PQ'

CHAPTER 4
1005 in
Nucleation

Solution

Coarse Particles

with

Occluded lmpurities

Recrystallization
Washing

Coarse Pure

Particles

Fig. 4.1 Processing flow (

SPECIAL INORGANIC CHEMICALS
drop. The solid phase is ~SUll
by calcination at a relatlvel
ground relatively easily to a
New and potential uses of ceramics in what are called high-performance or
high-technology applications have stimulated much interest in novel techniques
for preparing special ceramic powders wth special characteristics. Character Precipitation Techniques
stics sought include a purity in excess of 99.9%, a precsely controlled, re Chemical precipitation techn
producible chemical composition including dopants, chemical homogeneity on analyses can be used to pre
an atomic scale, and a precisely controlled and consistent submicron particle The addition of a chemical p
size. ln some applications, a special particle shape may be a goal. The variety or pressure may decrease th
of compounds prepared in the laboratory is extensive. Although ceramics have tation occurs by nucleatio~
been produced for years from these special powders on a laboratory scale, adsorbed on particular surt
relatively few of these special powders have been used n industrial processing. Relatively slow growth ratl
However, the successful commercial applicatons of special materiais for prod cause the precipitate particl
ucts such as optical fibers and thick film electronic ceramics, and large potential of supersaturation may incr
markets for more advanced ceramics have increased the interest in and the tide size, but jf precipitati<
evaluaton of these techniques for industrial fabrication. ln this chapter we c1uded in the particle. The
consider general technical aspects of different techniques and examples of ma obtain a controlled precipit
teriais that have been prepared. sarne size and chemically
cations in solid solution rr
geneous precipitation, the,
4.1 POWDERS FROM CHEMICAL SOLUTION TECHNIQUES in the solution, and the cc
cipitation progresses. Less
Chemical solution techniques provide a relatively convenient means for achiev The coprecipitation of
ing powders of high purity and fine size. First a suitable liquid solution con
has been studied in detail
taining the cations of interest is prepared and analyzed. A solid particulate
phase may be formed by precpitaton, solvent evaporation, or solvent extrac
*P. K. Gallagher, H. M. O'Bry
tion. Segregation is minimized by combining the ions in a precipitate or gel 48(ll), 1053-\059 (1969).
phase or by extracting the solvent n a few mlliseconds from a mcroscopic
54

HEMICALS
called high-performance or
interest in novel techniques
characteristics. Character
, a precisely controlled, re
, chemical homogeneity on
consistent submicron particle
may be a goaL The variety
Although ceramics have
on a laboratory scale,
used in industrial processing.
of special materiaIs for prod
ceramics, and large potential
the interest in and the
Dnc:atlclO. ln this chapter we
and examples of ma-
TECHNIQUES
means for achiev
<X>IIlVf:Dlt~nt
suitable liquid solution con
A solid particulate
,...""""""",, or solvent extrac
ions in a precipitate or gel
lSeCOIlds from a microscopic
POWDERS FROM CHEMICAL SOLUTION TECHNIQUES 55
lons in Nucleation Growth
Nuclei Colloidal Particles
Solution
",..\~
1
~ Adsorption
ollons
<>,0
Coarse Particles Fine Particles
with with Stabilized Colloid
Occluded Impurilies Adsorbed Impurities
('''''".':/
Washing ,,<,~
1 Coagula tion
>l'l'Z>'b~
Fillerable
Coarse Pure
Agglomerates wilh
Partiales Recrystallizalion Occluded Impurities
Washing
Fig. 4.1 Processing ftow diagram for the preparation of apure precipitate.
drop. The solid phase is usually a salt that can be decomposed without melting
by calcination at a relatively low temperature. A porous, friable calcine is
ground relatively easily to a submicron size.
Precipitation Techniques
Chemical precipitation techniques of the type used for c1assical wet quantitative
analyses can be used to prepare a wide variety of inorganic salts (Fig. 4.1).
The addition of a chemical precipitant to the solution or a change in temperature
or pressure may decrease the solubility limit and cause precipitation. Precipi
tation occurs by nucleation and growth. Impurity ions in solution that are
adsorbed on particular surfaces of the particles may alter their growth rates.
Relatively slow growth rates along particular crystallographic directions will
cause the precipitate particles to have an anisometric shape. A higher degree
of supersaturation may increase the nucleation rate and produce a smaller par
ticle size, but if precipitation is extremely rapid, foreign ions tend to be oc
cluded in the particle. The mixing rate and temperature must be controlled to
obtain a controlled precipitate. When the cations in solution are of about the
same size and chemically similar, the precipitation of a salt containing the
cations in solid solution may occur; this is called coprecipitation. ln hetero
geneous precipitation, the concentration of an ion in the salt differs from that
in the solution, and the composition of the coprecipitate may change as pre
cipitaton progresses. Less soluble somorphs tend to concentrate in the salto
The coprecipitation of ferrous oxalates for the preparation of soft ferrites
has been studied in detail by Gallagher et aI. * A nickel-iron solid solution
*P. K. Gallagher, H. M. O'Bryan, F. Schrey. and F. R. Monteforte, Am. Ceram. Soe. Buli.,
48(11), \053-\059 (1969).
56 SPECIAL INORGANIC CHEMICALS POW

oxalate is precipitated on admixing hot ammonium oxalate in a heated aqueous solutions of the alkoxides, barill
sulfate solution: oxide Ti(OC sH 11 )4, the simulU
ium titanate according to the R
NiS04 + 4FeS04 + 5(NH4hC 20 4 . H 20 --"--~

5Nio.2Feo.8C204 . 2H 20 + lONH; + 5S0~- (4.1 )

H,O(20'C) ... BaTi03(pow<
The thermal decomposition of the oxalate salt in air at a temperature below
500C produces a well-ordered nickel ferrite compound and is described by An oxide containing severa
the reaction prepared by admixing a solutio
very high degree of supersatur
4+x The precipitation system and I
3Nio.2Feo.8C204 . 2H 20(s) + - 2 - 02(g) reproducible precipitate; impo
pH, mixing and stirring rates,
---+ Nio.6F~A04(s) + xCO(g) + (6 - x)C0 2 (g) + 6H 2 0(g) (4.2) by digestion, washing, and, ii
(Fig. 4.1). Digestion is growth
The atomic scale mixedness in the salt crystal enables the direct formation of of the finer particles while the
the ferrite of fine particle size (see Example 4.3). impurities decrease as the spe
ln some cases, it may be possible to precipitate a specific compound con purity if surface-adsorbed iml
taining two cations, and the composition of the precipitate will be uniform ions in solution films on part
regardless of the concentration of ions in solution. An example of the latter is solution may redu ce the conce
Ba(TiO(C 20 4 h) . 4H 20, formed by the reaction* . 12H20 dissolves in a hot a(
on cooling has a lower concel

(4.3)
solution (cool) ... NH
The thermal decomposition of the barium titanyl oxalate salt produces bar
ium titanate indirectly, but at a relatively low temperature (700C), because
This technique is used comm
of the fine partic\e size and mixedness:
ing 99.995% (Fig. 4.2).
Precipitation technigues h
mcron-size, higl.!.:JlUrity oxi(
(4.4)
been prodced for some sY!
catalysts. Precipitation techr
'dtiStriaCprdi:ictlOn of more ,

(225-456'C).. BaC03(s) + Ti02 (S) + CO(g) + 2C02(g) (4.5) Solvent Evaporation and
An altemative procedure us
BaCO3(s) + T 1'O 2(s) (465-700C)
..
BaT'O
1 3(5) + CO 2(g) (4.6) solution containing the ion:
remove the solvent as a va:
The hydrolysis of mixed alkoxides has been used to produce a variety of homogeneity will be possibl
oxides with partic\e sizes finer than 20 nm. When water is admixed into alcohol ponents are of about equal s

*M. D. Rigterink, J. Cano Ceram. Soe., 37, LVI-LX (1968). *K. S. Mazdiyasni. R. T. Dolloff,
 POWDERS FROM CHEMICAL SOLUTION TECHNIQUES 57

in a heated aqueous solutions ofthe alkoxides, barium isopropoxide Ba(OC3H 7h and titanium amyl
oxide Ti(OC5 H II )4, the simultaneoUs hydrolytic decomposition produ ces bar
ium titanate according to the reaction*

(4.1)

a temperature below
and is described by An oxide containing several different but chemically similar ions may be
prepared by admixing a solution of the ion in an excess of the precipitant. The
very high degree of supersaturation causes the rapid precipitation of all ions.
The precipitation system and conditions must be well controlled to obtain a
reproducible precipitate; important variables inc1ude solution concentrations,
pH, mixing and stirring rates, and temperature. Precipitates may be purified
by digestion, washing, and, in sorne cases, reprecipitation prior to filtration
(Fig. 4.1). Digestion is growth of the larger precipitate particles at the expense
direct formation of
of the finer partic1es while the precipitate is in the solution; surface-adsorbed
impurities decrease as the specific area decreases. Washing will improve the
compound con
purity if surface-adsorbed impurities are removed without precipitating other
will be uniform
ions in solution films on particles. Dissolving and reprecipitation in a fresh
.x:amplle of the latter is
solution may reduce the concentration of minor impurities. Alum NH4Al(S04h
. 12H 20 dissolves in a hot aqueous solution. The reprecipitated alum formed
on cooling has a lower concentration of alkali and transition metal impurities:

+ 6CI- (4.3)

salt produces bar (4.8)

(700C) , because
This technique is used commercially to produce alumina with a purity exceed
ing 99.995% (Fig. 4.2).
Precipitation techniques haye beel} wiciely investigated for preparing sub
!!!i~fQJl"'!'!~' high-purity oxi~_J~wders. Particle sizes as small s 2 nm have
(4.4) been produced for sorne systel}1s, and these have been llSed as commercial
~ataly~~~_: _Precipitation techniql.l~~ __lire cUIT:ntly being considered for the in
dustrial production of m()re advanced ferrites.

(4.5) Solvent Evaporation and Extraction Techniques

An altemative procedure used to prepare special powders is to disperse the
CO2(g) (4.6)
solution containing the ions of interest into microscopic volumes and then
_ a variety of
.. _ _ '_vv
remove the solvent as a vapor, forming a salt. Maintenance of atomic-scale
homogeneity will be possible for multicomponent systems only when the com
admixed into alcohol
ponents are of about equal solubility or when the salt forms extremely rapidly.
*K. S. Mazdiyasn, R. T. Dolloff, and J. S. Smith, J. Am. Ceram. Soe., 52(10),523-526 (1969).
60 SPECIAL INORGANIC CHEMICALS

Other approaches for extracting the solvent have included spraying of the so Silica gel is produced by thi
lution into an..irrlll:t~~i!:>!e_desiccating liquid (lquidlliquid drying) or spraying tetraethyl orthosilicate in a soh
into a hot immiscible liquid to produce vaporization.
ln freeze d!Yi.t:!g, a salt solution is sprayed into a cold liquid such as hexane
(-60C) and quickly frozen into a salt and ice. The solvent is sublimated at
apressure below the triple point by slowly raising the pressure and temperature,
as indicated in Fig. 4.4. Calcination of the homogeneous salt yields porous
aggregates which are milled to a micron-size powder with good sinterability. *

SolGel Techniques
Polymerized gels may also b
mixed alkoxides such as tita
Sol-gel processing has attracted much interest both for the preparation of special formed when an aqueous sol
powders and for forming thin coatings and cast or extruded shapes. ln sol-gel
with a dehydrating agent; a h)
processing, colloidal particles or molecules in a suspension, a sol, are mixed
ing an aqueous boehmite AlO
with a liquid, which causes them to join together into a continuous network,
been used to produce titania s
called a gel. Polymerization greatly restricts chemical diffusion and segregation.
cess, citric acid is added to a
The gel is dried, calcined, and milled to form a powder.
hydration to a viscous liquid, t
by spraying into a furnace.

Freeze Orying (1 +2 +3 "'4 )

2 4.2 POWDERS FROM VI

o..,..
c ....
:;::
III ...
!:!
... c
o o
Q. .
Vapor phase reactions have t
powders (Fig. 4.5). Oxides I
water vapor at a high tempel
by the reaction
111
> III\)
C ...
.-0 )(
TiCl4 (g) .+
~w

C/)
/ Salts dissolved in alcohol ha
I
duce compound oxide powd'
3 4 by oxidizing evaporated mel
Silicon nitride powder mI
ammonia in a plasma below
Temperature

Fig. 4.4 A pressure-temperature phase diagram for an aqueous salt solution and the 3SiC141g) +
processing path for freeze drying. [After M. Rigterink, Am. Ceram. Soe. Bull., 51(2),
161 (1972).]
The thermal decomposition
used to produce high-purity
'"M. D. Rigterink. Am. Ceram. Soco Bull., 51(2), 158-161 (1972). Vapor phase techniques
 POWOERS FROM VAPOR PHASE REACTIONS 61

included sprnying ofth~

Silica gel is produced by the hydrolysis and polymerization of the alkoxide
drying) or spraying

OUlIIUUllll

tetraethyl orthosilicate in a solution, as indicated by the following reactions:

(4.10)

(4.11)

(4.12)

Polymerized gels may also be fonned by the hydrolysis of other simple or

mixed alkoxides such as titanium and zirconium esters. Gels may also be
fonned when an aqueous sol of a hydrated aluminum or iron oxide is mixed
with a dehydrating agent; a hydrogen-bonded alumina gel is produced by mix
ing an aqueous boehmite AIO(OH) sol with acetone. This technique has also
been used to produce titania and zirconium oxide powders. ln the citrate pro
cess, citric acid is added to a prepared salt solution; after partial alcohol de
hydration to a viscous Iiquid, the solution is further dehydrated and decomposed
by spraying into a fumace.

4.2 POWDERS FROM VAPOR PHASE REACTIONS

\
..
\
o
Vapor phase reactions have been used to produce special oxide and nonoxide

...
c"'"

;:0""+
...~ --c
powders (Fig. 4.5). Oxides can be fonned by reacting a metal chloride with
water vapor at a high temperature, as is indicated for the fonnation of titania

.
o0.o
> u
c ..
by the reaction

-~w
0
.. (4.13)

II)
I

I
Salts dissolved in alcohol have been pyrolyzed in an atomizing bumer to pro
duce compound oxide powders. Fine oxide powders have also been produced
by oxidizing evaporated metaIs.
Silicon nitride powder may be fonned by reacting slicon tetrachloride and
ammona in a plasma below 1000C:

salt solution and the

Ceram. Soe. Bull., 51(2), 3SiCI4 (g) + 4NH 3(g) -+ Si 3 N4(sJ + 12HCI(g) (4.14)

The thennal decomposition of (CH 3 hSiCI 2 and CH 3SiH s vapor has also been
used to produce high-purity silicon carbide SiC.
Vapor phase techniques produ ce submicron-size, well-dispersed particles
 SUGGESTED READING 63

700C in the presence of steam having apressure of 1-100 MPa. A mixed

oxide compound of fine grain size is fonned on ca1cining to a relatively low
temperature. This technique, called hydrothennal synthesis, has been used to
produce a variety of mixed oxide compounds. *
Decomposition of a salt commonly produces a relatively fine, reactive prod
uct. Mixtures of salts that decompose at a similar temperature, such as an
alkaline earth carbonate and an aluminum or iron hydroxide, may produce a
mixed-oxide compound of fine particle size at a relatively low temperature.
Silicon nitride and silicon aluminum oxynitride have been produced by heating
discrete oxide particles n a ntrogen atmosphere at a high temperature.
A special chemical technique may be used to dope a fine powder or gel.
After dispersion of the powder in a chemical solution, a precpitation or gelation
reaction may precpitate or immobilize the dopant on the surface. The doped
powder produced on drying and then heating to a relatively low temperature
may be finer and require less comminution to disperse the aggregates.

SUMMARV

Powders and colloidal materiaIs that have special or very precisely controlled
characteristics have been developed for research studies and for the industrial
production of some advanced ceramics. ln preparing the special materiaIs,
relatively pure precursors are first mixed on an atomic scale in a liquid or gas.
A salt or gel containing the ions of interest is fonned by a reaction producing
a precipitate or by very rapidly removing the solvent. Chemical segregation
which reduces the homogeneity must be prevented during the preparation pro
cesso Decomposition should occur at a temperature below that causing sintering
of the product into a hard aggregate. Powders prepared using special chemical
techniques may range widely in chemical and physical fonn. Special chemical
techniques continue to be developed and evaluated for the production of pow
ders for advanced ceramcs. To be beneficial, they must enable production of
a better product.

SUGGESTED READING
collection systems are re-
1. Tetsuo Yamada, "Preparation and Evaluaton of Sinterable Slcon Nitride Powder
by lmide Decomposition Method," Am. Ceram. Soe. Bull., 72(5), 99-106 (1993).
2. Edward S. Martin and Mark L. Weaver, "Synthesis and Properties of High-Purity
Alumina," Am. Ceram. Soe. Bull., 72(7),71-77 (1993).
3. N. Balagopal, H. K. Varrna, K. G. K. Warrier, and A. D. Damodaran, "Citrate
Precursor Derived Alumina-Ceria Composite Powders," Ceram. lnt., 18, 107
111 (1992).

*S. Komarneni et aI., Adv. Ceram. Mata., 1(1), 87-92 (1986).

64 SPECIAL INORGANIC CHEMICALS

4. Shigeyuki Somiya and Yoshihiro Hirata, "Mullite Powder Technology and Ap 4.5 Explain why the selectij
plications in Japan, " Am. Ceram. Soe. Bull., 70(10), 1624-1640 (1991). cipitation stage and the
5. Wolfgang F. Kladnig and Wilhelm Kamer, "Pyrohydrolysis for the Production of compound.
Ceramic Raw MateriaIs," Am. Ceram. Soe. Bull., 69(5), 814-821 (1990).
4.6 Describe the preparatiol
6. William H. Rhodes and Samuel Natansohn, "Powders for Advaneed Structural
cesso
Ceramics," Am. Ceram. Soe. Buli., 68(10), 1804-1812 (1989).
7. William J. Dawson, "Hydrothermal Synthesis of Advanccd Ceramic Powders," 4.7 Deseribe the eitrate pra
Am. Ceram. Soe. Buli., 67(10), 1673-1678 (1988). . . ,
4.8 Deslgn a specdk proc~
8. Shin-Ichi Hirano, "Hydrothermal Processng of Ceramcs," Am. Ceram. Soe. eobalt only in the near~
Buli., 66(9), 1342-1344 (1987).
9. Timothy J. Gardner and Gary L. Messing, "Preparation of MgO Powder by Evap 4.9 Calculate the volume ~
orative Decomposition of Solutions," Am. Ceram. Soe. Bull., 63(12), 1498-1502 vapor phase reaction.
(1984).
4.10 For a heterogeneous cq
10. K. S. Mazdyasni, "Fine Partcle Perovskite Processing," Am. Ceram. Soe. Buli.,
H at some moment in ~
63(4),591-594 (1984).
,~
II. "Better Ceramics through Chemstry," n MateriaIs Researeh Society Proeeed dlpptldH~
ings, Vol. 32, C. J. Brinker, D. E. Clark, and D. R. Ulrich, Eds., North Holland, ~
1
New York, 1984.
How does the amount of ~
12. D. W. Johnson Jr., "Powder Preparation-Ceramics," n Advanees in Powder Teeh
noIogy, Gilbert Y. Chin, Ed., American Society of Metais, MetaIs Park, OH, when the partition eoeffici,
1982, Chapter 2.

13. David W. Johnson Jr., "'Nonconventional Powder Preparation Techniques," Am. j
Ceram. Soe. BulI., 60(2), 221-224, 243 (1981). EXAMPLES j
14. P. E. D. Morgan, "Chemical Processing for Ceramics," in Proeessing oJ Crys
talline Ceramies, MateriaIs Scienee Researeh, Vol. 11, H. Palmour, R. E. Davies,
and T. M. Hare, Eds., Plenum, New York, 1978, pp. 67-77.
Example 4.1 Using the!
from aqueous solution of ' .,
15. D. W. Johnson Jr. and P. K. Gallagher, "Reactive Powders from Solution," in ference between simultan .,
Ceramie Proeessing BeJore Firing, George Y. Onoda Jr. and Larry L. Hench,
I
Eds., Wiley-Interscience, New York, 1978, Chapter 12.
16. P. K. Gallagher, H. M. O'Bryan, F. Schrey, and F. R. Monforte, "Preparation Solution. ln eaeh case a 111
of a Nickel Ferrite fTOm Coprecipitated Nio.2FeogC204 . 2H2 0," Am. Ceram. Soe. However, the much larger ~
BulI., 48(11), 1053-1059 (1969). to precipitate as a separai
coprecipitate in a single ~

PROBLEMS Example 4.2 How may :

surfaee of an oxide or hydl
4.1 Compare the reaction temperatures for the formation of BaTi03 by solid
state reaction versus the titanyl oxalate processo Solution. Submicron partit
4.2 Design two different chemical processes for making MgO powder doped persed in a liquid solution,
with NiO. pH, temperature, or preSSll
agent whieh causes a slow
4.3 Contrast spray pyrolysis and vapor phase reaction techniques. on the particle surface can
4.4 What is the difference between the growth and the recrystallization of a the dopant. Subsequent lo
precipitate? modified partieulate produ

Powder Technology and Ap
1624-1640 (1991).
"'lwclf>"" for Advanced Structural
812 (1989).
Ceramics," Am. Ceram. Soe.
rati()n of MgO Powder by Evap
Soe. Buli., 63(12), 1498-1502
" Am. Ceram. Soe. Buli.,
Researeh Society Proeeed
Ulrich, Eds., North Holland,
" in Advances in Powder Teeh
of MetaIs, MetaIs Park, OH,
tPre:paratc,n Techniques," Am.
" in Processing of Crys
11, H. Palmour, R. E. Davies,
. 67-77.
Powders from Solution." in
Jr. and Larry L. Hench,
12.
R. Monforte, "Preparation
. 2H20, " Am. Ceram. Soe.
of BaTi03 by solid
the recrystallization of a
EXAMPLES 65
4.5 Explain why the selection of the salt phase is important both at the pre
cipitaton stage and the calcination stage when preparing a mixed ion
compound.
4.6 Describe the preparation of a doped alumina using the freeze-drying pro
cesso
4.7 Describe the citrate process which may be considered a sol-gel processo
4.8 Design a specific process for producing an iron oxide powder doped with
cobalt only in the near-surface region .
4.9 Calculate the volume of HCI gas when producing 1 kg of Si3 N4 by a
vapor phase reaction.
4.10 For a heterogeneous coprecipitation, the distribution of dopant I and host
H at some moment in the surface layer of precipitate is
How does the amount of dopant I vaI)' with the amount of host precipitated
when the partition coefficient . I, and when . O.4?
EXAMPLES
Example 4.1 Using the precipitation of hydroxides of Ba2 t-. AI 3 +. and Cr H
from aqueous solution of the chlorides as an example, explain the basic dif
ference between simultaneous precipitation and coprecipitation in a solution.
Solution. ln each case a liquid solution is the precursor phase in the processo
However, the much larger cation size and lower valence of Ba2+ will cause it
to precipitate as a separate hydroxide phase Ba(OHh. The AI H and Cr 3 +
coprecipitate in a single solid-solution hydroxide phase AlxCrl _ x(OHh.
Example 4.2 How may a special chemical technique be used to dope the
surface of an oxide or hydroxide particle with another cation?
Solution. Submicron particles of the primaI)' oxide or hydroxde can be dis
persed in a liquid solution contaning the dopant ion of interest. A change in
pH, temperature, or pressure, or the addition of a precpitant or polymerizing
agent which causes a slow precipitation, geJlng, or adsorption of the dopant
on the particle surface can effectively produce a surface-film phase containing
the dopant. Subsequent low temperature calcination may produce a surface
modified particulate product.
66 SPECIAL INORGANIC CHEMICALS

Example 4.3 Why are the reaction temperatures for the preparation of a PART III
powder from the decomposition of a salt commonly much lower than the tem
perature for the solid-state reaction between mixed powders?

Solution. ln salt decomposition the cations are well mixed on an angstrom

scale and the diffusion length is on the nanometer scale. But for the solid-state
reaction of mixed powders the diffusion length is of micron dimensions (see
Fig. 3.7). Also, the nucleation and growth process during salt decomposition
produces particles smaller than the size of the parent particle, as is shown in
the figure below.

Gas Out
j
MATERIALS Cl
~
j
The properties of a fired p~
Product Phase the starting material and tl.f
order to select and contro~.
of their more important c
Satt Decomposition the material specifications
Example 4.3 Product grain sze fonned on nucleation and growth during decompo material sys~em wil~ have~.'.
sition of a salto the processmg engmeer
information obtained. The'
common specifications of
in Chapter 5. Chemical a~
6. Chapters 7 and 8 descri.
size, shape, density, surfa~
,

"() 7 'V o !'l(