME370/CE305 helped you get a better understanding of the nanomaterials area?
Strongly agree (23%) Agree (45%) Disagree (21%) Strongly disagree (5%) No opinion (6%)
8 Should the nanomodules be taught in a separate standalone course? Or should they be kept in the current modules form in ME370/CE305?
Keep it as modules in ME370/CE305 (65%) Offer it as a standalone course (31%) No opinion (4%)
9 Which of the following laboratories did you like the most or the least?
Nano Indentation SEM/TEM XRD
Most (26%) Least (44%) Most (48%) Least (22%) Most (26%) Least (34%)
10 Which specific topic would you would to have covered in more detail in this course?
Nanostructures and Nanosynthesis (56%) Carbon Nanotubes (26%) Ceramics Nanoparticles (9%) Nanocharacterization (9%)
11 Generally, are you interested in taking other courses in nanotechnology, if provided as technical electives?
Very interested (67%) Interested (13%) Little interested (11%) Not interested at all (9%)
12 Given your experience in ME370/CE305, would you be interested in taking ME461-E (Theory, Fabrication and Characterization of
Nano/micro Electromechanical Systems (NEMS/MEMS))?
Yes (61%) Possibly (26%) No (10%) No opinion (3%)
Note: Students were provided with the syllabus in advance
13 Given your experience in ME370/CE305, would you be interested in taking ME462 (Nanomaterials Preparation and Characterization)?
Note: Students were provided with the syllabus in advance
14 Do you see the term paper as a useful experience that assisted you in exploring and identifying useful and societal applications of nanomaterials?
Strongly agree (61%) Agree (30%) Disagree (9%) Strongly disagree (0%)
15 Would you recommend ME370/CE305 with nanomodules to your colleagues at the UNM College of Engineering?
16 Please explain briefly why you took this course (ME70/CE305).
17 Please provide any remarks, suggestions to improve the nanomodules.
22 J. Nano Educ. 2, 13–26, 2010

who took the materials science course felt strongly that

the nanomodules should be employed in the two mate-
RESEARCH ARTICLE
rials science courses (ME370/CE305); only 31% of the
survey population suggested offering these modules as a
standalone course. As far as probing the students’ inter-
ests in specific modules, mostly the students preferred to
focus more on nanosynthesis, nanostructures, and CNTs,
as compared to nanocharacterization or ceramic nanopar-
ticles. In general 67% of the students expressed that they
are very interested in another course in nanotechnology,
some of them indicated that they are somewhat interested
(13%) given that this will count as a technical elective
replacing one of the classical technical electives courses.
Specifically, 61% of the students expressed serious inter-
est in taking the ME461-E course. In actuality 34 students
have enrolled for ME461-E (NEMS/MEMS). The desire
to take another course in nanomaterials preparation and
nanocharacterization was not as assertive, only 44% of the
students expressed
Delivered by Ingenta to: a strong interest in that course.
The survey also
Virginia Polytechnic Institute & State University indicated that the students also pre-
ferred
IP : 128.173.163.164 to learn more about nano applications, nanoma-
terials,
Tue, 14 Jun 2011 23:11:51 and nanotechnology societal implications through
the term paper mechanism. The term papers reflected the
student awareness of the importance of nanotechnology,
nanomaterials, and systems in the society. Roughly 91%
of the students favored this mechanism as a means to
learn more about how nanotechnology affects an applica-
tion of their choice, such as energy, biomedical, imaging,
and sensors.
The survey also asked the students to provide sug-
gestions/critiques to improve the nanomodules. Students
who evaluated the nanomodules as good to excellent
asked for more hands-on exposure in smaller groups (typ-
ically nanoexperiment groups consisted of 4–6 students
per group) and earlier exposure to nanotechnology (both
courses are senior level). In response to this comment in
later semesters we involved the students more in operat-
Fig. 8. Sample students’ evaluation of the nanotechnology modules ing the instruments. The demand of earlier exposure to
introduced to ME370 and CE305. nanotechnology will be implemented in the renewed NSF-
REU proposal 2011–2012, where a freshman course will
students lack the major engineering background. The be developed toward this purpose.
significance of background difference on students’ perfor- Some students suggested that an instrumentation and
mance in civil engineering materials class have been dis- measurement course be placed as a prerequisite prior to
cussed elsewhere. taking the courses with nanomodules. This suggestion was
The majority of the students (70%) have indicated that posed based on the fact the nanoindentation experiment
they had some helpful background from earlier courses was demanding many calibration steps and data acquisition
(mainly chemistry) that they found to be useful in the using LabView software. The survey reflected this opin-
newly introduced nanomodules. As an outcome of the ion as 44% of the students indicated that they were less
implementation, 61% of the students have indicated that interested in the nanoindentation, while 22% indicated that
the nanolectures and experiments have equipped them with SEM was the least interesting module. This suggestion
a high to satisfactory level of knowledge on what qualify was communicated to the undergraduate curricula commit-
as nanomaterials and their impact on society. Despite the tee in the civil and mechanical engineering departments
rushed approach in the first semester, by the end of the for consideration. Other students suggested reducing the
two years’ implementation a significant percentage (65%) number of modules, considering that classical experiments
of the civil and mechanical engineering undergraduates needed to be covered as well. The investigators considered
J. Nano Educ. 2, 13–26, 2010 23

alternating the nanoexperiments each semester by intro-

ducing the TEM microscopy experiment in the spring and
RESEARCH ARTICLE
the XRD experiment in the fall semester. As an update

(both hardware and software) of the NanoTest is currently
underway, we hope to make it more user-friendly and less
demanding for the calibration so it could be received more
favorably in the future.
Based on the success of the nanomaterials modules 34
students have enrolled in ME461-E (MEMS). This course
aided them in the theoretical and experimental knowledge
of nanosystems. This course was appealing to minority
students, in particular 13 students were from underrepre-
sented groups (Hispanic, Native American and Asian) and
9 were females.
The investigators have mentored several students
who finished two of the nanotechnology courses
offered through the NUE program (ME370/ME352L and
ME461-E). Eighteen undergraduate students have partic-
ipated in nanomaterials and nanosystems research.
DeliveredThe by Ingenta to:
student participation resulted inVirginia
4 honorsPolytechnic
theses and 11 Institute & State University
refereed journals publications. IP : 128.173.163.164
The recruiting of undergraduate students Tue,
to participate
14 Jun 2011 23:11:51
in the research aspects prepared them to play teaching
assistant roles in the following semesters especially for the
SEM and nanoindentation modules. Some students became
involved in the investigators’ research groups to work
on other research projects with a nanotechnology theme.
Eighteen undergraduate students have participated in nano-
materials and nanosystems research. The student partici-
pation resulted in 4 honors theses and 11 refereed journals
publications. Some of these research projects: synthesis
of WS2 ( Tehrani et al., 2011), nanoindentation of den-
tal materials (Al-Haik et al., 2008), nanocreep behavior of
cements (Reinhardt et al., 2009) and growing CNTs on
carbon fibers (Al-Haik et al., 2009; Luhrs et al., 2009).
Figure 9 provides images produced by undergraduate stu-
dents during some of these projects. The education through
research involvement offered the students more guided,
formal and comprehensive training on SEM, TEM, nanoin-
dentation and XRD. Therefore some of the undergradu-
ate students involved in this research experience became
capable of running these instruments on their own with-
out supervision. We utilized some of this newly gained Fig. 9. Sample projects that involved participation of undergraduate stu-
technical expertise in the form of teaching assistance in dents: (a) SEM image of hybrid carbon fiber with surface grown CNTs
(Jeremy Chavez), (b) (SEM) micrograph of WS2 (Juanita Trevino), and
the nanoexperiments that required SEM/TEM/XRD and
(c) Optical micrograph of a thermal actuator (Ian Young and Dylan
nanoindentation. Wood).
Several students expressed an interest in graduate stud-
ies in nanomaterials-based research. Nine students (6 ME granting only MS and PhD diplomas. In the investigators’
and 3 CE) who participated in the undergraduate research research groups the number of U.S. students in general
projects with the investigators enrolled in graduate pro- and those who are from minority groups in particular had
grams at UNM. The nanotechnology education of under- improved.
graduates through our program at UNM has leveraged an The activities implemented during this nanotechnology
existing graduate program in nanotechnology—the Nano program at the UNM had an impact on under-represented
Sciences and MicroSystems (NSMS) program. This NSF groups in science and engineering. The ethnic and gender
IGERT program at UNM is strictly a graduate program distribution of these courses are shown in Figure 10.
24 J. Nano Educ. 2, 13–26, 2010

internships at Sandia National Labs, Los Alamos National

Labs, Intel Corporation, and Kirtland Air force Base. To
RESEARCH ARTICLE
their credit, all these entities have aggressive on- and off
campus recruiting programs. We believe that the intern-
ships made possible to the students through the NSF-
NEU grants to the investigators together with the hands-on
encounter with nanotechnology through the materials lab-
oratories, assisted significantly in attracting minority stu-
dents to conduct research in nanotechnology.
8. CONCLUSIONS AND FUTURE WORK

A new group of nanotechnology modules for undergradu-
ate engineering education was developed and introduced to
engineering students at the UNM. The new modules were
established in materials science courses serving mechan-
ical and civil engineering students. A preliminary survey
showed that the majority of students are in favor of the
nanotechnology modules.
Virginia Polytechnic InstituteThe & core
Statecurricula
University
of the Mechanical and Civil Engi-
IP : 128.173.163.164
neering Departments were not altered. Nanotechnology
Tue, 14 Jun 2011 23:11:51
modules were strategically inserted in the core classes and
an elective course on nano and micro systems was taught
in the senior year.
Based on the survey results, the authors will continue
the format of stand-alone modules and nano experiments.
Improvements based on the student surveys conducted so
far will include more hands-on experiments (for exam-
ple, synthesis of nanomaterials). We also plan to intro-
Fig. 10. Accumulative statistics of the ethnic and gender distributions duce term projects where students will still go through all
of the three courses employed in the investigation (ME370, CE305, and the nanomodules and nanoexperiments, but will be trained
ME461-E).
exclusively on an instrument of their choice (SEM, TEM,
XRD nanoindenter, etc.) to fulfill their project.
UNM is the only Carnegie, Very High Research Finally, the authors will continue to mesh the nano-
University in the country designated as a Minority and education and research via incorporating undergraduates in
Hispanic-Serving Institution (MHSI). Most of the under- their current research activities in nanotechnology. As evi-
graduate students at the School of Engineering at UNM denced by the investigators’ own experience, this approach
come from New Mexico, and the demographics reflect the appealed to the large community of minority students at
multicultural character of the state. UNM School of Engi- UNM.
neering graduation rates for Hispanic and Native American With nanotechnology becoming part of so many core
students are among the highest in the U.S. Currently courses and also having dedicated stand-alone courses
40% of engineering undergraduates come from under- in nanotechnology, we envision that a critical mass
represented groups (American Indian and Hispanic) and will have been reached to create a concentration in
20% of our students are female, on par with the national micro/nanotechnology at UNM.
average.
One major challenge throughout the nanotechnol- Acknowledgments: The authors acknowledge the sup-
ogy program has been improving the recruiting of port of the National Science Foundation support through
undergraduate students from minority groups to do the Nanotechnology Undergraduate Education (NUE)
research in nanotechnology or even research in general. grants #0936412 and 0741525. The authors would like
UNM is surrounded by several federal and industrial to thank Prof. Adrian Brearley for granting access to the
entities that, rightfully, are trying to diversify their work- electron microscopy facilities at the University of New
force by appealing to the large Hispanic students’ com- Mexico and Prof. John Wood for granting access to the
munity at UNM through summer internships. From the clean room facility at the Manufacturing Training and
investigators’ personal attempts to attract the undergrad- Technology Center (MTTC), University of New Mexico
uates from minority groups, students usually preferred (UNM). Finally, we would like to thank Prof. Jonathan
J. Nano Educ. 2, 13–26, 2010 25

Phillips (Los Alamos National Laboratory, retired) and Luhrs, C., Garcia, D., Tehrani, M., Al-Haik, M., Reda Taha, M., &
Prof. Hamid Garmestani (Georgia Institute of Technology) Phillips, J. (2009). Generation of carbon nanofilaments on carbon fibers
at 550 C. Carbon, 47(13), 3071–3078.
RESEARCH ARTICLE
for acting as external evaluators of the current NUE pro-

Maji, A. & Taha, M. M. R. (2008). Learning styles and integration of
gram at UNM. management and engineering students. ASEE Southwest Conference,
Albuquerque New Mexico.
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otechnology and nanomaterials. American Society for Engineering ence and Technology of Civil Engineering Materials, Prentice Hall,
Education Annual Conference & Exposition, Salt Lake City, Utah. USA.
Received: 17 November 2010. Accepted: 4 March 2011.
26 J. Nano Educ. 2, 13–26, 2010

INFORMATION PAPER
International Journal of Recent Trends in Engineering, Vol 1, No. 4, May 2009
Significance of Nanotechnology in Construction

Engineering
Ashwani K. Rana1, Shashi B Rana2, Anjna Kumari3 and Vaishnav Kiran4
1, 3, 4
National Institute of Technology, Hamirpur (H.P), India
Email: 1ashwani_paper@yahoo.com
2
Regional Campus G.N.D.U. Gurdaspur, Punjab, India
Emails: 2shashi_rana12@yahoo.co.in, 3anjna.paper@gmail.com,4vaishnav.rana@gmail.com,
Abstract— Nanotechnology is one of the most active improvements in characterization equipment and a new
research areas that encompass a number of disciplines understanding into the chemistry and physics of matter on
including civil engineering and construction materials. the nanoscale. Nanoscale science can be divided into
Traditionally, nanotechnology has been concerned with three broad areas, e.g. nanostructures, nanofabrication
developments in the fields of microelectronics, medicine and
materials sciences. However, the potential for application of
and nanocharacterization with typical applications in
many of the developments in the nanotechnology field in the nanoelectronics and life sciences & energy [5].
area of construction engineering is growing. In this paper a This article examines the potential areas where
broad overview of the potential application of various nanotechnology can benefit construction engineering.
nanotechnology developments in the construction The data and information collected is from current
engineering field is discussed, and the potential for further literature. The purpose is to point out clear cut direction
basic research that may lead to improved systems is among the nanotechnology development areas where the
evaluated. construction process would immediately harness
nanotechnology, by specifying clear recommendations.
Index Terms- Nanomaterials, Construction.
The information would be beneficial to both construction
engineering education and research.
I. INTRODUCTION
The rest of the paper is organized as follows. In
Nanotechnology is a field that is dominated by Section II, detailed applications of nanotechnogy in
developments in basic physics and chemistry research construction engineering/industry are presented. Section
[1], where phenomena on atomic and molecular level are III, presents the future challenges and directions. Finally,
used to provide materials and structures that perform concluding remarks are offered in Section IV.
tasks that are not possible using the materials in their
II. APPLICATION OF NANOTECHNOLOGY IN
typical macroscopic form. The evolution of technology
CONSTRUCTION
and instrumentation as well as its related scientific areas
such as physics and chemistry are making the research on Nanotechnology can be used for design and construction
nanotechnology aggressive and evolutional [2]. Not processes in many areas since nanotechnology generated
surprisingly, it is observed that expenditure on products have many unique characteristics. These include
nanotechnology research is significant. The U.S. National products that are for: Lighter structure; Stronger
Nanotechnology Initiative (NNI) expenditures exceed $1 structural composites e.g. for briges etc ; Low
billion each year, with the President’s 2008 budget for maintenance coating ; Improving pipe joining materials
NNI at $1.5 billion. However, the research is mainly and techniques ; Better properties of cementitious
moving forward motivated by immediate profitable return materials ; Reducing the thermal transfer rate of fire
generated by high value commercial products [3]. It has retardant and insulation ; Increasing the sound absorption
been established by study, nanotechnology in of acoustic absorber ; Increasing the reflectivity of glass.
construction ranked 8 of 10 applications that most likely
There are large numbers of applications of
have impact in the developing world [4].
nanotechnology in construction engineering/industry.
Nanotechnology covers the design, construction
Some of these applications are examined in detail below.
and utilization of functional structures with at least one
characteristic dimension measured in nanometers [5]. The A. Concrete
field of nanotechnology has developed in major leaps Concrete is one of the most common and widely used
during the past 10 years. These developments were construction materials. The rapid development of new
mainly driven by factors such as dedicated initiatives in experimental techniques makes it possible to study the
the field (e.g. the National Nanotechnology Initiative) [5], properties of cementitious materials at micro/nano-scale.
Research has been conducted to study the hydration
Ashwani K. Rana is with Department of Electronics and process, alkali-silicate reaction (ASR), and fly ash
Communication Engineering, NIT Hamirpur, India reactivity using nanotechnology [6]. The better
understanding of the structure and behavior of concrete at
Shashi B Rana is with Department of Electronics Technology,
G.N.D.U. Regional Campus Gurdaspur, Punjab, India micro/nano-scale could help to improve concrete
properties and prevent the illness, such as ASR.
Anjna Kumari and Vaishnav Kiran are with Department of Applied
Sciences and Humanities, NIT Hamirpur, India
46
© 2009 ACADEMY PUBLISHER

INFORMATION PAPER
Addition of nanoscale materials into cement through powerful catalytic reaction [10]. Furthermore, it
could improve its performance. In [7], Li (2004) found is hydrophilic, which allow the water to spread evenly
that nano-SiO2 could significantly increase the over the surface and wash away dirt previously broken
compressive for concrete, containing large volume fly down. Other special coatings also have been developed,
ash, at early age and improve pore size distribution by such as anti-fraffiti, thermal control, energy sawing, anti-
filling the pores between large fly ash and cement reflection coating.
particles at nanoscale. The dispersion/slurry of
D. Nanosensors
amorphous nanosilica is used to improve segregation
resistance for self-compacting concrete [8]. It has also Nano and microelectrical mechanical systems (MEMS)
been reported that adding small amount of carbon sensors have been developed and used in construction to
nanotube (1%) by weight could increase both monitor and/or control the environment condition and the
compressive and flexural strength [9]. materials/structure performance. One advantage of these
Cracking is a major concern for many structures. sensors is their dimension (10-9m to 10-5m) [11]. These
University of Illinois Urbana-Champaign is working on sensors could be embedded into the structure during the
healing polymers, which include a microencapsulated construction process. Smart aggregate, a low cost
healing agent and a catalytic chemical trigger [8]. When piezoceramic-based multi-functional device, has been
the microcapsules are broken by a crack, the healing applied to monitor early age concrete properties such as
agent is released into the crack and contact with the moisture, temperature, relative humidity and early age
catalyst. The polymerization happens and bond the crack strength development [12]. The sensors can also be used
faces. The selfhealing polymer could be especially to monitor concrete corrosion and cracking.
applicable to fix the microcracking in bridge piers and The smart aggregate can also be used for structure
columns. But it requires costly epoxy injection. health monitoring. The disclosed system can monitor
internal stresses, cracks and other physical forces in the
B. Structural Composites structures during the structures' life. It is capable of
Steel is a major construction material. Its properties, such providing an early indication of the health of the structure
as strength, corrosion resistance, and weld ability, are before a failure of the structure can occur.
very important for the design and construction. FHWA
III. FUTURE CHALLENGE AND DIRECTION
together with American Iron and Steel Institute and the
U.S. Navy started to develop new, low carbon, high- As with most developing technologies, a major number of
performance steel (HPS) for bridges in 1992 [10]. The challenges exist during the initiation of the application of
new steel was developed with higher corrosion-resistance the technology into reality. It is important to be realistic
and weld ability by incorporating copper nanoparticles and identify and plan for the limitations and challenges
from at the steel grain boundaries. Sandvik NanoflexTM inherent in this process. In this section a short summary
is new stainless steel with ultra-high strength, good of selected challenges and limitations affecting
formability, and a good surface finish developed by application of nanotechnology in construction
Sandvik Nanoflex Materials Technology. Due to its high engineering are provided. The following main challenges
performance, Sandvik NanoflexTM is suitable for and limitations can be defined: Fabrication, Health,
application which requires lightweight and rigid designs. Environment and Cost
Its good corrosion and wear resistance can keep life-cycle A. Fabrication
costs low. Attractive or wear resistant surfaces can be
achieved by various treatments (Sandvik Nanoflex Current efforts in the field of nanotechnology are focused
Materials Technology). MMFX2 is nanostructure- on the fabrication, characterization and use of these
materials on a nanoscale domain. This leads to most of
modified steel, produced by MMFX Steel Corp.
Compared with the conventional steel, it has a the development work focusing on very small quantities
fundamentally different microstructure- a laminated lath of material that is typically far removed from the type of
quantities required for typical construction infrastructure.
structure resembling “plywood”. This unique structure
provides MMFX2 steel with amazing strength (three One of the potential solutions to this is to focus on the
times stronger), ductility, toughness, and corrosion nano materials to act as catalyser, thereby reducing the
amount of nano material required substantially. Another
resistance. Due to high cost, the stainless steel
reinforcement in concrete structure is limited in high risk viewpoint is that for many applications, the material does
environments. The MMFX2 steel could be an alternative not necessarily have to be used on a nano scale to obtain
because it has the similar corrosion resistance to that of a major improvement in benefits. This would be the case
stainless steel, but at a much lower cost (MMFX Steel with reduction of the dimensions of cement, where a
substantial improvement in strength can already be
Corp.).
obtained through the large scale milling of the cement to
C. Coating a finer form than the traditional form. Although the
The coatings incorporating certain nanoparticles or cement may not be purely a nano material as yet, the
nanolayers have been developed for certain purpose. It is benefits obtained would already be substantial [13].
one of the major applications of nanotechnology in B. Health
construction. For example, TiO2 is used to coat glazing
Nanotechnology based construction products might be
because of its sterilizing and anti fouling properties. The
TiO2 will break down and disintegrate organic dirt harmful to health. For example, the nanotubes [14] might
47

INFORMATION PAPER
cause a lung problem to construction workers. In other Based on the information discussed in this paper, the
words, it creates an environmental challenge to the following directions are made:
construction industry as well. • Focused research into the timeous and directed
research into nanotechnology for construction
C. Environment
infrastructure should be pursued to ensure that the
The effect of various nanomaterials on the natural potential benefits of this technology can be obtained
environment is hotly debated in nanotechnology and to provide longer life and more economical transport
environmental research. Various ongoing investigations infrastructure.
focus on the uncertainty regarding the potential effects of
materials that exist on the nanoscale with properties that REFERENCES
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macro scale [15]. Some work in this regard shows that the and Materials”, J. of Physics & Chemistry of Solids, 65,
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infrastructure are provided in the natural environment, all [2] Chong, K.P. “Research and Challenges in Nanomechanics”
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environment and their effects on the natural environment “Introduction.” Proceedings of the International
should not be negative. Typical potential problems in this Conference – Application of Technology in Concrete
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of dust and exposure to potentially harmful materials of the Top Ten Answers to World’s Biggest Problems.
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[5] Goddard III, W.A., Brenner, D.W., Lyshevski, S.E. and
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Iafrate, G.J. 2007. Handbook of nanoscience, engineering,
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The costs of most nanotechnology materials and 2005.
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of the technology and the complexity of the equipment Incorporating Nano-SiO2.” Cement and Concrete
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[8] Bigley C. and Greenwood P. “Using Silica to Control
[9]. However, costs have been shown to decrease over
Bleed and Segregation in Self-Compacting Concrete.”
time and the expectations are that, as manufacturing Concrete, vol. 37, no. 2, p.43-45, 2003.
technologies improve, these costs may further decrease. [9] Mann, S. (2006). “Nanotechnology and Construction,”
Whether the expected decreases will render the materials Nanoforum Report. www.nanoforum.org, May 30, 2008.
as run-of-the-mill construction engineering materials will [10] Arafa, M.D., DeFazio, C. and Balaguru, B. 2005. Nano-
have to be seen, and depends largely on the benefits composite coatings for transportation infrastructures:
rendered through the application of these materials. Demonstration projects. 2nd International Symposium on
Current opinion is that in special cases, the materials will Nanotechnology in Construction, 13 to 16 November 2005,
enable unique solutions to complicated problems that Bilbao, Spain.
[11] Liu, R., Zhang, Z., Zhong, R.; Chen, X.; Li, J.
cause them to be cost effective, which will lead to large-
“Nanotechnology Synthesis Study: Research Report” 2007.
scale application of these specific technologies. In other [12] Song, Gl, Gu, H. and Mo, Y. “Smart Aggregates: Multi-
cases the traditional methods for treating the problem Functional Sensors for Concrete Structures-a Tutorial and
may still remain the most cost effective. It is the a review.” Smart Mater. Struct. vol.17, 2008.
challenge to the construction engineer to solve real world [13] Garcia-Luna, A. and Bernal, D.R. 2005. High strength
transportation infrastructure problems and provide a micro/nano fine cement. 2nd International Symposium on
facility to the general public at a reasonable cost. Nanotechnology in Construction, 13 to 16 November 2005,
Bilbao, Spain.
IV. CONCLUSIONS [14] Tong, Z., Bischoff, M. and Nies, L. “Impact of Fullerene
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following conclusions are drawn: Technol. 2007, 41, 2985-2991, 2007.
[15] NNI, Nanotechnology and the environment. Report of a
• Nanotechnology is a rapidly expanding area of
National Nanotechnology Initiative Workshop, May 8-9,
research where novel properties of materials Arlington, VA, 2003.
manufactured on the nanoscale can be utilized for the
benefit of construction infrastructure
• A number of promising developments exist that can
potentially change the service life and life-cycle cost
of construction infrastructure.
48

Hindawi Publishing Corporation
Journal of Nanomaterials
Volume 2012, Article ID 427310, 6 pages
doi:10.1155/2012/427310
Research Article
Fabrication of Magnetite/Silica/Titania Core-Shell Nanoparticles
Suh Cem Pang, Sze Yun Kho, and Suk Fun Chin
Department of Chemistry, Faculty of Resource Science and Technology, Universiti Malaysia Sarawak, Kota Samarahan,
94300 Sarawak, Malaysia
Correspondence should be addressed to Suh Cem Pang, suhcem@gmail.com
Received 25 September 2012; Revised 26 November 2012; Accepted 27 November 2012
Academic Editor: Yanbao Zhao
Copyright © 2012 Suh Cem Pang et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles were synthesized via a sol-gel method with the aid of sonication. Fe3 O4 nanoparticles
were being encapsulated within discrete silica nanospheres, and a layer of TiO2 shell was then coated directly onto each silica
nanosphere. As-synthesized Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles showed enhanced photocatalytic properties as evidenced
by the enhanced photodegradation of methylene blue under UV light irradiation.
1. Introduction could increase the lifetime of photogenerated holes which

in turn, resulted in increased photoreactivity [3, 4]. This is
Over the past decades, titanium dioxide (TiO2 ) nanoparticles attributed to the SiO2 layer which serves as an insulating layer
have gained much attention as a photocatalyst and catalyst between Fe3 O4 nanoparticles (hole-electron trap center) and
support [1, 2]. TiO2 nanoparticles have many advantages as the TiO2 shell.
compared to other photocatalysts, which include excellent However, there are currently very few literature which
high stability against chemical and photonic corrosion report on the synthesis of Fe3 O4 /SiO2 /TiO2 core-shell
and high photocatalytic activity [3]. TiO2 nanoparticles of nanoparticles and their photocatalytic properties. Besides,
small mean particle sizes possess high surface area and the reported synthesis methods for Fe3 O4 /SiO2 nanoparticles
photocatalytic activity. However, TiO2 nanoparticles of high were generally complicated and time consuming. Besides, the
surface area are thermally unstable and lose their surface coating of Fe3 O4 with SiO2 using TEOS was a very slow pro-
area readily [3]. Therefore, much effort has been focused on cess which required 12 to 48 hours of mechanical stirring at
coating of TiO2 on high surface area supports such as silica room temperature [5]. Santra et al. used the microemulsion
or alumina in order to stabilize TiO2 nanoparticles. method for the preparation of Fe3 O4 /SiO2 /TiO2 core-shell
TiO2 nanoparticles could be difficult to recover and nanoparticles which was a lengthy process and involved the
lost readily upon being dispersed into wastewater. One use of several types of surfactants [6]. Gad-Allah et al. and
of the ways to overcome this problem is to coat TiO2 Watson et al. reported the preparation of Fe3 O4 /SiO2 /TiO2
onto magnetite (Fe3 O4 ) cores and the resulting Fe3 O4 /TiO2 nanocomposites [4, 7]. However, Fe3 O4 /SiO2 /TiO2 core-
core-shell nanoparticles can be recovered easily through shell nanoparticles prepared by them were in the form of
manipulation by external magnetic field. Li et al. synthesized patches and not discrete nanoparticles. As such, these core-
Fe3 O4 /TiO2 nanocomposite photocatalyst using a sol-gel shell nanoparticles exhibited in reduction on their surface
method [3]. However, it was difficult to achieve complete area and photocatalytic properties. Song and Gao reported
coating of Fe3 O4 nanoparticles with TiO2 at nanometer scale the use of the sol-gel process to synthesize Fe3 O4 /SiO2 /TiO2
using the sol-gel method. Besides, TiO2 would oxidize Fe3 O4 nanoparticles but the particles synthesized were very big size
nanoparticles and lead to a reduction of magnetic moment. of about 500 nm [8].
Some researchers had attempted to coat a thin layer of SiO2 Herein, we have reported a facile and efficient synthesis
between Fe3 O4 nanoparticles and TiO2 shell. The presence approach for the fabrication of Fe3 O4 /SiO2 /TiO2 discrete
of a SiO2 layer between TiO2 shell and Fe3 O4 nanoparticles core-shell nanoparticles by the sol-gel method with the aid
2 Journal of Nanomaterials
The dispersion was homogenized by sonication for about 10

minutes. 3.3 mmol of TEOS was then added into the mixture
and sonicated for another 20 minutes. Finally, 30 mmol of
aqueous ammonia was added and the mixture was sonicated
for 60 minutes. Fe3 O4 /SiO2 core-shell nanoparticles were
isolated by magnetically separation and then washed with
ultrapure water.
2.4. Preparation of Fe3 O4 /SiO2 /TiO2 Core-Shell Nanoparti-

cles. A layer of TiO2 shell was coated directly onto Fe3 O4 /
SiO2 nanoparticles via the hydrolysis and condensation of
TIPP in the presence of Fe3 O4 /SiO2 nanoparticles as seeds.
0.36 mL of TIPP was added into Fe3 O4 /SiO2 suspension
and stirred continuously for 18 hours at room temperature.
50 nm The resulting Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles were
dried in an oven and finally calcined at 450◦ C for 3 hours
Figure 1: Fe3 O4 nanoparticles were used as seeds for coating of SiO2 to convert the TiO2 outer shell from amorphous phase to
and TiO2 shells. photocatalytically active crystalline anatase phase [10].
2.5. Photocatalytic Activity Evaluation. The photocatalytic

of sonication. Fe3 O4 nanoparticles were being encapsulated activity of Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles was
inside discrete SiO2 nanospheres within 90 minutes, and investigated by measuring the photodegradation rate of an
a TiO2 layer was then coated directly onto each SiO2 aqueous solution of MB in the presence of Fe3 O4 /SiO2 /
nanosphere via the sol-gel method. The photocatalyst prop- TiO2 core-shell nanoparticles and under UV irradiation.
erties of as-synthesized Fe3 O4 /SiO2 /TiO2 core-shell nanopar- 0.02 mmol MB solution (25 mL) and a measured amount
ticles were evaluated by the photodegradation of methylene of Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles were placed
blue (MB) with or without UV light irradiation. inside a glass vial. A 6 W UV tube with a wavelength of
254 nm was used as the irradiation light source. During
2. Materials and Methods the photocatalytic reaction, the core-shell nanoparticles were
being well dispersed by stirring the suspension continuously.
2.1. Materials. Iron (II) chloride tetrahydrate, FeCl2 ·4H2 O At predetermined intervals of UV irradiation, a subsample of
(Merck); Iron (III) chloride 6-hydrate, FeCl3 ·6H2 O the suspension was collected and analyzed by UV-Vis spec-
(AnalaR); tetraorthosilicate, TEOS (99.3%, J.T. Baker); trophotometer at its characteristics absorption wavelength
absolute ethanol, EtOH (99.0%, HmBG Chemicals); hydro- (λmax = 642 nm) of MB.
chloric acid, HCl (37%, HmbG Chemicals); ammonia
solution, NH4 OH (28%, R&M Chemicals); titanium (IV) 2.6. Morphological Characterization. The morphologies of
isopropoxide, TIPP (97%, Aldrich); and Milli-Q water all samples were examined using a scanning electron
(18.2 MΩ cm−1 ) were used throughout the experiment. All microscopy (SEM) (JEOL Model JSM-5300LV) and a trans-
chemicals were used as received without further purification. mission electron microscopy (TEM) (JEOL JSM-6710F). The
elemental composition of the core-shell nanoparticles were
2.2. Preparation of Fe3 O4 Nanoparticles. Fe3 O4 nanoparti- analysed by SEM associated energy-dispersed X-ray micro-
cles were prepared using a simple chemical coprecipita- analysis (EDX) operated with the beam energy of 20 kV. The
tion method [8]. Typically, 0.15 moL of FeCl2 ·4H2 O and BET surface area analysis was conducted using the nitrogen
0.30 moL of FeCl3 ·6H2 O were freshly prepared in aqueous absorption-desorption method at 77.30 K (Micromeritics
HCl (2 M), respectively. Both FeCl2 ·4H2 O and FeCl3 ·6H2 O ASAP 2010). The phase of the Fe3 O4 /SiO2 /TiO2 core-shell
aqueous solution were then added rapidly to 20 mL of de- nanoparticles was identified using an X-ray diffractometer
aerated Milli-Q water under nitrogen flow at 80◦ C with (XRD) (RIGAKU, Getgerflex D/MAX-1C).
the mixture being continuously stirred under nitrogen.
Upon adding an aqueous NH4 OH solution (28%, 4 mL), 3. Results and Discussion
a distinctive black precipitate of Fe3 O4 nanoparticles was
formed immediately. Fe3 O4 nanoparticles were isolated and 3.1. Preparation of Fe3 O4 /SiO2 Nanoparticles. In this study,
purified by centrifugation and then washed with Milli-Q Fe3 O4 nanoparticles with mean diameter of approximately
water three to four times to remove excess NH4 OH solution. 10 nm (Figure 1) were prepared by a chemical coprecipita-
tion method [11]. These Fe3 O4 nanoparticles were subse-
2.3. Preparation of Magnetite/Silica (Fe3 O4 /SiO2 ) Core-Shell quently used as seeds for coating of SiO2 shell.
Nanoparticles. A modified Stöber method was used to coat Fe3 O4 nanoparticles were being encapsulated within
Fe3 O4 nanoparticles with SiO2 shell [9]. About 30 mg of the SiO2 shells upon the hydrolysis and condensation of
freshly prepared Fe3 O4 nanoparticles were dispersed in a TEOS as new bonds of Fe–O–Si were formed between the
mixture of 30 mL of ethanol and 6 mL water as seeds. interface of Fe3 O4 and TEOS. Ultrasonication was used
Journal of Nanomaterials 3
Fe3 O4
SiO2
100 nm 50 nm
(a) (b)
Figure 2: TEM micrographs of (a) Fe3 O4 /SiO2 nanoparticles prepared by sonication; inset shows an individual Fe3 O4 /SiO2 nanoparticles
and (b) Fe3 O4 /SiO2 nanoparticles prepared by the stirring method.
to accelerate the hydrolysis of TEOS. This was followed study, no surfactant was necessary during the formation
by lateral polymerization, and the formation of a three- of Fe3 O4 /SiO2 nanoparticles. Stjerndahl et al. reported that
dimensional network via siloxane formation (Si–O–Si), to Triton-100 was used in the emulsion method for preparing
produce a homogenous SiO2 coating [4]. TEM micrographs Fe3 O4 /SiO2 core-shell nanoparticles [14]. Kobayashi et al.
as shown in Figure 2(a) show that Fe3 O4 nanoparticles were also reported on the need to modify the surfaces of
fully encapsulated within the SiO2 shell using the sonication Fe3 O4 nanoparticles with silane coupling agent before the
method. The mean diameters of Fe3 O4 /SiO2 core-shell preparation of Fe3 O4 /SiO2 nanoparticles [15].
nanoparticles were observed to be approximately 120 nm.
Fe3 O4 nanoparticles were observed to have dispersed 3.2. Preparation of Fe3 O4 /SiO2 /TiO2 Core-Shell Nanopar-
uniformly within the SiO2 matrix. However, Fe3 O4 /SiO2 ticles. TiO2 was deposited on SiO2 nanoparticles by the
hydrolysis of TIPP precursor. Figure 3(a) shows the TEM
core-shell nanoparticles obtained in this study were not
micrograph of SiO2 /TiO2 nanoparticles without inclusion of
spherical in shape after the inclusion of Fe3 O4 nanoparticles.
Fe3 O4 nanoparticles. All of these SiO2 /TiO2 nanoparticles
This could be due to the dispersing status of magnetic were spherical in shape with rough surfaces. The direct
nanoparticles which was related to their surface charge den- coating of TiO2 onto surfaces of Fe3 O4 /SiO2 nanoparticles
sity and in turn directed the formation of Fe3 O4 /SiO2 core- resulted in the formation of core-shell type structures with
shell nanoparticles of various morphologies and structures Fe3 O4 nanoparticles being the cores and SiO2 and TiO2 are
[12]. the shells (Figure 3(b)). The EDX spectrum as shown in
Besides the sonication method, the stirring method was Figure 3(c) revealed the presence of four types of elements
also being used for coating Fe3 O4 nanoparticles with SiO2 (Si, Fe, O, and Ti). This suggested that TiO2 was being
shell. However, this approach had failed to encapsulate all coated onto the surfaces of Fe3 O4 /SiO2 nanoparticles. On
the Fe3 O4 nanoparticles within the SiO2 shells, as shown in the basis of the above analysis and observations from TEM
Figure 2(b). This shows that sonication is an effective way images, we could conclude that a thin layer of TiO2 layer
for rapid coating of Fe3 O4 nanoparticles core with the SiO2 of approximately 20–30 nm in thickness had been coated
shells. Besides, the high speed of coating by the sonication onto the surfaces of Fe3 O4 /SiO2 nanoparticles (Figure 3(b)).
method had prevented the oxidation and aggregation of The overall mean diameters of Fe2 O3 /SiO2 /TiO2 core-shell
Fe3 O4 nanoparticles. Fe3 O4 /SiO2 core-shell nanoparticles nanoparticles were approximately 140 nm.
prepared in this study were more discrete and uniform in Figure 4 shows the XRD pattern of Fe2 O3 /SiO2 /TiO2
size as compared to that reported by Morel et al. who core-shell nanoparticles after calcination at 450◦ C in air.
had also used the sonication method for coating Fe3 O4 The broad peaks were characteristic of the SiO2 matrix
nanoparticles with SiO2 shell [5]. Deng et al. had reported [15]. The XRD patterns also demonstrated that the appar-
on the effect of reaction parameters such as the types of ently amorphous nature of TiO2 coated on the surface of
alcohol, the volume ratio of alcohol to water, the amount of Fe2 O3 /SiO2 nanoparticles. In this case, the anatase phase
catalyst, and the amount of precursor on the formation of of TiO2 could have been formed after heat treatment at
Fe3 O4 /SiO2 nanoparticles [13]. Although they were able to 450◦ C for 3 hours [3, 8]. The BET specific surface area
prepare nanoparticles of spherical shape, their preparation of Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles prepared in
method was lengthy and required 12 hours of stirring. In this this study was 138 m2 /g, and this value was substantially
Fe3 O4
SiO2 TiO2
50 nm 50 nm
(a) (b)
002
6000
SiKa
5500
5000
OKa
4500
4000
3500
Counts
TiKa
3000
TiLl TiLa
2500
FeLl FeLa
2000
CKa
TiKb
FeKesc
1500
FeKa
FeKb
1000
500
0
0 0.8 1.6 2.4 3.2 4 4.8 5.6 6.4 7.2
(keV)
(c)
Figure 3: TEM micrograph of (a) SiO2 /TiO2 nanoparticles, (b) Fe3 O4 /SiO2 /TiO2 nanoparticles, and (c) EDX spectra of Fe3 O4 /SiO2 /TiO2
core-shell nanoparticles.
higher than that of Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles 22

reported by Gad-Allah et al. at 21–54 m2 /g [4]. 20
18
Figure 5 presents a photograph of the Fe3 O4 /SiO2 /TiO2 16
aqueous dispersion before and after a magnet was being 14
Lin (Cps)
attached to the outside of the sample vial. Fe3 O4 /SiO2 /TiO2 12

core-shell nanoparticles were observed to be attracted to the 10
magnet being attached outside of the sample vial. The result 8
indicated that even after coating of both SiO2 and TiO2 6
4
layers unto Fe3 O4 nanoparticles, their magnetic property had
2
remained intact. As such, these Fe3 O4 /SiO2 /TiO2 core-shell 0
nanoparticles could be easily recovered after their application 5 10 20 30 40 50 60 70 80 90
in the aqueous medium. 2θscale
3.3. Photocatalytic Properties of Fe3 O4 /SiO2 /TiO2 Core-Shell Silica

Magnetite
Nanoparticles. Figure 6 shows the degradation of MB dye
Anatase
with and without Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles
added at various duration with and without UV irradi- Figure 4: XRD pattern of Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles
ation. It was observed that without UV irradiation, the after being calcined at 450◦ C in air.
Journal of Nanomaterials 5
1.4 (a)
(b)
(c)
1.2 (d)
1
(e)
Absorbance
0.8
0.6 (f)
Magnet
0.4
0.2
(a) (b) 0
500 550 600 650 700 750 800
Figure 5: Photographs of a vial containing (a) Fe3 O4 /SiO2 /TiO2 Wave number (nm)
core-shell aqueous dispersion and (b) when a magnet was attached
Figure 7: Absorption of MB dye solution (10−5 M, 20 mL), (a)
to the outside of the sample vial.
alone, no UV irradiation, (b) alone, UV irradiation, (c) with
Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles (5 mg) added, no UV
irradiation, (30 mg) (d) Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles
1 (30 mg) added, no UV irradiation, (e) with Fe3 O4 /SiO2 /TiO2
core-shell nanoparticles (5 mg) added, UV irradiation, and (f)
0.9 with Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles (30 mg) added, UV
irradiation.
Methylene blue (C/Co )
0.8
0.7
of Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles. The intensity
0.6
of absorption of MB dye had remained the same without UV
0.5 irradiation.
0.4 4. Conclusion
0 200 400 600 800 1000 1200 1400
Time (minutes) In this study, a simple and facile synthesis approach was
developed for the preparation of a magnetically separable
a c photocatalyst consisting of an Fe3 O4 core, an SiO2 inter-
b d mediate layer, and a photocatalytically active TiO2 shell.
This synthesis method was rapid and did not require the
Figure 6: Changes in concentration of MB dye (a) alone, no UV
addition of any surfactant to direct the formation of SiO2
irradiation, (b) alone, UV irradiation, (c) with Fe3 O4 /SiO2 /TiO2
core-shell nanoparticles, no UV Irradiation, and (d) with Fe3 O4 / or TiO2 shells. The photocatalytic activity of TiO2 surface
SiO2 /TiO2 core-shell nanoparticles, UV irradiation. shell was not affected by the intermediate SiO2 layer and
Fe3 O4 core. The Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles
possessed high specific surface area of 138 m2 /g and exhibited
a good photocatalytic activity for the photodegradation of
concentration of MB dye alone remained almost con- MB dye in aqueous solution.
stant after 24 hours. However, its concentration decreased
by about 20% with UV irradiation. The degradation of Acknowledgment
MB dye was substantially enhanced by the addition of
Fe3 O4 /SiO2 /TiO2 core-shell nanoparticles with its concen- This work was supported in part by the Universiti Malaysia
tration being degraded by up to 70% with UV irradiation Sarawak under the special fundamental research Grant
(Figure 6(d)). We can therefore conclude that the degrada- 01(K03)/557/2005(56).
tion of MB dye was attributed to the photocatalytic activities
of the TiO2 layer on the core-shell nanoparticles. References
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Curso: Ingeniería de

Facultad de Ingeniería, UABC

Profesor: Franklin Muñoz-Muñoz

 Ofrecer las herramientas para aprender a presentar

Que son las propiedades?

Que son las aplicaciones?

Por un lado se considera a la ciencia de materiales como la sub-rama que

En contraste, en el otro extremo se considera a la ingeniería en materiales

El fin del científico es desarrollar o sintetizar nuevos materiales.

El fin del ingeniero es crear nuevos productos o sistemas usando los

Síntesis, propiedades y aplicaciones de nanomateriales

El científico busca que estructura y que composición nos llevan a

Sin embargo todos dependen de la misma raíz: el procesamiento.

Por lo tanto, quienes trabajen en el área de materiales

R. Una propiedad es la respuesta del material a un estimulo especifico.

Por ejemplo, la reflectividad (la capacidad de reflejar luz) es una propiedad de

El estimulo en este caso es la incidencia de luz.

La superconductividad es una propiedad a conducir corriente con cero

Importante: Una propiedad queda definida por el tipo y magnitud de la

En breve, la estructura de un material refiere al arreglo de sus componentes

•La estructura atómica es la organización de átomos o moléculas relativa a

•La estructura que puede ser discernida a simple vista se denomina

Nota: No siempre la estructura refiere a arreglos cristalinos!

Sin embargo es también posible hablar de propiedades subjetivas (solo

Albrecht Durer : Adan y eva. Museo Del Prado

Hoy son necesarios engranes de transmisiones,

En muchos de estos dispositivos el diseño requerirá

Es común que los ingenieros civiles, mecánicos,

Metales.- Muchos electrones no localizados. Ejemplos, aluminio, acero,

Un decimo de micra= 1E-7 m = 100 nm

En una propiedad en particular adquiere relevancia el carácter discreto de

Sugerencia: Usar el siguiente texto

Nanotecnology: The Future is Coming Sooner Than You Think

Composición elemental de la corteza terrestre (hasta 1000 m de profundidad).

El modelo de la oferta y la demanda describe la interacción en el mercado de

Este modelo predice que, en un mercado libre y competitivo, el precio se

El aumento en el precio del cobre (a) esta relacionado en la disminución

Las variaciones de corto periodo son relacionadas

“La actual concentración de minerales de cobre es aproximadamente un

El consumo de polímeros crece aproximadamente 5% por año. Se duplica

Moraleja, las tasas de consumo también son variables, lo que hace

Aproximadamente el 20 % de las importaciones de una país son en materiales

•El tamaño de la reserva

•La energía ($) necesaria para extraerlo y procesarlo.

La reserva son los depósitos conocidos que pueden ser extraídos

El recurso (reserva potencial) incluye la actual reserva. Pero también

Económicamente Incrementar la tecnología minera

La reserva potencial es como el potencial de dinero que podríamos ganar

Diseños eficientes. Usar solo la cantidad necesaria del recurso escaso.

Sustitución. Es la propiedad –no el material en si mismo- lo que el

Reciclaje. Aunque costosa, el reciclaje es la solución a varios problemas,

Sin embargo ahora vemos que también poseen propiedades económicas.

El riego del empleo de materiales peligrosos ocurre durante el transporte,

Formas comunes de materiales peligrosos son los explosivos, los venenos,

2.1 Gases inflamables. Incluyen generalmente a hidrocarburos procedentes de la

2.2 Gases no inflamables, no venenosos y no corrosivos. Son gases que no se

4.2 Sustancias que pueden presentar combustión espontánea. Son espontáneamente

Por ejemplo, el uso de carbono y nitrógeno en ciertas circunstancias

Esto no es raro en el uso de los acetonitrilos.

R.- Desgraciadamente cuando lo vemos en las noticias.

A massive explosion and fire occurred at an agricultural chemical packaging facility in

Es un error del diseñador de materiales hacerlo solo

Facultad de Ingeniería, UABC