for the preparation of a

much lower than the tem-

micron dimensions (see
salt decomposition
particle, as is shown in
ln
growth during decompo-
PART III
MA TERIALS CHARACTERIZA TION
The properties of a fired product are very dependent on the characteristics of
the starting material and their subsequent modification during processing. ln
order to select and control these materiais, it is necessary to have a knowledge
of their more important characteristics. Some of this information is supplied in
the material specifications provided by the raw-material supplier. However, the
material system will have to be characterized at different processing stages, and
the processing engineer must be familiar with the techniques used and the
information obtained. The general characteristics of a material system and
common specifications of severa I commercial ceramic materiais are presented
in Chapter 5. Chemical and microstructure analyses are discussed in Chapter
6. Chapters 7 and 8 describe principies and techniques for characterizing the
size, shape, density, surface area, and porosity of ceramic particle systems.
, ~ "I
67
CHAPTER 5
CHARACTERISTICS ANO
SPECIFICATIONS OF CERAMIC
MATERIALS
The characteristics of a material are those parameters that specify the chemical
and physical aspects of its composition and structure. "Composition" denotes
the proportions of chemically and physically different constituents. "Structure"
refers to the spatial distribution, orientation, and association of these constit-
uents.
The properties of a material are its responses to changes in the physical or
chemical environment. Every particle system will have particular properties-
for example, a particular thermal conductivity, elastic modulus, and dielectric
constant. Flow and deformation properties are commonly referred to as !:heo-
logical properties. Responses to the chemical environment such as adsorption
or dissolution are chemical properties. Porous particle systems may have special
properties such as capillarity, permeability, and electroosmotic flow. Dispersed
systems have special properties such as settling rate, electrophoretic mobility,
and optical scattering. A system is said to be with respect to a
particular property if the property varies with direction in the material.
This chapter will consider the general characteristics of particle systems and
specifications provided for ceramic raw materiais. The student should keep in
mind the distinct difference between the properties and characteristics of a
material system.
5.1 PARTICLES, POWOERS, COLLOIOS, ANO AGGLOMERATES
The size range of particles used in ceramics processing covers a wide range of
sizes, as is indicated in Fig. 5.1. A particle is a discrete, solid unit of material
and may be single or multiphase in composition. Groups of particles that are
69
I
!
70 CHARACTERISTICS AND SPECIFICATIONS OF CERAMIC MATERIALS
10
18
Colloidal Powder
Sand
Cemenl
10
1
'

-
:2
10
13
li
Q.
eaclerla

10
10
c
::l
:;

PalnlPlgmenl
10
7
E
TobaeeoSmoke
o
II.
10
4
Vlru.e.
10
1
ParticleOlameter(tlm)
Fig. 5.1 Increase in fonnula units per AI
2
0
3
particle with particle size and particle
size range ofgranular materiaIs, powders, and col\oidal materiaIs and some common
substances.
bonde<.tJogether may behave as a fragile, larger pseudoparticle called
an agglomerate (see Fig. 3.5). If bonded together, the larger particle
is noteasilydispersed and is referred to asan aggregateorahard agglomerate.
Bonds in hard agglomerates are generally primary chemcal bonds formed by
achemical reactionorsintering. lnsoftagglomerates, therelativelyweakbonds
may beofelectrostatic, magnetic, Van derWaals, orcapillary adhesion type.
The magnitude ofthe inertial force ofa particle relative to surface forces
hasamajoreffecton particle behavior. Aparticlesystem is said to begranular
ifthegravitational force is predominant(thematerial isfree-flowing), apowder
ifthe surface force is ofthe sarne order as the gravitational force (naturally
agglomerates), and colloidal ifthe particles are so fine that the inertial force
ofa particle is insignificant and the surface forces dominate the behavior. The
surface forces aredependent on theenvironment ofthe particles. But for prac-
tical purposes, particles largerthan 44 pm (opening in a 325-mesh sieve) can
generally be considered to be granular and particles smaller than I pm as
colloidal. Colloids dispersed in a low-viscosity Iiquid typically exhibitBrown-
ian motion at 20C. The behavior ofpowders and colloids can be markedly
altered by adsorbed surfactants that modify the surface forces.
5.2 RAW-MATERIAL SPECIFICATIONS
The general characteristics ofone particle and a system ofparticIes are listed
in Table 5.1. Complete characterization is an impossible task, and for each
TABLE5.1 Characterisdc
Single ParticIe'
'.
1. PrimaI)' chemical complj
2. Impurity composition, d
and partitioning
3. Phase compositon
4. Point and line defects, d
5. Structureofphases, boII
6. Porosity and pore
7. Size
8. Shape
9. Density
10. surface area
TABLE5.2
Characteristici
""
cI)'stal phase .1
Purity (%)1
Impurity analysis of
grade (ppm)
Na!
Pb
Si
Cr
Fe
Ga
Ca
Mg
Zn
Ti
Mn
V
Cu
Si0
2
Fe203
CaO
Na20
Ga203
Others
Ultimate partic\e size (ILm]
Specific surface area (mll.
Agglomerate size (ILm) mi
Cl)'stal density (Mg/m
3
)
Apparent bulk density (M.
"Products of8aikowskiInterl
bproductofAluminum Comp
RAW-MATERIAL SPECIFICATIONS 71
TABLE5.1 Characteristicsofa ParticleSystem
Sing1e Particle Particle System
1. Primary chemical composition 1. Distribution ofchemical composition
2. lmpurity composition, distribution, 2. Distribution ofimpurities
and partitioning 3. Distribution ofphase composition
3. Phase composition 4. Distribution ofcrystal defects
4. Point and line defects, domains, etc. 5. Porosity and pore structure
5. Structure ofphases, boundaries 6. Particle structure distribution
6. Porosity and pore structure 7. Particle size distribution
7. Size 8. Particle shape distribution
8. Shape 9. Particle density distribution
9. Density 10. Bulkdensity
10. Specific surface area 11. Specific surface area
TABLE5.2 Speciftcation ofSpeciaIHigh-Purity Aluminas
Characteristic Calcined
G
Calcined
G
Calcined
b
particle size and particle
Crystal phase >90% gamma 85% alpha alpha
materiais and some common
Purity (%) 99.99 99.99 99.99
Impurity analysis ofceramic
grade (ppm)
Na 20 20
pseudoparticle called
Pb 4 4
, the larger particle
Si 18 18
orahardagglomerate.
Cr 4 4
bonds formed by
Fe 10 10
therelativelyweakbonds
Ga 15 15
capillary adhesion type. Ca 10 10
relative to surface forces
Mg 5 5
is said to be granular
Zn 4 4
Ti 5 5
is free-flowing), a powder
Mn 3 3
force (naturally
V 3 3
fine that the inertial force
Cu 2 2
the behavior. The
Si0
2
<50
particles. But for prac-
Fe20J <20
in a 325-mesh sieve) can
CaO
<10
smaller than 1 Ilm as
Na
2
0
<10
typcally exhibitBrown-
Ga203 <10
colloids can be markedly Others
<10
forces. Ultimate particle size (Ilm) 0.01 0.15 <0.5
Specific surface area (m
2
/g) 115 10 5-50
Agglomerate size (JLm) mean 2 0.6 0.5
Crystal density (Mg/m
3
) 3.67 3.98 3.98
Apparent bulk density (Mg/m
J
) 0.12 0.51
"Products ofBaikowski Intemational Corp., Charlotte, NC.
bProduct ofAluminum Company ofAmerica, Pittsburgh, PA.
72 CHARACTERISTICS ANO SPECIFICATIONS OF CERAMIC MATERIALS
material and application we must consider what characterization is necessary
and sufficient. Sorne ofthis information may be supplied by the raw-material
vendoron a specification sheet for the material. Table 5.2 lists typical speci-
fications forspecial very high purity, very fine aluminamateriais. Theimpurity
composition is quite complete, and the crystalline phase is identified. The
specific surfacearea and nominal information about agglomeration and crystal
sizearepresented. Sincethese are relatively expensive materiais, thecustomer
will certainly determine additional characteristics ofeach lot and perhaps pro-
cess and fabricate a small amount ofthe material in the laboratory orfactory
to verify that it is satisfactory.
Typical specifications ofthree calcined Bayerprocess aluminas arelisted in
Table5.3. Theparameters specifiedaresimilarto those forthe pureralumina,
but we can readily see from the specifications that these aluminas are quite
different in chemical purity and particle size (see Figs. 3.5 and 4.2). A plant
TABLE5.3 Speci6cationsofThreeBayerProcess Aluminas
Calcined
Intennediate Reactive Tabular
Characteristic Soda Low Soda (-325 Mesh)
Chemical analysis (wt%)
AI
2
0
3
99.4 99.7 99
Si0
2
0.02 0.02 0.2
Na20 0.25 0.08 0.10
Fe
2
O) 0.04 0.01 0.3
CaO 0.04 0.01 0.07
LOI (l100C) 0.2
Total water" 0.3
ex Alumina phase (%) 90+ -100 -100
Ultimate crystal size (/Lm) <5.0 >0.5
Particle size distribution >95
Sieve analysis (wt %)
+100 mesh
+200mesh
+325 mesh
-325 mesh
Sedimentation analysis
b
(/Lm)
90%< 40 1.5
50%< 12 0.5
10%< 3 0.2
Specific surface area
c
(m
2
/g) 1.0 3-6
Specific gravity 3.8 3.98 >3.4
Bulk density (Mg/m
3
) 1.0
Source: Products ofAlumnum Company ofAmerica, Pittsburgh, PA.
"I100C gnton loss afteradsorption ai 44% relatve humidity.
hOravity settling.
'Nilrogenadsorption.
engineer examines the preshiprn
lhe particular10t ofmaterial. De
applcation, aseIofcharacteristic
standardized test procedures, in
orrejecting a shipment.
Specifications for threedilfere
ceramics are listed in Table 5.4
chemicalandparticlesizechame
concentrationofCO
2
and S03m
tants during calcination. DilfereJ
reflectthe variations in thecheIJI
ofthe raw materiais and microsl
Specifications for the COIIllll4
basic chemical and particle size
eral types and mineral impuritie
index is a relative indication 01
sorption ofmethylene blue dye.
sions, and the pH index ofa
TABLE5.4 TypicalSpecificatio
Character
Chemical analysis (wt%)
Si0
2
AI
2
0)
Ti0
2
srO
BaO
Na20
S03
CO
2
LOI
Size analysis (/Lmt
90%<
50%<
10%<
+325 Mesh (%)
Bulkdensity (Mg/m
3
)
Electrical Property Analyses (bodl
magnesium zirconate):
Dielectric constant (25C)
Dissipation factor(% at 25C)
.:l Dielectric constant (\00C)
.:l Dielectric constant (- 10C)
Fired density (Mg/m
J
)
"Products ofTAM Ceramics lnc., NI
cha.racterization is necessary
by the raw-material
5.2 lists typicaJ speci-
materiais. The impurity
phase is identified. The
agglomeration and crystal
materiais, the customer
each lot and perhaps pro-
in the laboratory or factory
aluminas are listed in
for the purer alumina,
these aluminas are quite
3.5 and 4.2). A plant
Reactive
Tabular
Low Soda
(-325 Mesh)
99.7
99
0.02
0.2
0.08
0.10
0.01
0.3
0.01
0.07
-100
-100
>0,5
>95
1.5
0.5
0.2
3-6
3.98 >3.4
PA.
RAWMATERIAL SPECIFICATIONS 73
engineer examines the preshipment specifications supplied by the vendor for
the particular lot of material. Depending on past experience and the particular
application, a set of characteristics may be determined for a small sample using
standardized test procedures, in the purchaser' s labo rato ry , before authorizing
or rejecting a shipment.
Specifications for three different barium titanate powders used for electronic
ceramics are listed in Table 5.4. These materiaIs are prepared with different
chemical and particle size characteristics, as indicated in the specifications. The
concentration of CO
2
and S03 indicates the incomplete decomposition of reac-
tants during calcination. Differences in the electrical properties of a fired body
reflect the variations in the chemical stoichiometry and physical characteristics
of the raw materiaIs and microstructure developed during firing.
Specifications for the commercial kaolins listed in Table 5.5 include the
basic chemicaI and particle size characteristics. The composition of c1ay min-
eral types and mineral impurities such as free quartz are not listed. The MBI
index is a relative indication of the specific surface area determined by ad-
sorption of methylene blue dye. Clay bodies are usually processed as suspen-
sions, and the pH index of a suspension may suggest the compatibility or
TABLE 5.4 Typical Specifications of Calcined Barium Titanates
Character Capacito r MLC Piezoelectric
Chemical analyss (wt %)
8i0
2
0.10 0.12 0.15
AI
2
0
i
0.10 0.14 0.16
Ti0
2
34.64 33.95 33.38
8rO 0.90 0.78 0.91
BaO 63.59 64.28 64.18
Na20
0.10 0.17 0.15
80
3
0.15 0.14 0.18
CO
2
0.09 0.15 0.43
LOI 0.17 0.32 0.57
8ize analysis (/lmt
90%< 4.5 5.5 5.4
50%< 1.6 2.3 2.0
10%< 0.8 1.0 0.8
+325 Mesh (%) 0.02 0.02 0.02
Bulk density (Mg/m
3
) 1.8 2.4 2.0
Electrical Property Analyses (body contains 10% calciurn zirconate and 1 %
magnesium zirconate):
Dielectric constant (25C) 5250 4000 4400
Dissipation factor (% at 25C) 1.18 0.83 0.67
Ll Dielectric constant (l00C) -52.9 -48.9 -54.0
Ll Dielectric constant (-10C) -33.7 -2.4 -4.9
Fired density (Mg/rn
J
) 5.30 5.54 5.60
"Produets of TAM Ceramics Ine., Niagara Falis, NY.
74 CHARACTERISTICS ANO SPECIFICATIONS OF CERAMIC MATERIALS
cations ofthe lot-to-Iol reprocl
TABLE5.5 Typical SpecificationsofCeramic-Grade Kaolins
material cost. Processing alten
Characteristic NC
a
GA-p
b
GA-C
b
terials processors should deter
Chemical analysis (%)
uisite for control ofthe proces
Si0
2
47.72 45.36 45.74
AIP3
37.53 38.26 38.25
Fe
l
O) 1.16 0.36 0.41
SUGGESTED READING
Ti0
2
0.08 1.52 1.55
CaO 0.47 0.06
1. F. H. Norton, Fine Ceramics,
MgO 0.04 0.12
2. W. M. Flock, "Characterizati
Kp 1.17 0.21 0.06
before Firing, GeorgeY.Ono
Na20 0.15 0.11 0.14
New York, 1978, Chapter4.
LOI 14.04 13.47 13.66
3. G. Y. Onoda]r. and L. L. f
Total 99.85 99.80 99.99
Ceramic Processing before Fil
Particle sizeanalysis
Wiley-Jnterscience. New Yorl
(cumulative mass percent finer)
20 (/-tm) 97.5 98.0 97.0
4. Y. S. Kim, "EffectsofPowd
10 89.0 93.5 88.0
and Technology, Vol. 9, Fm
5 75.0 83.0 74.5
1976, pp. 51-67.
2 53.0 65.0 54.0
I 35.0 48.5 38.0
0.5 32.0 21.5
PROBLEMS
0.2 15.0 11.0
c
MBI (meq/IOO g) - 7.8 2.0
5.1 What is the relatonship
pH 5 7.2 4.3
porting the impurity in a
PCE 33-34 34-35 34-35
Dry MOR (MPa) 1.2 3.4 0.9
5.2 Calculate and compare t
in the two alphaalumil1ll
"North Carolina kaolin, Harris Mining Co. Inc., Spruce Pine, NC.
bGeorgia kaolin, Cyprus Industrial Minerais, Inc., Sandersville, GA. (GA-P torplastic forming,
5.3Calculateandcomparetil
GA-C for casting.)
size 50%< for thetwo
'Contains halloysite with tubular particle shape.
5.4Calculate the bulkdensi
and compare your resull
5.3.
changein pHifoneclay is substituted foranother. Thepyrometricconeequiv-
alent (PCE) indicates the relative resistance ofa material to vitrification and
5.5 Ca1culate the impurity I
creep on heating. The MOR is the flexural strength ofdried bars formed by
barium titanate powders
extrusion. The pH, PCE, and MOR are not characteristics; rather, they are
rities?
indices that indicate something about effects ofsoluble chemical impurities,
impurity phases, and the particle size distribution on the chemical, thermal,
5.6Thechemicalanalyses(
and mechanical behavior, respectively.
grade barium titanate3.1
SrO
SUMMARV
BaO
Ti0
2
The characteristics ofa material are the parameters necessary for its identifi-
cationordescription. Specifications provided by suppliersofmateriais provide
What is the reproducibi
some ofthese characteristics. More complete specifications or tighter specifi-
MATERIALS
Kaolins
45.36
38.26
0.36
1.52
0.47
0.04
0.21
0.1I
13.47
99.80
98.0
93.5
83.0
65.0
48.5
32.0
15.0
7.8
7.2
34-35
3.4
45.74
38.25
0.41
1.55
0.06
0.12
0.06
0.14
13.66
99.99
97.0
88.0
74.5
54.0
38.0
21.5
11.0
2.0
4.3
34-35
0.9
(GA-P for plastic fonning,
pyrometric coneequiv-
to vitrification and
dried bars fonned by
; rather, they are
chemical impurities,
the chemical, thennal,
.ece:ssalty for its identifi-
ofmateriaIs provide
_ltiOllS ortighter specifi-
PROBlEMS 75
cations ofthe lot-to-Iot reproducibility ofa material commonly increase the
material cost. Processng alters the characteristics ofthe particle system. Ma-
teriaIs processors should detennine the materiaIs characteristics that are req-
uisite for control ofthe processing and the properties oftheirproducts.
SUGGESTED READING
l. F. H. Norton, Fine Ceramics, Krieger, Malabar, FL, 1978.
2. W. M. Flock, "Characterizationand Process Interactions," in Ceramic Processing
before Firing, George Y. OnodaJr. and LanyL.Hench, Eds., Wiley-Interscience,
New York, 1978, Chapter4.
3. G. Y. Onoda Jr. and L. L. Hench, "Physcal Characterization Tennnology," in
Ceramic Processing before Firing, GeorgeY. OnodaJr. andLanyL.Hench, Eds.,
Wiley-Interscience, New York, 1978, Chapter5.
4. Y. S. Kim, "EffectsofPowderCharacteristics," in Treatise on MateriaIs Science
and Technology, Vol. 9, Franklin F. Y. Wang, Ed., Academic Press, New York,
1976, pp. 51-67.
PROBLEMS
5.1 What is the relationship between parts per million and percent when re-
porting the impurity in a solid substance?
5.1 CaIculate and compare the impurity analysis ofthe five major impurities
in the two alpha aluminas in Table 5.2. Use an elementary oxide basis.
5.3 Calculateandcomparethesharpnessindex (size90%< size 10%<)1
size 50%< for the two Bayerprocess aluminas in Table 5.3.
5.4 Calculate the bulk density as a percent forthe two aluminas in Table 5.2
and compare your results to the value for the calcined alumina in Table
5.3.
5.5 Calculate the impurity leveI ofCO
2
and S03 in parts per million for the
barium titanate powders in Table 5.4. What is the source ofthese impu-
rities?
5.6 Thechemicalanalyses (wt%)ofthreeproductionlotsofcaIcinedcapacitor
grade barium titanate areas follows:
SrO 0.95 0.82 0.84
BaO 63.71 64.00 63.94
Ti0
2
34.67 34.61 34.59
What is the reproducibilty ofthe molar ratio (BaO +SrO)/Ti0
2
?
76 CHAAACTEAISTICS ANO SPECIFICATlDNS DF CEAAMIC MATEAIALS
5.7 Which parameters in Table 5.5 are characteristics and which are pro per-
ties? Explain your reasoning.
5.8 Compare the content of colloidal sizes for the two Georgia kaolins in Table
5.5.
5.9 Explain why the tubular particles in NC kaolin may cause a misinterpre-
tation of dye adsorption index MBI (see Table 5.5).
EXAMPLES
Example 5. 1 What are diferences n agglomerate characteristics for the spe-
cial caIcined aluminas in Table 5.2.
Solution. The mostly gamma phase alumina has the largest mean agglomerate
size of 2 ,um and the smallest crystallite size (ultimate particle size) of 0.01
,um; the size ratio is 2/0.01 or 200. For the other aluminas calcined at a higher
temperature, the agglomerate size is smaller and the crystallite size is larger;
therefore, the agglomerate size and the number of particles in a mean agglom-
erate is lower. The greater agglomeration of the gamma alumina is reftected in
its lower apparent bulk density.
Example 5.2 What is the nominal purity of the barium titanates in Table
5.4?
Solution. The elementary oxides forming the perovskite structure are BaO,
SrO, and Ti0
2
Summing the weights of these gives 99.1 % purity for the
capacitor, 99.0% for the MLC, and 98.5% for the piezoelectric type of ma-
terial. The nominal purity is 99 % .
Example 5.3 Compare the stoichiometry for the three types of barium titan-
ates in Table 5.4.
Solution. Ideally, stoichiometric barium ttanate contains 1 mole of alkaline
earth oxides (BaO + SrO) and 1 mole of Ti0
2
The moles of the oxide com-
ponents are found by dividing each by its molecular weight. For the capacitor
grade material,
moles BaO = 63.54 g/153.34 g/mol = 0.415
moles SrO = 0.90 g/103.62 g/mol = 0.009
moles Ti0
2
= 34.64 g179.88 g/mol = 0.434
(BaO + SrO)/Ti0
2
mole ratio (0.415 + 0.009)/0.434 = 0.976
Calculating in a similar mannel

Piezoel
It is observed, after sintering,
the mole ratio > I; the grain s
Example 5.4 What are the in
powders, and colloids?
Solution. The diferences in p:
in the table below:
Parameter

Size (/km)
>44
F
A
vs. Fw
F
A

Flowabilty GoodC
Agglomeration

Vol. Ads./Vol. Par.
InsigniJ
Note: F
A
is Van der Waals attractivl
volume of adsorbed processing additi
EXAMPLES 77
and which are proper-
Calculating in a similar manner, the mole ratio for the other types is
MLC Type 1.005
Georgia kaolins in Table
Piezoelectric 1.02
may cause a misinterpre-
It is observed, after sintering, that a much larger grain size is obtained when
5.5).
the mole ratio > 1; the grain size strongly influences the electrical properties.
Example 5.4 What are the important differences between granular materiais,
powders, and colloids?
characteristics for the spe-
So/ution. The differences in particle characteristics and behavior may be seen
in the table below:
largest mean agglomerate
Parameter Granular Material Powder Colloid
particIe size) of O. O 1
Size (ltm) >44 44 - 1 <1
calcined at a higher
F
A
vs. Fw F
A
Fw F
A
= Fw F
A
Fw
crystallite size is larger;
Flowability Good (free ftowing) Poor Very poor
in a mean agglom-
Agglomeration Minimal Spontaneous Spontaneous
alumina is reftected in
Vol. Ads.lVol. Par. Insignificant Significant Very significant
Note: F
A
is Van der Waals attractive force. Fw is particle weight. Vol. Ads.lVol. Par. is lhe
volume of adsorbed processing additive relative to the volume of the partcle.
barium titanates in Table
structure are Ba,
99.1 % purity for the
piezoelectric type of ma-
types of barium titan-
I mole of alkaline
moles of the oxide com-
weight. For the capacitor
.434 = 0.976