POWDER SYNTHESIS METHODS

POWDER SYNTHESIS METHODS

chemical methods
Desirable Powder Characteristics for 
Advanced Ceramics
d d i
Summary of the 
common 
powder 
preparation
methods for 
ceramics
CVD (Chemical vapour deposition)
Chemical vapor deposition techniques
use either gas
phase reactions or gaseous
decomposition as the source of
material.
CVD is often used to produce thicker
films (i.e., films >1 mm in thickness).
the growth rate by CVD is on the order
of microns per
minute (e.g., 2 mm/min),
PVD (Physical vapour deposition)
PVD techniques rely on excitation of a
solid
source (target), to produce the
necessary material for film formation.
Thinner films
for PVD techniques the growth rate is
often orders of magnitude lower
(growth rates in the range 0.01–0.03
mm/min
/ i are typical).
t i l)
 CVD Process
Chemical vapor deposition involves either:
• Chemically reacting a volatile compound of a material to be 
Chemically reacting a volatile compound of a material to be
deposited with other gases to produce a nonvolatile solid
• Pyrolysis (decomposition) of a compound at high temperature 
to produce a solid.
In either case, the solid forms as a film on a suitably placed 
substrate. 
substrate
• It is important that the reaction takes place only on the 
substrate surface.
• If the reaction takes place in the gas stream above the 
substrate, particulates form. Then, the film has a low density 
and a large number of voids
and a large number of voids.
Different geometries for a CVD reactor
CVD Process contd...

• The substrates placed on a graphite slab

which acts as a susceptor for radiofrequency
induction heating.
• The gases are introduced into the reactor
chamber sometimes in the presence of an
chamber,
inert carrier gas such as argon.
• The reacting compounds must exist in a
y reactive
volatile form and must be sufficiently
in the gas phase.
Formation of SiC film from silicon tetrachloride (SiCl4) 
and methane (CH4) 1400 C. o

SiCl4(g) + CH4(g) = SiC (s) + 4HCl (g)

Silicon tetrachloride is a liquid at RT, vaporizes (it boils) at 57.6oC -

transported to the reactor chamber.
chamber

High-purity Methane gas supplied directly from a gas cylinder.

.
T aspects
Two t off the
th temperature
t t are important.
i t t
▪ It must be sufficiently high that the reaction occurs.
▪ If an epitactic deposit is required, it must be high enough to allow the
condensing g species
p to diffuse across the crystal
y surface to find their
required lattice crystal positions.

• CVD is also used in composites.

• It is used to form SiC fibers by the reaction between CH3SiCl3
(Methyltrichlorosilane) and H2 on a tungsten wire.
• It is also used to form the matrix phase in a ceramic matrix composite
(CMC) by a process known as chemical-vapor infiltration.
• All of the electronic grade silicon (EGS) used in the fabrication of silicon
wafers is made by CVD. The highest-purity EGS is made by
decomposition of silane (SiH4),
 THERMODYNAMICS OF CVD
TiCl4(g) + CH4(g) = TiC (s) + 4HCl (g)

At 1200 K, the ∆Go for the individual reactions

The negative value of ∆Go

indicates that the reaction
proceeds spontaneously
at 1200 K to produce TiC.
 Ceramic films by CVD

A variety of oxide, carbide, nitride, and boride films and coatings can be
readily prepared by CVD techniques
Chemical Vapour Deposition (CVD)
Chemical Vapour Deposition (CVD)
Cutting tools with Titanium Nitride
Cutting tools with Titanium Nitride
• Tools heated in graphite tray to 950‐1050oC
• Titanium Tetra
Titanium Tetra‐Chloride
Chloride and Nitrogen are pumped 
and Nitrogen are pumped
into chamber
• Chemical reaction on surface of part deposits 
Chemical reaction on surface of part deposits
layer of Titanium Nitride
• For Titanium Carbide, Methane is second gas
, g
 CVD
Layer thickness from
nm to µm

Long process
 Chemical Vapor Deposition CVD
Chemical Vapor Deposition CVD
Reactantsg → Products
→ Productss
SiH4(g) +   N2O(g) →   SiO2(s) +   NH3(g)
• Low pressure LPCVD C
• Plasma enhanced: PECVD, PE‐LPCVD
• Temperature, pressure, flow, power
• Well understood system used extensively in 
Well understood system used extensively in
microelectronics

13
 Silane Reactions
Silane Reactions
Deposition

SiH4(g) + N2O(g) → SiO2(s) + NH3(g)

Hydrolosis
H3C
O CH3

O Si O
+ H2O → CH3OH +
H3C O
CH3

14
Silica

15
 POWDER SYNTHESIS BY CHEMICAL
METHODS FROM LIQUID SOLUTIONS
METHODS FROM LIQUID SOLUTIONS

1. Evaporation of the liquid
1 Evaporation of the liquid
2. Precipitation by adding a chemical reagent 
that reacts with the solution
that reacts with the solution
• Principle: random thermal fluctuations give 
rise to local fluctuations in density and free 
i l l fl i i d i df
energy of the system. Density fluctuations 
produce clusters of atoms referred to as 
d l f f d
embryos which grow by addition of atoms
Precipitation from Solution
•Two basic steps:
(1) nucleation of fine particles and 
(2) their growth by addition of 
th i th b dditi f
more material to the surfaces.
•Promote Homogeneous 
nucleation  and avoid 
l d d
heterogeneous nucleation
•Heterogeneous nucleation can be 
used to good advantage for the 
synthesis of coated particles
 Major Steps in Homogeneous nucleation
Major Steps in Homogeneous nucleation

• In
In aqueous solution metal ions are hydrated
aqueous solution metal ions are hydrated
• Embryos of hydrated metal ions form by 
progressive addition of ions to one another by a
progressive addition of ions to one another by a 
polymerization process
• These polynuclear
These polynuclear ions are the precursors to 
ions are the precursors to
nucleation.
• When the concentration of the polynuclear
When the concentration of the polynuclear ions 
ions
increases above some minimum supersaturation
concentration nucleation occurs
concentration, nucleation occurs
 Particle Growth by Solute Precipitation
• Growth
Growth by transport of solute species (ions or molecules) through 
by transport of solute species (ions or molecules) through
the solution to the particle surface, desolvation, and alignment on 
the particle surface.
• Two types of growth mechanism :
1. Diffusion towards the particle
Flux J through any spherical shell of radius x is given by

2. Addition of new material to the particle by a form of surface reaction
p y
• mononuclear growth: a nucleation step is formed on the particle 
surface, a layer has the time to achieve its completion before a new 
step appears. Growth proceeds layer by layer
• polynuclear growth: mechanism, formation of nucleation steps on 
the particle surface is fast enough to create a new layer before the 
previous one has been completed. Growth rate is independent of the 
surface area of the existing particles
surface area of the existing particles
Mononuclear growth and Polynuclear growth
 Controlled Particle Size Distribution
(LaMer diagram )
d )
(precipitation from solution by homogeneous nucleation and growth)

growth stops after a 
time t3 when Cx = Cs.

one short burst of 
nucleation should 
occur in a short time 
i
interval, t
l 2 ‐ t1 to get 
particles with a fairly 
uniform size

Use of a fairly low 
reactant 
concentration 
recommended
 LaMer diagram
• concentration of the solute to be precipitated, Cx
i f h l b i i d C
• Saturation value Cs
• critical supersaturation concentration , Css reached after some 
critical supersaturation concentration Css reached after some
time t1 provided solution is free of foreign inclusions and the 
container walls are clean and smooth
• homogeneous nucleation and growth of solute particles will 
occur, leading to a decrease in Cx to a value below Css after a 
time t2.
time t2.
• Further growth of the particles occurs by diffusion of solute 
through the liquid and precipitation on to the particle surfaces. 
Finally, particle growth stops after a time t3 when Cx = Cs.
• to produce particles with a fairly uniform size, then one short 
burst of nucleation should occur in a short time interval t2 ‐ t1.
burst of nucleation should occur in a short time interval, t2  t1
• uniform growth of the particles requires that the solute be 
released slowly
 Particle Growth by Aggregation
• HR
HR‐TEM show that the particles consist of aggregates of much 
TEM show that the particles consist of aggregates of much
finer primary particles
• Particle growth occurs by aggregation of fine particles rather 
than by diffusion of solute to existing particles
than by diffusion of solute to existing particles
• Barrier to aggregation increases with the size
• Fine particles aggregate more quickly with large particles than 
they do with themselves
• During a precipitation reaction, 
‐The
The first nuclei grow rapidly by aggregation to a colloidally
first nuclei grow rapidly by aggregation to a colloidally
stable size. 
‐These particles then sweep through the suspension, picking
up freshly formed nuclei and smaller aggregates.
f hl f d l i d ll t
‐The formation of particles with uniform size is thus achieved
through size‐dependent aggregation rates
g p gg g
 Particle Growth by Ostwald Ripening
(Lifshitz
Lifshitz‐Slyozov‐Wagner (LSW) theory)
Slyozov Wagner (LSW) theory

• Smaller particles/precipitates dissolve and the solute 
p /p p
precipitates on the larger particles (coarsening)
• Matter transport from the smaller particles to the 
l
larger particles can be controlled by 
ti l b t ll d b
(1) diffusion through the liquid or 
(2) an interface reaction (dissolution of the solid or
(2) an interface reaction (dissolution of the solid or 
deposition of the solute onto the particle surfaces).
• The average radius r
g of the particles (assumed to be 
f p (
spherical) is predicted to increase 2r for the interface 
reaction mechanism and (3/2) r for the diffusion 
mechanism
Procedures for Precipitation from Solution
(
(commonly achieved by hydrolysis reactions)
)
• Two main routes:
o a outes:
1. Hydrolysis of metal‐organic compounds (e.g., 
g y
metal alkoxides) in alcoholic solution, generally 
referred to as the Stober process and
2. Hydrolysis of aqueous solution of metal salts
Precipitation of Complex Oxides (coprecipitation)
• A solution of mixed alkoxides, mixed salts, or of a 
combination of salts and alkoxides is generally 
used