SUDSOE project E-Learning Course

Physical and Chemical Synthesis Methods

of Nanomaterials

Abdusalam Uheida
salam@kth.se
l
kh
Royal Institute of Technology
Technology--KTH
Functional Materials (FNM)
November, 2013

Lecture 2

Nanomaterials Synthesis and Processing

Nanoparticles Synthesis Techniques

Gas-Phase Methods

Vapor Evaporation/Condensation

Chemical Vapor deposition

Laser Ablation
Chemical Methods

P
Precipitations

Micro-emulsion Synthesis

Sol ggel synthesis

y

Spray Drying / Spray Pyrolysis

Thermal Decomposition
Mechanical Deformation

Mechanical alloying
y g

Chemo-mechanical alloying

Severe mechanical deformation

Gas Phase Synthesis of Nanoparticles

Chemical Vapor Deposition (CVD)

Flame Assisted Ultrasonic Spray Pyrolysis & Gas Condensation

Processing (GPC)

Gas Phase Synthesis

Processes for Producing Ultrafine Powders:

Mechanical Grinding

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Ch i l Solution
Chemical
S l ti Methods
M th d for
f Nanoparticles
N
ti l synthesis
th i
Precipitation

Condensation

Evaporation

Templates

Others

Homogenousprecipitation
Coprecipitation
Hydrolysis
Hydrolysis
Oxidativehydrolysis
Reductiveprecipitation
Electrochemical reduction
Electrochemicalreduction
Solgeltechnique
Macromolecularchemistry
Spraydrying
Spraypyrolysis
Free e dr ing
Freezedrying
Aerosoltechnique
Precipitationinmicroemulsion
Precipitationinpresenceofsurfactants
Sonochemicalreactions

11

Wet Chemical S
Synthesis
nthesis of Nanomaterials

Schematic representation of sol-gel process of synthesis of nanomaterials

12

SolS l-Gel
Sol
G l Process
P
and
d Liquid
Li id S
Solid
lid Reactions
R
i

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Chemical Precipitation /Co/Co-precipitation

Formationofinsolublecompound(s)foroneormoreconstituentnanoparticles
Severalprecipitationagentscanbeused(OH,Oxalate,carbonate,..
Aprecursorcanbeformedfirstthenprocessedtotherequirenanoparticles
A
b f
d fi t th
d t th
i
ti l
needed

Me+OxalateMetaloxalate(S)HeattreatmentOxide
Chemicalgrinding
h i l i di
Canbecarriedoutinaqueousnonaqueoussolutionsoramixture
Can be carried out in aqueous nonaqueous solutions or a mixture
Needtoavoidparticlegrowth
Needtoavoidagglomeration=>Gooddispersion

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S
Superparamagnetic
ti Iron
I
O
Oxide
id
Nanoparticles (SPION)

Co precipitation method
Co-precipitation

Thermal Decomposition of
Iron Precursor Method

15

Solubility Product Constants, Ksp

16

Chemical Precipitation /Co/Co-precipitation

Canbecarriedoutin
aqueousnonaqueous
q
q
solutionsoramixture
Needtoavoidparticle
N d
id
i l
growth
Needtoavoidagglomeration
=> Gooddispersion
Useofsurfactants

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Chemical Precipitation /Co/Co-precipitation

G
Governing
i factors
f t
for
f growth
th off nanostructures
t t

Kinetics of nucleation and growth

Concentration of the stabilizing agent
Structure of the stabilizing agent
pH
H off the
h medium
di
Temperature

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Sol--Gel S
Sol
Synthesis
nthesis

19

Sol--Gel S
Sol
Synthesis
nthesis

20

Sol--gel Reactions
Sol

21

Sol--gel Synthesized Materials

Sol

22

Microemulsion Synthesis
Definition of microemulsion
---coined by J. H. Schulman in 1959

Components: surfactant, water, organic phase;

Thermodynamics: stable, even when centrifuge;
Size of droplets:10-100nm;
Optical character: transparent/subtransparent, isotropy.

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Microemulsion Synthesis

24

Microemulsion Synthesis
Survey from the Literature of Oxides Prepared from Microemulsions
SurveyfromtheLiteratureofOxidesPreparedfromMicroemulsions

25

Microemulsion Synthesis
Fe3O4 Core SiO2 ShellNanoparticles

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Microemulsion-- Shape Evolution

Microemulsion

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Microemulsion
Advantages of Microemulsion Technique
Metalparticlesarereduceddirectlyinmicroemulsionandcan
be used as a catalyst in suspension without further thermal
beusedasacatalystinsuspensionwithoutfurtherthermal
treatment.
Anarrowparticlesizedistributioncanbeobtained.
Theparticlesizecanbecontrolledtoagreatextent.
Bimetallicparticlescanbeobtainedatroomtemperature.
No effect of the s pport on the formation of the particles
Noeffectofthesupportontheformationoftheparticles.
Coreshellnanoparticlescanbeobtained.
Disadvantages of Microemulsion Technique
Amountofproductislimitedinabatchofmicroemulsion.
Recoveryandrecyclingoftheliquidphase.

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Self Assembly

Self Assembled Monolayers, SAMs

Surfactant Self Assembly

Polymer-Nanoparticle Self Assembly
Coacervate Formation

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Self Assembly
SAMs: Alkane thiolates on Gold

30

Self Assembly
Substrate and Ligand Pairs forming SAMsFirst

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Self Assembly
S f t tS
Surfactant
Self-Assembly
lf A
bl

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Fabrication of Complex Structures

33

Core--shell Processing
Core

34

Core--shell Processing
Core
Templated Gold-Magnetite
Gold Magnetite Nanoparticles
Filling sequence into gold hollow shell

35

Core--shell Processing
Core
Au shells-hollow spheres

36

Electrochemistry
Oxidation-Reduction
O
dat o
educt o Reactions
eact o s

37

Electrochemistry
Electrodeposited
ect odepos ted Nanowires
a o es

38

Reading Materials

Muhammet S.
S Toprak,
Toprak Gulaim A.
A Seienbaeva,
Seienbaeva Vadim G.
G
Kessler. Synthesis of Engineered Nanomaterials.