Hydrothermal synthesis (HS)

• It is a laboratory scale method for low-cost production of advanced ceramic

powders.

• It involves heating reactants - often metal salts, oxides, hydroxides or metal

powders – as a solution or a suspension, usually in water, at elevated
temperature (critical temperature for water is 374C) and pressure (up to
nearly 20 MPa).

• Precipitation under these conditions can lead to;

• crystalline,
• anhydrous powder with quite distinctive characteristics,
 very fine size (typically 10-100 nm),  agglomeration problem!
 narrow size distribution,
 single crystal particles,
 high purity,
 good chemical homogeneity.
 Hydrothermal synthesis

• The process is carried out in a hardened steel autoclave, which can be heated
to the desired temperature. The inner surfaces of the vessel normally lined with
a plastic (e.g., TeflonR) to limit corrosion of the vessel.

• Mineralizers, which are fluorides, chlorides and hydroxides of sodium,

potassium and lithium, are added to increase the solubility for sparingly soluble
compounds with high melting points.

•This technology has an advantage of offering dense ceramics at relatively low

temperatures.

•This method is a wet-chemical technique for directly forming complex oxide

powders.
 Hydrothermal synthesis

Figure 2.25 shows powders of Ce02 doped with 6 atomic percent (at %) Ca that
were produced from a solution of cerium nitrate and calcium nitrate under
hydrothermal conditions (4 h at 300°C and under a pressure of 10 MPa). The
particle size of the powder is 13  3 nm. Ce02 has a cubic crystal structure; the
faceted nature of the particles is an indication that they are crystalline.
 Hydrothermal synthesis

Hydrothermal processing of ceramics is generally classified as follows:

• Hydrothermal reaction synthesis: synthesis of a compound by the reaction of

starting materials in the presence of a hydrothermal solution (for example,
ilmenite (FeTiO3) is hydrothermally decomposed to form K2O.4TiO2 or
K2O.6TiO2 and magnetite (Fe3O4), which are separated from each other by
magnetism)

• Hydrothermal crystal growth: crystal growth of a compound, which is hardly

soluble in an ordinary solution below the boiling temperature, with aid of the
solubility increase in hydrothermal solution (for example, -quartz and -AlPO4
single crystal)

• Hydrothermal treatment: purification and character improvement of materials

prepared by other methods in the presence of a hydrothermal solution (for
example, pyrolysis of organic compounds)
 Hydrothermal synthesis

Hydrothermal Process Steps

Reagents Growth control agents

Oxides / hydroxides / salts

Gels
Feedstock preparation Organics
Acids / Bases

Batch or continuous oxidizing or reducing atm.

Temperature (100 to 350°C)
Reactor Pressure (up to ~20 MPa)
Residence time ( 5 to 60 min)

Pressure let-down

Filtration
Product recovery Washing
Drying

Hydrothermal powder
 Hydrothermal synthesis

Hydrothermal Reaction

• The feedstock solution may undergo one of the two crystallization mechanisms
when forming the desired composition

• The two mechanisms could be influenced by a variety of processing variables

such as solubility and composition of starting materials, heating rate, pH,
mineralizers, feedstock concentration and hydrothermal reaction T and time

• As precursors, normally oxides or hydroxides, of component oxides are heated,

their solubility increases

• Eventually, a sufficient concentration of the components exists in solution to

begin formation of a more stable oxide phase

• The driving force in these reactions is the difference in solubility of the oxide
phase from the least soluble precursor or intermediate.
 Hydrothermal synthesis

In-situ transformation of amorphous precursors

H2O
H2O

M(OH)xOy Ma O b
H2O

H2O H2O
X-ray amorphous
precursor Structural water loss Polycrystalline aggregate

Dissolution-recrystallization of precursor particles

M(OH)xOy Mb+ (aq) + OH- (aq) Ma O b

X-ray amorphous
precursor Transient dissolution Single crystal particles
 Hydrothermal synthesis

Advantages
• No need for high-T calcination which, in turn, eliminates the need for milling.
Thus, no impurity or structural defects associated with milling
• Possible to produce anhydrous crystalline powders with controlled particle
size, controlled stoichiometry and in some cases controlled particle shape
• Powders produced by this method have been demonstrated to be highly
reactive toward sintering
• Relatively inexpensive raw materials
• A noninclusive list of these includes perovskite titanates and solid solutions
with niobates and tantalates, many spinel structure oxides and wide range of
simple oxides.

Disadvantages
• Extensive washing is necessary both before the synthesis to remove any ionic
impurities (such as Cl-), and after the synthesis to remove any mineralizers that
may have been used.
• Pressure vessels that are used for maintaining the hydrostatic conditions are
susceptible to corrosion during the reaction if mineralizers are present in the
feedstock solutions.
 Hydrothermal synthesis

Electronic ceramic powders

• The advantage of HS, particularly for dielectrics, is the ability to produce solid-solution
particles of controlled size. Most modern capacitor applications require complex
perovskite (ABO3) compositions involving BaTiO3 and up to eight dopant oxides, such
as CaZrO3, MgZrO3, CaTiO3, etc.

• Coprecipitation/calcination processes have been developed for above compositions.

However, coprecipitation, even at temperatures as high as 100°C, does not result in solid-
solution formation with many of the important dopants. Therefore, calcination step is
required to promote solid-state diffusion of the dopants into the crystal structure. The
resulting powders must then be milled to the required fine particle size (<1µm).

• Other important powders produced by HS are Pb(Zr,Ti)O3 (PZT), PLZT, ZnO powders
and magnetic oxide powders.
 Hydrothermal synthesis

Structural Ceramics

• Hydrothermal synthesis has been considered for production of alumina and

zirconia, which are the predominant advanced structural oxides today.

• The Bayer process for alumina is the largest-scale production process which
employs a hydrothermal step for production of a ceramic oxide. A hydrothermal
treatment step is employed at 120°C to 300°C to form soluble sodium
aluminates, leaving the other ore components in the solid fraction.
 Hydrothermal synthesis

Hydrothermal reaction sintering

• This is the technique for sintering of oxides at low T using the hydrothermal reaction of
metal powders with water in a capsule permeable to formed hydrogen gas. For example,
fully dense sintered body of magnetite can be obtained at temperatures as low as 550°C
at 100 MPa by the reaction

3Fe + 4H2O  Fe3O4 + 4H2

• The sintering time necessary for the theoretical density depends strongly on parameters
such as the total fill percentage of starting materials, the ratio of starting metal to water,
the capsule material and the pressure – temperature conditions.

• The low sintering T strongly tends to hinder grain growth in the sintered body without
any inhibiting additive and gives a fully dense sintered body with a homogeneous
texture.
 Hydrothermal synthesis

HYDROTHERMAL SYNTHESIS OF NANO ZrO2 POWDERS

C. Duran et al., Key Engineering Materials 317-318 pp.195-198, (2006)
C. Duran et al., Ceramics International, 41(4), pp.5588-5593 (2015)

Experimental procedures
Aqueous Zr solution precursor, • 0.2, 1 and 2 M
using ZrOCl2.8H2O (pH <1)

Hydrothermal reaction • Fill volume: 50 % of 100 mL Teflon vessel

• Temperature: 100 to 200C
• Time: 1 min to 24 h
• Heating rate: 1, 3, 5, 10C/min
• Rotation speed: 0, 150, 311 rpm

Characterization • Laser particle size analyzer: mean size and distribution

• XRD: phase and crystallite size
• DTA: Crystallinity
• ICP: ZrO2 fraction
• TEM: Crystallite size and morphology
 Hydrothermal synthesis

Mean particle size as a function of reaction temperature and time

0.2 M, Heating rate 1C/min, 150 rpm

0.130
175C 100
125C
0.120 200C

Cumulative Volume %
Mean particle size, m

80
0.110
150C
0.100 60
125C 4, 6, 15 hours
0.090 135C
40
0.080

20
0.070

0.060 0
0 2 4 6 8 10 12 14 0 16 0.05 0.1 0.15 0.2 0.25 0.3
Time, hour Particle size, m
Measured by laser particle size analyzer
Mean particle size increases with increasing temperature and time
 Hydrothermal synthesis

TEM observation

2M, Heating rate 1C/min, 200C for 1 min (+20 h), 311 rpm

Crystallite size < 5 nm

 Evaporation of liquid

Evaporation of the Liquid

Evaporation of the liquid provides another method for bringing a solution to
supersaturation and thereby causing the nucleation and growth of particles with
desired characteristics.

The simplest case is for a solution of a single salt. For the production of fine
particles nucleation must be fast and growth slow  the solution be brought to a
state of supersaturation very rapidly so that a large number of nuclei are formed
in a short time: One way of doing this is to break the solution up into very small
droplets so that the surface area over which evaporation takes place increases
enormously.

For a solution of two or more salts a further problem must be considered.

Normally the salts will be in different concentrations and will have different
solubilities. Evaporation of the liquid will cause different rates of precipitation,
leading to segregation of the solid.
 Evaporation of liquid

Here again, the formation of very small droplets will limit the segregation to
the droplets since no mass is transferred between individual droplets.
Furthermore, for a given droplet size, the size of the particle becomes smaller
for more dilute solutions. This means that we can further reduce the scale of
segregation by the use of dilute solutions.

We now consider some of the practical ways of producing

powders by the evaporation route:
• Spray drying
• Spray pyrolysis
• Freeze drying
 Evaporation of liquid
Spray Drying
In spray drying, fine droplets produced by a fluid atomizer are sprayed
into a drying chamber and the powder is collected. Contact between the spray
and drying medium (commonly hot air) leads to evaporation of moisture.

rotary atomizer
pneumatic atomizer
ultrasonic atomization

Droplet sizes ranging from less

than 10 m to over 100 m can be
produced by these atomizers. In
the drying chamber, the flow
pattern of the hot air determines
the completeness of moisture-
removal and the maximum
temperature that the produced
particles will experience.

(Figure 2.29).
 Evaporation of liquid

The variables that must be controlled in spray drying are:

• the size and morphology of the droplet,

• the concentration and composition of the solution (sulfates and
chlorides are often used due to their high solubility),
• the temperature (typically less than 300C),
• flow pattern of the air in the drying chamber,
• the design of the chamber.

Under suitable conditions, spherical agglomerates with a primary particle

size 0.1 m or less can be obtained.
 Evaporation of liquid

Suspensions of fine particles (sometimes referred to as slurries) can also be dried

by spray drying. In this case, the liquid is removed in such a way as to limit the
agglomeration of the dried powder to a scale equal to or less than the size of the
droplet. Limiting the scale of the agglomeration should provide benefits in terms
of better overall uniformity of the compacted body, which leads to benefits in
sintering.

Spray drying is used on a

large scale industrially for
the drying of slurries (e.g.,
produced by wet milling) for
the production of powders
for dry compaction.

Fig 2.33. lead zirconate titanate powder

The process provides good control of the agglomerate size, the flowability of the
powder, the moisture content, and the density strength of the compacted body.
 Evaporation of liquid
Spray Pyrolysis
(Spray roasting, spray reaction, or evaporative decomposition of solutions)
By using a higher temperature and a reactive (e.g.; oxidizing) atmosphere in the
chamber, the salts can be dried and decomposed directly in a single step. The stages in
the formation of a dense particle from a droplet are shown below:

EVAPORATION PRECIPITATION DRYING DECOMPOSITION SINTERING

(heating)
Solvent vapor
diffusion
Solvent vapor
Heat transfer

Precipitate
Solution

The droplet undergoes Precipitation is followed by a Decomposition of the

evaporation and the solute drying stage in which the precipitated salts produces
concentration in the outer vapor must now diffuse a porous particle made up
layer increases above the through the pores in the of very fine grains, which
supersaturation limit, leading precipitated layer. is finally heated to produce
to the precipitation of fine a dense particle.
particles.
Messing et. al., J. Am. Ceram. Soc. 76[11], 2707-26, 1993
 Evaporation of liquid

Aqueous solutions are commonly used because of their ease of handling,

safety, and low cost combined with the availability of a wide range of soluble
metal salts.

The solute must also have a high solubility in order to increase the yield of the
powder produced. Decomposition is a kinetic process, so for a given set of
conditions, salts with relatively high decomposition rates may be decomposed
completely whereas others with lower decomposition rates may be incompletely
decomposed. For small-scale laboratory equipment in which the reaction times are
small, nitrates and acetates are preferable to sulfates because of their lower
decomposition temperatures. However, acetates have a low solubility whereas
nitrates, acetates, and sulfates can introduce impurities into the powder. Chlorides
and oxychlorides are used industrially because of their high solubilities, but the
corrosive nature of the gases produced during decomposition and the deleterious
effect of residual chlorine on subsequent sintering can be problematic.

The particles should be sintered in situ to take full advantage of

the spray pyrolysis process.
 Evaporation of liquid

For advanced ceramics, dense particles are preferred over those with highly
porous or hollow shell-like morphologies. The major factors that influence the
particle morphology are believed to include the solubility of the metal salt and
the degree of supersaturation of the solution.

The following factors are believed to be necessary for the preparation of

dense solid particles:
• There should be a large difference between the critical supersaturation
concentration and the saturation concentration of the solute.
• The solute should have a high solubility and a positive temperature
coefficient of solubility.
• The precipitated solids should not be thermoplastic or melt during
decomposition.
• The droplet size generated by the atomizer should be small.
 Evaporation of liquid

Effect of precipitation conditions and precursor characteristics on

particle morphology
Dense particle

Solvent vapor
diffusion

Fig 2.32a
 Evaporation of liquid

Effect of precipitation conditions and precursor characteristics on

composite particle microstructure.

Fig 2.32b
(seeding)
 Evaporation of liquid
A variety of particle morphologies are possible as a result of the
drying of a droplet of a salt solution.

ZrO2 ZrO2

Al2O3/Pt Al2O3/Pt
nano composite nano composite

Catalyst Y2O3-stabilized
particles ZrO2 fibers

Fig 2.31
 Evaporation of liquid

Freeze Drying
In freeze drying, the solution is broken up by an atomizer into fine droplets (in the
range of 10–500 nm) which are then frozen rapidly by being sprayed into a cold bath
of immiscible liquid such as hexane and dry ice or directly into liquid nitrogen. The
frozen droplets are then placed in a cooled vacuum chamber, and the solvent is
removed, under the action of a vacuum, by sublimation without any melting. The
system may be heated slightly to aid the sublimation.

Finally, the dried powder is decomposed at elevated temperatures to produce an oxide.

The technique produces spherical agglomerates of fine partic1es with the agglomerate
being of the same size as the frozen droplets.

The size of the particles in the agglomerates depends on the concentration of the
solution and decomposition step. Because the solubility of the most salts decreases
with temperature, the rapid cooling of the droplets in freeze drying produces very
rapidly a state of supersaturation of the droplet solution.
 Evaporation of liquid

Particle nucleation is therefore rapid and growth slow, so the size of the
particles in the frozen droplet is very fine.

Because the freezing of the droplets can be carried out very rapidly
compared to the evaporation of the liquid in spray drying, the surface area
of the powders can be significantly higher than that for spray-dried
powders. Surface are as high as 60 m2/g have been reported for freeze-
dried powders.
Finally, as we outlined for spray drying, the freeze-drying technique is
also used for drying slurries.

Freeze-drying gives softer agglomerates and higher surface area because

of the absence of capillary forces (present in conventional drying and
spray drying).
Gel route: Sol-gel processing
• A solution of metal compounds or a suspension of very fine particles in a liquid
(referred to as a sol) is converted into a highly viscous mass (the gel).
• It is a fabrication route for ceramics.
• With careful drying, the process can be used for producing monolithic ceramics, but
it is best applied to the formation of films and fibers.
• Although expensive, it can also be used for the production of powders. The gel
formed by hydrolysis, condensation and gelation of the initial solution (normally
with a polymeric structure) is dried and ground to produce a powder.

Sol Gel

http://www.rsc.org/chemistryworld/2012/10/injectable-hydrogels-medicinal-use
 Gel route

• Because the mixing of the constituents in the gel formation is achieved at a

molecular level, the powders have a high degree of chemical homogeneity.

• Controlled drying is not needed in the production of a powder. However,

dried gels with lower strength are easier to grind, and the extent of
contamination introduced during grinding is lower.

• For powders produced from dried gels, the benefits in sintering are due to
the amorphous structure and high surface area.

• A crystallization step is necessary for the production of crystalline bodies. If

the crystallization occurs prior to full densification, then the sintering
benefits may be reduced significantly.

• Also, a significant volume change during crystallization may cause cracking

of the body.
 Gel route
Procedures
• Prepare a solution of metal alkoxides (metal-organic compounds) in an appropriate alcohol.
Metal alkoxides have the general formula M(OR)z where M is metal (e.g., Si, Al, B etc) and
R is an alkyl group (e.g., CnH2n+1).
• Add water to this solution either in the pure state or diluted with more alcohol.
• Stirring at temperatures normally 50–90C and with suitable concentration of reactants and
pH of the solution, hydrolysis and condensation reactions may occur, leading to the
formation of polymer chains.

Taking the example of a tetravalent metal (e.g., M=Si), the reactions may be
expressed as:
hydrolysis reaction  M(OR)4 + H2O → M(OR)3OH + ROH
condensation reaction  M(OR)3OH + M(OR)4 → (RO)3-M-O-M-(OR)2 + ROH
(Polymer with metal ions )

• Polymerization interlinking and cross-linking of the polymer chains  a marked

increase in the viscosity of the reaction mixture and the production of a gel.
• The gel has a continuous solid network and a finite shear modulus.
• The solids content of the gel can be quite low due to excess water and alcohol used
(i.e., <5–10 vol% in many cases). The remainder of the volume consists of liquid
that must be removed prior to firing.
 Gel route

Solution Dashed line indicates that

(of metal alkoxides (metal-organic compounds)) we can start directly with
«sol».
Hydrolysis and
condensation Hydrolysis

Sol (suspension of fine

Sol (solution of polymer)
particles)
Gelation Gelation

liquid «Polymeric» gel liquid

«Particulate» gel

drying drying
A network of fine
A network of
Dried gel Dried gel particles (or
polymer
particulate gel) due to
chains formed
surface forces.
by hydrolysis firing firing
and
condensation
Dense product Dense product
reactions

Sol-gel process Sol-gel process using a

using a solution suspension of fine
particles
 Gel route

Electronegativity of the main element is an important factor in the choice of

synthetic route so that strongly electropositive metals with valances up to 3
react directly with alcohols to give alkoxides together with the liberation of
hydrogen.

HgCl2
2Y + 6C3H7 iOH 2Y(OiC3H7)3 + 3H2 

where Hg is a catalyst and HgCl2/Y mole ration is 10-3 – 10-4. In the description
of alkoxides, the superscripts n, t, s, and i refer to normal, tertiary and secondary
and iso alkyl chains, respectively.

SiCl4 + 4C3H7iOH 2Si(OiC3H7)4 + 4HCl 

 Gel route

Hydrolysis of tetraethoxysilane

Solution of Hydrolysis Calcine Oxide

alkoxides (sol) Gel
product

Si(OC2H5)4 + 4H2O  Si(OH)4 + 4C2H5OH

Si(OH)4  SiO2 + 2H2O

Partial or total hydrolysis of an alkoxide, referred to as the sol, liberates

alcohol and results in gel formation either as stiff monolith, fibers,
coatings, or powders.
The sol-gel conversion for alkoxides is irreversible.
 Gel route

Advantages:
• Materials with high purity can be produced
• Materials with exceptionally good chemical homogeneity (mixing at the
molecular level)
• Lower densification (or sintering) temperature

Disadvantages:
• The starting materials (e.g., the metal alkoxides) can be fairly expensive
• Cracking, warping, and considerable shrinkage (e.g., 90 vol% during drying
and 50 vol% during firing) are common problems during drying.

Mainly because of these problems in drying, the sol–gel route has

seen little use for the fabrication of monolithic ceramics. Instead it
has seen considerable use for the fabrication of small or thin articles,
such as films, fibers, and powders.
 Gel route

The Pechini method (also referred to as citrate gel process or amorphous citrate process) is
used to prepare wide variety of oxide powders.

In this method, metal ions from starting materials such as carbonates, nitrates, and
alkoxides are complexed in an aqueous solution with -carboxylic acids such as citric acid.
When heated with a polyhydroxy alcohol, such as ethylene glycol, polyesterification
occurs, and on removal of the excess liquid a transparent resin is formed. The resin is then
heated to decompose the organic constituents, ground, and finally calcined to produce the
powder.

Ti(OC4H9)4

Fig 2.34 Flowchart for the

preparation of SrTiO3.
 Gel route
Advantage:
• Very good chemical homogeneity because as in the sol-gel process mixing occurs on the
atomic scale during the polymerization process and this is kept in the resin formation.
Disadvantage:
• Material formed from the decomposition of the resin is not in the form of a powder but
consists of charred lumps. These lumps have to be ground and then calcined to produce a
powder. The grinding step may introduce impurities into the powder, and the calcination step
generally produces hard agglomerates.

Degree of agglomeration
depends on the calcination
temperature
Gel route
 Gel route

The glycine nitrate process is one of a general class of combustion methods for the
preparation of ceramic powders. A highly viscous mass formed by evaporation of a
solution of metal nitrates and glycine is ignited to produce the powder. Glycine, an amino
acid, forms complexes with the metal ions in solution, which increases the solubility and
prevents the precipitation of the metal ions as the water is evaporated  good chemical
homogeneity is achieved as in the case of the Pechini method. Glycine also serves
another important function  it provides a fuel for the ignition step of the process as it is
oxidized by the nitrate ions.

The reactions occurring during ignition are highly explosive. Under well controlled
conditions, a loose mass of very fine crystalline powder (particle size less than tens of
nanometers) is obtained after ignition  no grinding is required.

This process offers a relatively inexpensive route to the preparation of very fine,
chemically homogenous powders.

Used for the preparation of simple oxides as well as complex oxides (e.g., manganites,
chromites, ferites, oxide superconductors)
Molten salt synthesis (MSS) uses a molten salt as a solvent for the constituent
oxides (e.g., reactants).

MSS has been used extensively to prepare ferrites, titanates, niobates, and
mullite.

The desired compound will form if it is thermodynamically more stable than the
reactants.

Because of the short diffusion distances in an intimate mix of the reactants and
the relatively high mobility of species (1x10-5 to 1x10-8 cm2/s compared to as low
as 1x10-18 cm2/s in the solid state), complete reaction is accomplished in a
relatively short time.

It is desirable to have a molten salt viscosity of 1–100 MPa.s because high

viscosity can retard the growth process.

Toshio Kimura, Molten Salt Synthesis of Ceramic Powders, Advances in Ceramics - Synthesis and
Characterization, Processing and Specific Applications, Edited by Prof. Costas Sikalidis, 76-100, 2011
 MSS

• The vapor pressure of the salt must be low at the reaction temperature to
maintain constant salt bath chemistry and to prevent salt evaporation.

• It is advantageous to have a common cation between the salt and the solute to
minimize contamination by other metal ions.

Preparation procedure in molten salt synthesis.

Toshio Kimura, Molten Salt Synthesis of Ceramic Powders, Advances in Ceramics - Synthesis and
Characterization, Processing and Specific Applications, Edited by Prof. Costas Sikalidis, 76-100, 2011
 MSS

Powders with grains of various shapes are obtained by molten salt synthesis, depending on
the chemical composition and reaction conditions.

• Powder particles are formed in two stages in molten salt synthesis:

• Reaction and particle-growth stages (supersaturation is high during the reaction
stage and almost zero during the particle-growth stage)

• The particle shape is determined by the reaction conditions, such as the chemical
species of the salt used, the reaction temperature and its duration, and the powder
characteristics of the reactants.

Similar to hydrothermal
reaction on page 7

Schematic diagrams of the formation of product particle P from reactant particles

A and B by (a) solution-precipitation and (b) solution-diffusion processes.
Toshio Kimura, Molten Salt Synthesis of Ceramic Powders, Advances in Ceramics - Synthesis and
Characterization, Processing and Specific Applications, Edited by Prof. Costas Sikalidis, 76-100, 2011
 MSS
Molten salt synthesis of anisometric particles in the SrO–Nb2O5–BaO system
C. Duran et al., Materials Research Bulletin 39 (2004) 1679–1689

Product: KSr2Nb5O15
Salt: KCl

Phase formation and morphology evolution in the KCl and SrNb 2O6 system; (a) 900°C (b)
1025°C (c) 1050°C, and (d) 1100°C for 4 h (CR=2°C/min).
 MSS

Powders synthesized by MSS

Messing et al., Critical Reviews in Solid State and Materials Sciences Vol. 29, pp. 49-96 (2004)
 MSS

Powders synthesized by MSS

(Hydrothermal)

Messing et al., Critical Reviews in Solid State and Materials Sciences Vol. 29, pp. 49-96 (2004)
Nonaqueous Liquid Reaction (NLR)
Reactions involving nonaqueous liquids have been used for the preparation of Si3N4
powders. The advantage of these methods is the higher purity and finer particle size of the
powder produced compared with methods that involve grinding of a solid product.

The reaction between liquid SiCl4 and liquid NH3

Polymeric silicon diimide decomposes according to the overall reaction

The products formed by the interfacial reaction between the two liquids were collected
and washed with liquid NH3 and calcined at 1000°C to produce an amorphous Si3N4
powder. Subsequent calcination at 1550°C in N2 yielded a crystalline powder with a
particle size of nearly 0.2 µm (Fig 2.35 next slide). Metallic impurities (Fe, Ca, and Al)
were <0.02 wt %.
FIGURE 2.35 Scanning electron micrograph of a commercially available
Si3N4 powder (UBE-SN-E10) produced by the reaction between SiCl4 and
NH3 liquids
Oxide powder process comparison

• MSS
• Glycine Nitrate

Dawson, W. J., “Hydrothermal Synthesis of Advanced Ceramic Powders”, Am. Ceram. Soc. Bull., 67 [10] 1673-78 (1988).
Cousin, P., and Ross, R. A., “Preparation of Mixed Oxide: A Review”, Mater. Sci. & Eng., A130, 119-125 (1990).
C. Vapor-Phase Reactions

Reactions involving the vapor phase have been used extensively for the production
of powders of refractory oxides and nonoxides.

Crystalline Si3N4 exists in two different hexagonal polymorphs designated  and

β, with the  form having the slightly higher free energy at the formation
temperature. Powders of -Si3N4 have a more equiaxial particle shape and sinter
more readily than β-Si3N4, the particles of which grow in a more elongated shape.
The preparation conditions are therefore selected to maximize the amount of -
Si3N4 produced.
SiC exists in many polytypes, with the two major forms being designated  and β.
The β form is more stable at lower temperatures and transforms irreversibly to the
 form at nearly 2000°C. Powders produced above 2000°C therefore consist of  -
SiC. Powders of either the  or β form are used in the production of SiC bodies.
However, the sintering of β-SiC powders above 1800-1900°C results in the
transformation to the  phase, which is accompanied by growth of platelike 
grains and a deterioration of mechanical properties. The use of β-SiC powder
therefore requires very fine powders so that the sintering temperature can be kept
below ~1800°C.
 Vapor phase preparation methods:
(i) reactions between a gas and a solid
(ii) reactions between a gas and a liquid
(iii) reactions between two or more gases.

(i) Gas-Solid Reaction

A widely used method for the

preparation of Si3N4 powders is
direct nitridation, in which Si
powder (particle size typically in
the range 5-20 m) is reacted
with N2 at temperatures between
1200 and 1400°C for 10-30 h.
The method is used
commercially.

FIGURE 2.36 Scanning electron micrograph of a

commercially available Si3N4 powder produced by the
nitridation of silicon.
For powder production a loose bed of Si powder, the reaction may be written as

3Si + 2N2 → Si3N4

The thin Si02 layer covering the Si particles severely reduces the rate of the
reaction. it is found that a nitriding gas of N2 with ~5% H2 or a pretreatment in
H2, Ar, or vacuum prior to nitridation to volatilize the Si02 layer can improve the
nitriding reactivity.

The dominant process is believed to be the volatilization of Si and the vapor-

phase reaction with N2 leading to the formation of -Si3N4 by a chemical vapor
deposition process (1250-1370ºC). A minor reaction is the nucleation and growth
of β-Si3N4 on the solid silicon by surface diffusion of Si to the reaction site. For
silicon powder containing impurities (e.g., Fe), solution of N2 in liquid silicon
alloys (formed at the nitriding temperature) occurs with the precipitation of β-
Si3N4. The nitridation process therefore leads to a mixture of - and β-Si3N4.
However, the reaction temperature, the partial pressure of the N2 gas in the
nitriding atmosphere, and the purity of the Si provide some control of the amount
of β-Si3N4 produced.
Si3N4 powder is also produced by the carbothermal reduction of SiO2 in a
mixture of fine SiO2 and C powders followed by nitridation at 1200-1400C.

The mechanism is believed to involve the reaction of gaseous SiO as follows;

Any carbon remaining after the reaction must be burn out in an oxidizing
atmosphere, and this may cause some reoxidation of the Si3N4 surfaces.

The two methods described above produce a strongly agglomerated mass of

Si3N4 that requires comminution, washing and classification. The impurities
introduced into the powder during these steps can cause a significant reduction in
the high-temperature mechanical properties of the fabricated materials.
Sintering behaviour of silicon nitride powders produced by carbothermal
reduction and nitridation Advanced Powder Technology 24 (2013) 697–702

Fig. 2. SEM images of initial powders from the CRN process;

(a) SN-M, (b) SN-Y and (c) SN-LY. (All scale bars show 5 m.)
ii) Gas-liquid reaction

The reaction between liquid SiCl4 and NH3 gas in dry hexane at OC can be used
to prepare a fine Si3N4 powder with very low levels of metallic impurities
(<0.03wt%). The initial reaction may be written as;

But involves a more complex set of reactions. The overall decomposition of

silicon diimide to produce Si3N4 is

The powder produced is amorphous to X-rays but crystallizes to -Si3N4 after

prolonged heating between 1200C and 1400C.
 iii) Gas-gas reaction

Several gas-phase reactions are used to produce ceramic powders industrially as

well as on a laboratory scale. The methods employ a variety of techniques for
heating the reactant gases in the reactor, including flame, furnace, plasma, and
laser heating.

Flame synthesis of TiO2 and SiO2 forms two of the largest industrial processes
for synthesizing powders by gas phase reactions. The reactions can be written;

In the formation of fumed SiO2, SiCl4 reacts in an H2 flame (1800C) to form single
spherical droplets of SiO2. These grow by collision and coalescence for to form
larger droplets. As the droplets begin to solidify, they stick together on collision but
do not coalesce, forming solid aggregates, which in turn continue to collide to form
agglomerates.
A disadvantage of the process is the agglomerated nature of the particles (as
shown below for SiO2). The advantages include a high-purity product resulting
from the use of high-purity gases, the simplicity of the reaction system, and scale
up of the process.

FIGURE 2.39 Scanning electron micrograph of flame-synthesized SiO2.

Furnace, plasma, and laser heating have been used to produce Si3N4 and
SiC powders by several gas-phase reactions, including the following:

The use of silicon tetrachloride SiCl4 leads to highly corrosive HCl as a

byproduct so that silane, SiH4, despite being expensive and flammable in
air, is generally preferred as the reactant. For Si3N4 production, NH3 is
used because N2 is fairly unreactive.