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JUSTIFICACIN
En la industria qumica, las cetonas y los aldehdos se utilizan como disolventes, como
sustancias iniciales y como reactivos para la sntesis de otros productos. A pesar de que el
formaldehdo se suele encontrar en solucin (formol), utilizado para preservar muestras
biolgicas, la mayora de los cuatro millones de toneladas de formaldehdo que se producen
cada ao se utilizan para la obtencin de Bakelita, resinas de fenol-formaldehdo,
pegamentos de urea-formaldehdo y otros productos polimricos.1
Los plsticos y resinas de fenol-formaldehdo (tambin denominados jlmlicos) tienen muchas
uniones cruzadas ya que cada anillo fenlico tiene tres posiciones (dos orto y una para) que
se pueden unir con el formaldehdo por condensacin.
La Bakelita puede moldearse a medida que se forma y endurece al solidificarse. No conduce
la electricidad, es resistente al agua y los solventes, pero fcilmente mecanizable. Su
permitividad dielctrica relativa es de 0,65. El alto grado de entrecruzamiento de la estructura
molecular de la baquelita le confiere la propiedad de ser un plstico termoestable: una vez
que se enfra no puede volver a ablandarse. Esto lo diferencia de los polmeros termoplsticos,
que pueden fundirse y moldearse varias veces, debido a que las cadenas pueden ser lineales
o ramificadas pero no presentan entrecruzamiento.
El brillo de la baquelita y el buen envejecimiento dan un aspecto inigualable a estas piezas
que cada da se revalorizan por su escasez y singularidad, con bonitas ptinas en sus ms
diversos colores y tonalidades.
Otro aspecto, nico, de la Baquelita es su olor caracterstico, debido al formaldehdo,
apreciable cuando la baquelita toma una cierta temperatura.
HISTORIA Y ANTECEDENTES
La Bakelita o baquelita fue uno de los primeros plsticos comerciales (una resina de
termofraguado) que se obtuvieron, llamada as en honor de su inventor, esta reaccin fue
descubierta en 1872 por L. Baekeland; un qumico americano nacido en Blgica.
Baekeland ha sido un claro ejemplo de lo que se podra denominar un cientfico- empresario,
pues utiliz los conocimientos cientficos a su alcance para inventar un producto de gran
utilidad social que le reporto grandes beneficios econmicos. La baquelita es solamente un
2
IMPORTANCIA Y USOS
Consecuentemente con sus propiedades la baquelita se convirti en un material alternativo al
vidrio, los metales y las maderas, pasando a constituir el principal material en elementos
decorativos y funcionales. Se introdujo con rapidez en su aplicacin a utensilios tradicionales
de la cocina y el menaje, pasando en muy poco tiempo a elementos habituales del hogar.
Las primeras aplicaciones de la baquelita fueron como aislante elctrico y ms tarde empez
a utilizarse en la construccin de accesorios plsticos para las industrias del automvil y de
la radio. Fue el precursor de gran cantidad de plsticos de tipo fenol- formaldehido. El propio
Baekeland registr ms de 400 patentes durante la investigacin y desarrollo de la baquelita.
Por sus propiedades como resina de termofraguado, se utiliza ampliamente en partes
moldeadas, adhesivos, recubrimientos e incluso en otras aplicaciones resistentes a alta
temperatura, como los conos de la nariz de los misiles.
Se usa en la fabricacin en grandes series de enchufes, tomas de corriente piezas de
aparatos, zcalos, etc. La adicin de colorantes apropiados permiten obtener efectos
artsticos.
PRODUCCIN
La baquelita, que fue el primer polmero completamente sinttico, se obtuvo por condensacin
escalonada de fenol y formaldehido.
Su sntesis se realiza a partir de molculas de fenol y formaldehdo (Proceso de Baekeland),
en proporcin 2 a 3. La baquelita presenta tres aspectos distintos que corresponden a tres
etapas de su fabricacin:
1.- El producto A es slido y tiene el aspecto de una resina amarillenta, se disuelve en el
alcohol. Funde bajo la accin del calor.
2.- El producto B procede de la accin del calor sobre el A cuando ste se lleva ms
all de la temperatura de fusin. Menos quebradizo que A, el producto B es slido a todas
las temperaturas e insoluble en todos los disolventes corrientes. El calor lo reblandece
dndole la consistencia del caucho, pero no produce nunca la fusin.
3.- El producto C resulta de la accin prolongada del calor o de polimerizacin del
producto B. Es el producto definitivo y el que posee las cualidades correctas. El cambio del
estado B al C puede coincidir con un moldeado, permitiendo obtener formas muy diversas
y realizar economas substanciales de mecanizado.
Reaccin General
Se sintetizo a partir de dos monmeros abundantes y baratos, el fenol y el formaldehido, que
pueden condensarse fcilmente en presencia de una base. La reaccin entre el ion fenxido
y el formaldehido es semejante a la reaccin de Kolbe de carboxilacin del fenol para dar
cido saliclico.
Pasos:
La reaccin se lleva a cabo por etapas: el formaldehido se adiciona en primer trmino a las
posiciones 2 y 4 de la molcula de fenol.
Condiciones de reaccin.
La condensacin del fenol con formaldehdo es semejante a la condensacin del fenol con
acetona.1
La polimerizacin se lleva a cabo en varias etapas, siendo uno de los intermedios una
resina termoplstica que se reblandece al calentarla. Este material puede moldearse de
la manera adecuada y se somete posteriormente a temperaturas y presiones elevadas
hasta que se convierte en una resina termoestable- material rgido insensible a los cambios
de temperatura debido a su estructura entrecruzada.
Mecanismo de reaccin.
El formaldehdo sirve de puente entre molculas de fenol, perdiendo su oxgeno por sufrir dos
condensaciones sucesivas, mientras que las molculas de fenol pierden dos o tres de sus
tomos de hidrgeno, en orto y para, de forma que cada formaldehdo conecta con dos
fenoles, y cada fenol con dos o tres formaldehdos, dando lugar a entrecruzamientos. En
exceso de fenol, la misma reaccin de condensacin da lugar a polmeros lineales en los que
cada fenol slo conecta con dos formaldehdos.
Produccin industrial
En ELECTROPARTES DE INDUCCION S. DE R.L. tienen el siguiente proceso de fabricacin
de baquelita en placa y en tubos.
El proceso de fabricacin del Celoron y de la Baquelita es muy semejante, y tiene dos grandes
divisiones, el proceso de fabricacin de placas y el proceso de fabricacin de tubos. Ambos
procesos se realizan en ambientes controlados y con materia prima especial para
aplicaciones elctricas.
continuacin
se
describe
cada
uno
de
los
procesos:
2.
3.
Una vez impregnado para el estrato a travs de un horno de precurado para que la resina
empiece su proceso de curado, dejando el material en un estado semipegajoso conocido
como etapa B.
4.
5.
Las hojas son alimentadas en la prensa de compresin final, donde se apilaran un nmero de
hojas relacionado a cada espesor a fabricar.
6.
7.
DE
FABRICACION
1.
DE
TUBOS
El papel
algodn
es
desenrollado de
manera
continua en la tina
3.
Una vez impregnado para el estrato a travs de un horno de precurado para que la resina
empiece su proceso de curado, dejando el material en un estado semipegajoso conocido
como etapa B.
4.
5.
6.
El material entra en una serie de rodillos tensores y posteriormente es rolado sobre un mandril
de dimetro exterior igual al dimetro interior del tubo a fabricar.
7.
8.
9.
En caso de ser requerido, los tubos se rectifican en su dimetro exterior para alcanzar las
especificaciones de cada cliente.
PROPIEDADES DE LA BAQUELITA
Este polmero presenta una estructura del tipo reticular a base de uniones covalentes, con
entrelazamiento transversal de cadenas producido por el calor o por una combinacin de calor
y presin durante la reaccin de polimerizacin.
A menudo, los polmeros termoestables se obtienen en forma de dos resinas. Una contiene
los agentes de curado, endurecedores y plastificantes, la otra materiales de relleno y/o
reforzantes, estos agentes reforzantes pueden ser orgnicos o inorgnicos.
En general, las ventajas de los plsticos termoestables como la baquelita puede tener algunas
aplicaciones dentro del campo de la ingeniera los cuales son:
1.
2.
3.
4.
5.
6.
Los usos ms extendidos de la baquelita son: compuestos de uso general con cargas que
aumentan su resistencia al impacto desde harinas de madera a celulosa con fibra de vidrio;
compuestos de aislamiento de electricidad, con crgas del tipo mica para aumentar
resistencias elctrica y compuestos resistentes al calor de 150 a 180C.
Tambin se usa en dispositivos de instalacin e interruptores elctricos, conectores, rels
telefnicos, en el sector de automocin como adhesivos y en las arenas de moldeo de
metales.
Propiedades fsicas y toxicolgicas de las materias primas y productos Fenol:
Propiedades fsicas y qumicas bsicas
Aspecto
Forma: slido
pH
6.0
Punto de fusin/ punto de
Punto/intervalo de fusin: 40 - 43 C (104 - 109
congelacin
F) - lit.
Punto inicial de ebullicin e 182 C (360 F) - lit.
intervalo de ebullicin
Punto de inflamacin
79.0 C (174.2 F) - copa cerrada
Inflamabilidad superior/inferior Lmites superior de explosividad: 8.6 %(V) Lmites
o lmites explosivos
inferior de explosividad: 1.7 %(V)
Presin de vapor
6.3 hPa (4.7 mmHg) a 55.0 C (131.0 F) 0.5
hPa (0.4 mmHg) a 20.0 C (68.0 F)
Solubilidad en agua
84 g/L a 20 C (68 F)
Coeficiente de
reparto
log Pow: 1.46
noctanol/agua
Temperatura
de 715.0 C (1,319.0 F)
autoinflamacin
Tensin superficial
38.2 mN/m a 50.0 C (122.0 F)
Informacin toxicolgica:
Solubilidad en agua
totalmente soluble
Coeficiente de
reparto
octanol/agua
Densidad relativa del vapor
Informacin toxicolgica:
Sensibilizacin respiratoria o cutnea: Posibilidad de sensibilizacin en contacto con la
piel.
Carcinogenicidad: Carcingeno regulado especficamente por OSHA
Contiene metanol. Puede ser mortal o causa de ceguera en caso de ingestin. No
puede neutralizarse
Baquelita:
Propiedades fsicas y qumicas bsicas
10
Estado fsico
Apariencia y olor
Concentracin
Peligros de fuego o explosin
Densidad a 20 C
Solubilidad en agua y otros disolventes
Resistencia a la flexin
Resistencia a la traccin
Resistencia a la compresin
Informacin toxicolgica:
Toxicidad a corto plazo: no hay
Toxicidad a largo plazo: no existe
Efectos locales o sistmicos: irritacin local leve
Sensibilizacin alrgica: no debera producirse
Propiedades del producto: pticas, magnticas, tribolgicas, biodegradables Baquelita:
La baquelita es una resina sinttica a base de fenol y de formol. Rene un conjunto de
ventajas difciles de encontrar en otras materias:
Resistividad de 6 millones de M/cm/cm2, gran rigidez dielctrica, resistencia al ataque de
los cidos, del oxgeno y del ozono, resistencia mecnica elevada, opacidad a los rayos X,
excelentes propiedades elctricas de los laminados fenlicos, ayuda a las aplicaciones tanto
la industria elctrica como la industria qumica
No conduce la electricidad, es resistente al agua y los solventes. El alto grado de
entrecruzamiento de la estructura molecular de la baquelita le confiere la propiedad de ser un
plstico termoestable: una vez que se enfra no puede volver a ablandarse.
La baquelita en realidad es un copolmero. A diferencia de los homopolmeros, que estn
formados por unidades monomricas idnticas (por ejemplo, el polietileno), los copolmeros
estn constituidos, al menos, por dos monmeros diferentes.
11
12
mejor a nuestras necesidades aplicando los conocimientos que hemos adquirido y de esa
forma hacer nuestro trabajo eficiente y de manera apropiada.
3.- Los polmeros constituyen la mayor parte de las cosas que nos rodean, estamos en
contacto con ellos todos los das e incluso nosotros mismos estamos compuestos casi en
nuestra totalidad de estas, tan variadas macromolculas.
Nuestro pas tiene una importante oportunidad de convertirse en proveedor, con ganancias
superiores a las que deja la exportacin de petrleo, ya que podran alcanzarse mayores
ingresos por barril, una vez transformado el crudo en productos plsticos, la industria del
plstico en nuestro pas se ubica principalmente en el rea metropolitana y en los estados de
Mxico, Jalisco, Nuevo Len y Guanajuato, pero se puede ampliar a otras zonas.
4.- Hoy en da los polmeros constituyen gran parte de nuestras vidas ya que absolutamente
todo es polmero desde la ropa que nos ponemos hasta los envases para los alimentos,
lamentablemente estos polmeros no se degradan tan rpido como quisiramos y tambin
gracias a nuestras irresponsabilidades hemos contaminado el medio ambiente ms de lo que
creamos y ahora debemos de tener una mayor conciencia para seguir aprovechando estos
materiales para el bien del hombre y no como material contaminante y saber reciclar cada
polmero nos hara menos contaminantes.
Anexos
Artculos cientficos
Govt. Research Centre, Sahyadri College of Engineering & Management, Adyar, Mangalore
575 007, India
E-mail: cr@physics.uni-mysore.ac.in:crang1@rediffmail.com
Abstract. In order to explore the structural modification induced electrical conductivity, samples of Bakelite
RPC polymer detector materials were exposed to 8 MeV of electron beam with the irradiation dose from 20
kGy to100 kGy in steps of 20 kGy. The microstructural changes upon electron beam irradiation have been
studied using Positron Annihilation Lifetime Spectroscopy (PALS) and Fourier Transform Infrared (FTIR)
Spectroscopy. Positron lifetime parameters viz., o-Ps lifetime and its intensity show chain scission at lower
doses (20 kGy, 40 kGy) followed by cross-linking beyond 40 kGy due to the radical reactions. The reduction in
electrical conductivity of Bakelite material beyond 60 kGy is correlated to the conducting pathways and crosslinks in the polymer matrix. The appropriate doses of electron beam irradiation of Bakelite material may reduce
the leakage current and hence improves the performance of the detector.
13
1. Introduction
Resistive plate chambers (RPCs) [1] have found extensive applications in high energy and astrophysics
experiments as the active detectors for muon detection. The RPCs made up of high resistive materials like
Bakelite and glass are being used as the detectors for iron calorimeter (ICAL) to study atmospheric neutrinos in
the proposed India based neutrino observatory (INO) project in India [2]. As the RPC detectors are continuously
exposed to charged particles like cosmic ray muons, there will be some modification in the microstructure of
RPC material in the long run. The vital problem faced in such experiments is that Bakelite RPCs exhibit
undesirable high leakage current compared to the glass RPCs [3]. However, Bakelite has several advantages
over glass detector material like low cost, easy to handle in the fabrication of RPCs and as such it is very
important to understand the origin of this leakage current. This problem has not been rectified in the past and
it is interesting to find whether the high leakage current owes its origin to the microstructural changes of the
Bakelite material upon exposure to charged radiation. In recent years, irradiation is treated as an effective tool
for structural modification of polymers and plays a significant role in the material modifications. In the present
study, authors carried out experimental investigations on the effects of electron beam irradiation on the
microstructure of the polymer based Bakelite RPC detector material by one of the well established techniques
viz., Positron Annihilation Lifetime Spectroscopy (PALS) [4] and an attempt has been made to correlate the free
volume change due to the electron beam irradiation on the electrical conductivity.
2. Experimental
Content from this work may be used under the terms of theCreativeCommonsAttribution 3.0 licence. Any further distribution of this work must maintain
attribution to the author(s) and the title of the work, journal citation and DOI.
Published under licence by IOP Publishing Ltd
1
Bakelite samples (P-120, Matt finished NEMA LI-1989, Grade XXX) of density 1.22 g/cm3, manufactured by
Bakelite Hylam, India were procured from VECC Kolkata (INO-Lab), India. The chemical structure of Bakelite is
shown in figure 1. The pairs of rectangular samples having dimensions 1 cm x 1 cm x 0.175 cm were exposed
to the electron beam of energy 8 MeV in air at Microtron Centre, Mangalore University, India, for different
doses up to 100 kGy in the interval of 20 kGy. These samples were used for PALS, electrical conductivity and
FTIR measurements.
14
free
15
This may further leads to the formation of OH- and H+ ions [12, 13]. The decrease in % of transmittance of O-H
group at higher electron doses suggests the cross linking of polymeric chains of Bakelite. This is possibly due to
the formation of hydrogen bonds by the radicals released during the scission of phenolic groups [11, 14]. The
absorbance band at 1053 cm-1 corresponding to single bond C-O stretching vibrations of -CH2OH- group shifted
to 1036 cm-1 at 20 kGy and then increases to 1055 cm-1 and remains at 1055 cm-1 for higher dosages. These
results indicate that the chemical changes due to the rearrangement of free radicals after the chain cleavage
seems to contribute to the microstructural modifications in the Bakelite sample. These results agree well with
the PALS results.
Acknowledgement
The authors are grateful to DST, Govt of India for sanctioning the INO-DST Project to UOM, Mysore.
16
References
[1] Santonico R and Cardarelli R 1981 Nucl. Instr. Meth. 187 377-380
[2] Biswas S, Bhattacharya S , Bose S, Chattopadhyay S, Saha S, Sharan M K and Viyogi Y P 2009
Instr. Meth. Phys. Res. Sect. A 602 749-753
Nucl.
[3] Carlson P, Crotty et al. 2001 Study and optimization of RPCs for high rate applications IEEE
Nuclear Sci. Symp. Medical imaging Conf. (USA, 4-10 November 2001) pp 1-17
[4] Shaojin J, Zhicheng Z, Yangmeib F, Huimingb W, Xianfengb Z, Rongdiana H 2002 Eur. Polym.
J. 38 2433
[5] Aneeshkumar K V, Ravikumar H B and Ranganathaiah C 2013 J. Appl. Polym. Sci.130 793-800 [6] Nakanishi
H, Wang S J and Jean Y C 1988 Microscopic surface tension studied by positron
annihilation, in: Sharma
S C (Ed.) Positron annihilation in fluids Singapore, World Scientific
pp 292- 93
[7] Tao S J 1972 J.Chem. Phys. 56 5499-5510
[8] Eldrup M, Lightbody D and Sherwood 1981 Chem. Phys. 63 51-58
[9] Ismayil, Ravindrachary V, Bhajantri R F, Praveena S D, Poojary B, Dutta D and Pujari P K 2010
Degrad.Stab. 95 1083-91
[10] Shariff G, Sathyanarayana P M, Thimmegowda M C and Ranganathaiah C 2002 Polymer.43 2819
[11] Lee Y, Kim D, Kim H J, Hwang T S and Rafailovich M 2003 J. Appl. Polym. Sci. 89 2589-96
[12] Loo J S C, Ooi C P and Boey F Y 2005 Biomaterials.26 1359-67
[13] Chen Y, Chen Z, Xiao S and Liu H 2008 Thermochim. Acta. 476 39-43
[14] Roczniak K, Biernacka T and Skarzynski M 1983 J. Appl. Polym. Sci. 28 531-542
[15] Va'vra J 2003 Nuclear Symp. Conf. Record 2003 IEEE. 5 3704-08
Polym.
[16] Siti A, Mohd N, Azizan A, Mohd Y A R and Ibrahim A T T 2010 J. Nat. Sci. 2 190
[17] Liu H, Hu X B, Wang J Y and Boughton R I 2002 Macromolecules.35 9414-19
Resumen del artculo cientfico Electron beam induced microstructiral changes and
electrical conductivity in bakelite polymer RPC detector material: A positron lifetime
study.
La baquelita es un material RPC que sirve como detector y que tiene grandes aplicaciones en
astrofsica ya que ayuda a detectar muones en el espacio y para estudiar los neutrinos
atmosfricos como este detector esta hecho de baquelita y se encuentra en constante
contacto con rayos csmicos necesitan una modificacin en su estructura, el principal
problema que enfrentan en estos experimentos es que baquelita RPC exhibe alta corriente
de fuga no deseable en comparacin con los RPC de vidrio.
Sin embargo, la baquelita tiene varias ventajas sobre el material detector de vidrio como de
bajo costo, fcil de manejar en la fabricacin de RPC y, como tal, es muy importante para
entender el origen de esta corriente de fuga. Este problema no se ha corregido en el pasado
y es interesante saber si la alta corriente de fuga debe su origen a los cambios
microestructurales del material de baquelita con la exposicin a la radiacin cargada. La
irradiacin se trata como una herramienta eficaz para la modificacin estructural de los
polmeros y juega un papel significativo en las modificaciones materiales.
Al momento de experimentar con la baquelita se puso en presencia de una una irradiacin de
electrones de hasta 40 kGy y el volumen neutro del polmero aumenta de 64.90 a 69.46m,
Esto se atribuye a la reticulacin de cadenas de polmero de baquelita debido a los radicales
formados por la escisin de las cadenas polimricas en las etapas iniciales de la irradiacin;
esto va a dificultar la movilidad de la cadena de polmero.
Las variaciones de intensidad o-Ps de 60 a 100 kGy se debe a la modificacin estructural de
la baquelita inducida por la escisin de la cadena seguido de la reticulacin de las cadenas
17
DOI: 10.1002/srin.201100104
Use of Waste Bakelite as a Raw Material Resource for Recarburization in Steelmaking Processes
Somyote Kongkarat1)*, Rita Khanna1), Pramod Koshy1), Paul OKane2), and Veena Sahajwalla1)
1)
Centre for Sustainable Materials Research and Technology, School of Materials Science and Engineering, The University of
New South Wales, Sydney, Australia
2)
18
wt%; these were generally higher than that observed from coke alone (0.1 wt%). The dissolution rate (K) was also found to improve and the observed
trend was BK2 (0.045 103 s1) > BK3 (0.023 103 s1) > BK1 (0.005 103 s1) > coke (0.003 103 s1). The reaction products formed at the interface after 30 minutes
of contact between liquid steel and bakelite/coke blends were observed to be a CaS-Al2O3 complex. The presence of CaS in the interfacial layer due to
the CaO in the ash, lowered melting temperature of the layer, thereby allowing for increased removal of the ash layer and greater carbon pick-up. The
CaO is formed from the decomposition of CaCO3, and its presence was found to have a positive effect on modifying the
properties of the coke, and thereby enhancing the carbon
onthedissolutionof carbon from both graphitic and
dissolution behaviour.
Keywords: Bakelite, Carbon dissolution, Steelmaking, Recycling
Introduction
The global demand for plastics has grown significantly
over the past few decades, with the worldwide
consumption
approaching100milliontonnesperyear,withthenumbe
rs rising further each year. In Australia, more than 1.5
million tonnes of plastics were consumed in 2009 [1].
Among these, a small fraction of waste plastics
(18.5%) were recycled; the majority of these recycled
plastics were thermoplastics such as polyethylene
(PE) and polyethylene terephthalate (PET).
Thermosets make up for only 0.4% of plastics that are
recycled1), and limited published research exists on
the recycling of thermosets. These polymers cannot
be remelted to form a new product, and are generally
landfilled or incinerated, both of which lead to
environmental problems. Bakelite is a thermosetting
amorphous polymer with a
3dimensional cross-linked network structure [2],
which gives it high hardness, rigidity and strength
along with good thermal and electrical insulating
properties. It is used for parts of automobiles,
electronic components and kitchenware, and is
formed from the thermosetting phenol formaldehyde
resin. Its chemical composition varies with the molar
19
(1)
(2)
SiOg C ! Si COg
(3)
Ash (wt%)
53.4
4.0
11.6
0.017
CaCO3
30.03
SiO2
SO3
0.91
0.06
20
Coke
BK1
BK2
BK3
SiO2
61.4
56.9
52.8
47.3
Al2O3
31.5
28.9
26.2
22.8
Fe2O3
2.0
2.3
2.3
2.2
CaO
0.55
5.40
10.80
18.30
P2O5
0.9
0.59
0.55
0.52
TiO2
1.0
1.00
0.90
0.77
MgO
0.16
0.61
1.00
1.70
K2O
0.29
0.36
0.33
0.35
Na2O
0.20
0.22
0.20
0.18
SO3
0.16
1.9
2.8
3.5
Mn3O4
0.04
0.07
0.08
0.13
Composition (wt%)
Fixed Carbon
Volatile
Coke
79.8
3.0
BK1
76.3
3.2
BK2
73.4
3.1
BK3
68.4
3.3
Ash
17.2
20.5
23.5
28.3
Sulphur
0.29
0.27
0.25
0.27
samples
21
ln
sCt
dCt Ak
CsCt dt V
K t (6) C
22
(5)
CsC0
(7)
23
30minutes) was observed to keep on increasing bakelite was significantly below the saturation level slowly with
the dissolution rate of 0.005103 s1. The of 5.28wt% at level of carbon pick-up from coke and its blends with
Figure 4. Images of liquid metal droplets while reacting with carbonaceous substrate at 1550 8C.
24
15508C; the longer reaction times may be required for the system to reach a state of thermodynamic
equilibrium.
The overall rate of carbon dissolution into liquid metal depends on types and properties of
carbonaceous materials. Khanna et al. [14] reported the overall carbon dissolution rate from a range
of chars into Fe-C melt at 15508C to be 0.08-0.64103 s1. Recently, the rate of carbon dissolution from
metallurgical cokes into Fe-C melt at 15508C determined using the sessile drop technique was
reported by Chametal.[28]tobe1.1103 s1 and14.7103 s1.In the present study, the coke used is a poor
carburizing material; high ash oxide content in the coke is expected to significantly affect the
carburization [7], especially the presence ofAl2O3,whichcomprised32wt%oftheashinthe coke
sample. The carbon dissolution from the coke occurred at a very slow rate. However, rate of carbon
dissolution was enhanced when bakelite/coke blends were used.
Sulphur Transfer from Coke and Bakelite/Coke Blends. Sulphur can transfer to the melt concurrently
with the dissolution of carbon. The variation in the amount of sulphur transferred to liquid steel
from coke and bakelite/
Region I
Region II
Coke
0.003
BK1
0.005
BK2
0.045
BK3
0.023
0.005
25
coke blends is shown in Fig. 7. Sulphur transfer from the coke into liquid steel stabilized to 0.05wt%
within a few minutes.ForblendsBK1 andBK2,asimilar trendofsulphur transfer was observed, with the
levelof sulphur picked up by the melt increasing from approximately 0.08wt% (after 2minutes of
contact) to 0.1wt% after 30minutes of contact. With further increase in the bakelite content (for
blend BK3) the overall sulphur pick-up was lower. Sulphur picked up stabilized to 0.06wt% after
30minutes of reaction. The decreased sulphur pick-up in the case of blend BK3 compared to the
other blends could be attributed to the greater desulphurization of the melt which could have
occurredduetotheCaOcontentbeingthehighestamongthe blends.
Formation of Interfacial Reaction Products. The volatile matter content in the bakelite/coke blends
was observed to be quite similar (3wt%) to that of coke (see Table 2). Thus, the effect of volatiles on
carbon dissolution was not considered in the present study. The blending of bakelite with coke
mainly resulted in a change in the chemical composition of the materials, and this influenced the
relative proportions of the ash oxide layer formed at the metal/carbon interface. SEM images of the
steel/carbon interface as well as the EDS analysis ofthe interfacial region in the case of coke are
shown in Fig. 8. It was found that the interface was predominantly covered by Al2O3 even after
4minutes of contact, as the coke used had high alumina content in the ash. Moreover, this ash layer
was observed to grow with time. The reduction of silica is one factor that can decrease the level of
solute carbon in the liquid metal by converting silica into silicon in the melt [18, 19]. This
correspondswiththeEDSspectrawhereaverysmallpeakof silica was detected even though it is the
major component of the coke ash. After 30minutes of reaction, the interface was also observed to
be covered by Al2O3.
The relative strength of the interfacial layer formed between the solid carbon and molten steel
depends on its fusion temperature which in turn depends on the chemistry of the layer [7, 17]. If the
melting point of the ash layer is lower than the liquid metal temperature, it could be easily removed
from the interface. This increases the contact area between the liquid metal and the solid carbon,
and thus enhances carbon dissolution. Orsten and Oeters [17] studied the influence of additives like
CaO on the carbon dissolution and found that the addition of CaO can reduce the ash melting
temperature. These authors concluded that the dissolution of coke was limited by the fusion
temperature of ash. Gudenau et al. [7] reported that the influence of ash on the interactions
26
Figure 7. Variation in the sulphur transfer from bakelite/coke blends into liquid steel at 1550 8C compared to coke.
of industrial and special cokes with liquid iron was an important factor in controlling the coke
dissolution. They suggested that phases that have lower fusion temperature than coke ash would
aid the carburizing of iron by allowing the ash to be removed from the interface. These authors [7]
also investigated the effect of additives and found that the addition of CaO, Al2O3, MgO and SiO2
decreased the dissolution of carbon, while Fe2O3 increased the dissolution. The differences in the
results of the two authors [7, 17] may be attributed to the experimental conditions and materials.
In the present study, a major component of the coke ash is SiO2 and Al2O3, while CaCO3 is the key ash
constituent in the case of bakelite. Therefore, the blending of bakelite with coke results in the
material having significant difference in ash chemistry compared to its parent coke. The thermal
27
Figure 8. SEM images of the metal/carbon interface for coke and the EDS spectra of the interfacial region.
decomposition of CaCO3 is shown by Eq.8, which can occur during the combustion of the blend in
the furnace, thereby increasing the CaO content in the blend. This will result in the Al2O3 content
decreasing proportionally (see Table 3). CaO would act as a fluxing agent and will reduce the ash
melting temperature [17], which in turn would increase the relative fluidity oftheash
layer.Thechange inthe properties of the ash layer would produce differences in carbon and sulphur
pick-up observed from bakelite/coke blends.
CaCO3s ! CaOs CO2g
(8)
From Table 3, only the relative contents of SiO2, Al2O3, CaO and MgO varied significantly across the
different blends compared to its parent coke. All the other ash components were low in content and
did not show any significant variations in the different blends. The high CaO in the bakelite/coke
blend can decrease the melting temperature of the reaction products formed at the metal/carbon
interface during reactions.
Toestimatetheproportionofthesolid/liquidcomponents of the interfacial products in the case of coke
and bakelite/ coke blends at 15508C, FactSage 6.0 [27], athermodynamic software, was used.23) The
percentage of the different reaction products formed and the proportions of the solid / liquid
components in these interfacial products were calculated using this software. The following
assumptions were made for the thermodynamic calculations:
1. OnlySiO2,Al2O3,CaOandMgOwereincludedastheash oxides in the calculation.
2. Fe2O3 was not included because it is assumed to be reduced under the experimental condition.
28
3. Sulphur was included in the calculations to assess itsinfluence on the reactions at the metal/carbon
interface.
4. Allthecomponentsoftheashareassumedtobedistributedhomogeneously throughout the sample.
Cham et al.[23] used FactSage to estimate the solid/liquid ratio of the reaction products formed at
the interface at temperatures of 15008C and 15508C in order to investigate
theinfluenceofthecontentandcompositionofashoxideson the carbon dissolution behaviour from
cokes. In their study, it was found that over 80% of reaction products formed at the interface was
liquid. These authors explained that the differences in the melting temperature and viscosity of the
interfacial product resulted in the differences in the carbon dissolution behaviour of the different
cokes. They also showed that the composition of ash oxides in the coke influences the viscosity of
the interfacial products and hence the kinetics of reaction between coke and iron.
In the present study, the estimated proportions of the solid and liquid components of the interfacial
products formed in the case of coke and bakelite/coke blends at 15508C as obtained from FactSage
6.0 are listed in Table 5. The estimated major constituents of the liquid and solid components are
shown in Tables 6 and 7.
The constituents of the liquid component were found to be SiO2, Al2O3, CaO, CaS and Mg2SiO4, while
the major
Table 5. Relative percentages of solid / liquid components of the interfacial products for bakelite/coke blends and coke at 1550 8C
(calculated using FactSage 6.0).
Carbonaceous
samples
Solid %
Liquid %
Coke
40
60
BK1
23
77
BK2
93
BK3
97
Table 6. Relative constituents in the liquid component of the interfacial products for bakelite/coke blends and coke at 1550 8C (calculated
using FactSage 6.0).
Liquid Constituents (%)
Carbonaceous
samples
SiO2
Coke
90.6
8.13
0.77
BK1
71.7
20.9
5.79
0.04
1.54
BK2
59.9
27.4
10.5
0.14
2.07
BK3
52.3
25.9
18.1
0.45
3.34
Al2O3
29
CaO
CaS
0.0007
Mg2SiO4
0.51
Table 7. Relative constituents in the solid component of the interfacial products for bakelite/coke blends and coke at 1550 8C (calculated
using FactSage 6.0).
Solid Constituents (%)
Carbonaceous
samples
3Al2O3.Si2O13 (Mullite)
CaS
Coke
99.6
0.4
BK1
92.2
7.8
BK2
63.7
36.3
BK3
100
constituent of the solid component was 3Al2O3.Si2O13 (mullite) and CaS. With increasing bakelite
content in the blend, the contents of SiO2 and Al2O3 in both the liquid and solid components of the
interfacial layer were found to decrease, while the contents of CaO and CaS increased expectedly.
The estimated results show that the presence of CaO and CaS atthe interfacecan lower themelting
temperature ofthe interfacial layer. As shown in Table 5, the interfacial reaction products in the case
of bakelite/coke blends were moreliquidcomparedtothecaseofcoke,andthepercentage of liquid
component increased with increasing bakelite content in the blend. The liquid oxide layer which is
readily removed from the interface can increase the metal/carbon contact area. These could explain
the greater carbon pick-up values in the case of bakelite/coke blends compared to coke alone. This
provides the evidence that the CaO generated from bakelite has a beneficial effect in decreasing the
ash fusion temperature of the materials, and this is in agreement with the results
30
Figure 9. SEM images of the metal/carbon interface for BK1 and the EDS spectra of points in the region.
from
literature [17].
The differences in the percentages of the solid/liquid components estimated using the FactSage 6.0
could explain the differences in carbon dissolution behaviour between the bakelite/coke blends and
coke alone. However, the formationofinterfacial products isinfluencedbythekineticsof the reaction
as the dissolution reactions continue, the interfaciallayerwillchange duetothedepositionofreaction
products. Once solid carbon is in contact with liquid iron, carbon and sulphur atoms will dissociate
from its host lattice into the interface and then dissolve into liquid iron. Ash oxides in the solid
carbon will also form a layer at the interface. In the case of bakelite/coke blends, the ash layer
formed is assumed to be composed of SiO2 - Al2O3 - CaO MgO. Once the carbon and sulphur atoms
transfer across the interface into the liquid metal, they will react with the mineral oxides in the
interfacial layer, and thus transfer reaction productsintothe interface.Theinterfacial reactions that
take place include desulphurization of liquid iron and reduction of silica. The CaO generated from
the bakelite can react with the dissolved carbon and sulphur atoms, and form CaS at the interface
as a reaction product. SiO2 can also be reduced by the dissolved carbon through both direct and
indirect reduction. The reduced Si is transferred into liquid iron. The final composition and
morphology of the interfacial layer is the result of the reactions which occur at the metal/carbon
interface.
The reaction products formed at the metal/carbon interface in the case of bakelite containing blends
were observed tobeacombination ofCaSandAl2O3.ForblendBK1, white regions representing mineral
oxides were observed at the interface after 4minutes of contact and these were predominantly
composed of CaS-Al2O3 mixture (Fig. 9). With ongoing dissolution, the composition of the ash layer
was found to change and become calcium enriched due to the formation of CaS complex. A
corresponding decrease in Al2O3 contents was seen from the interfacial images after 30minutes of
reaction. In the case of blend BK2 and BK3, the interfacial layer formed after 4 and 30minutes of
reaction was also found to be composed of CaS-Al2O3 mixture as shown in Fig. 10 and Fig. 11,
respectively.
By increasing the bakelite content in the blends, the presence of CaS at the interface was observed
to increase proportionally with the decrease in Al2O3 (see Figs. 9 to 11). The highest amount of CaS
formed at the interface was seen in the case of blend BK3. These results correspond to the
thermodynamic results obtained using FactSage 6.0 (Tables 6 and 7). This provides evidence that
the
greater desulphurization
of
the
melt hadoccurred in
the
case
of
BK3 comparedtothecaseofBK2andBK1andthuscouldexplain the lower sulphur pick-up in the
case of blend BK3 compared to BK2 and BK1.
The formation of CaS and Al2O3 phases at the iron/carbon interface have been reported previously
[19, 21]. Using the sessile drop technique, Wu et al. [19] investigated the iron/ natural graphite
31
Figure 10. SEM images of the metal/carbon interface for BK2 and the EDS spectra of the points in the region.
interface and found that although natural graphite contained 8.8wt% ash, with the majority being
SiO2 (72wt%), no SiO2 was observed at the interface. These authors also reported that Al2O3 was
observed at the interface initially, and as the reaction proceeded, the proportion of CaO increased
and Al2O3 decreased. Therefore, the interface was found to be replaced by Fe/ Ca/S complex
thereafter. They described the formation of the sulphide based complex as the effect of the
desulphurization of the iron droplet. However, the mechanisms related to the decrease in Al2O3 and
the increase in CaO was not provided. McCarthy et al.[21] studied the iron/coke interface and also
reported the formation of CaS complex at the interface. In the iron/coke system used in their study,
the dissolution of carbon from coke was limited with the carbon pick-up after 30minutes of contact
being approximately 0.1wt%. The low carbon dissolution was attributed to a combination of both
poor dissolution rate and carbon consumption by reducible oxides in the coke ash. These
authorsconcludedthattheproductionofsemifusedashatthe interface will reduce the interfacial area.
This occurred due to the selective removal of silica at the interface initially and the later removal of
CaO and its conversion into CaS [21].
The presence of Al2O3 (which is a non wetting compound with high melting point >20008C) would
hinder the liquid metalreactionwiththecokeinterface.Ontheotherhand,the presence of CaS and
Al2O3 mixture at the interface in the case of bakelite/coke blends would aid the dissolution of
carbonbyreducingthemeltingtemperatureoftheinterfacial
products.Themetal
droplets
whichreactedwithblendsBK2 and BK3 were found to show faster dissolution rate compared to coke,
and a similar trend of sulphur transfer compared to coke was seen in blend BK3. This suggests that
there is a potential for using bakelite/coke blends as a replacement of coke as a recarburizing
material.
32
Conclusions
An in-depth investigation has been conducted on the dissolution of carbon from bakelite/coke
blends into liquid steel at 15508C to examine the potential ofrecycling bakelite
asasourceofcarbonandlimeforrecarburizationprocessesin steelmaking. The major findings from this
study are:
1. Bakelite was partially blended with coke in a range ofproportions for carbon dissolution
experiments. The measured carbon pick up value after 30minutes of reaction for metallurgical
coke was approximately 0.10wt%, whereas it was 0.13, 0.16 and 0.17wt% for blends BK1, BK2 and
BK3 respectively. The overall carbon dissolution rate for coke was 0.003103 s1. A slightly faster
carbon dissolution rate was observed in the case of BK1 with the dissolution rate determined as
0.005103 s1. The fastest carbon dissolution was observed in the case of BK2 for a first few minutes
of reaction with the overall carbon dissolution rate constant (K) was 0.045103 s1. A similar trend
was seen in the case of BK3 with the overall carbon dissolution rate constant was 0.023103 s1. The
addition of bakelite generally enhanced the carbon dissolution kinetics;
Figure 11. SEM images of the metal/carbon interface for BK3 and the EDS spectra of points in the region.
the
carbon pick up was also seen to increase with increasing bakelite levels.
2. The presence of CaCO3 (present as a filler in the waste bakelite) was found to have a beneficial
effect on modifying the chemical properties of the carbonaceous substrate which in turn affected
the composition of the interfacial ash layer. The CaO arising from CaCO3 decomposition
participates in desulphurization reactions to form CaSat the interface.Moreover, itacts as afluxing
agenttolowertheashfusiontemperatureoftheinterfacial
33
RESUMEN
En el mundo la demanda de plsticos ha ido creciendo enormemente siendo el
consumo cerca de 100 millones de toneladas por ao, aumentando cada vez ms.
Un estudio en Australia mostro que cerca de 1,5 millones de toneladas de plsticos
se consumieron en el ao 2009 y solo un 18,5% fueron reciclados; la mayora de
34
35
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37