Alumina : sintering and optical properties

Peelen, J.G.J.

DOI:
10.6100/IR4212

Published: 01/01/1977

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Peelen, J. G. J. (1977). Alumina : sintering and optical properties Eindhoven: Technische Hogeschool
Eindhoven DOI: 10.6100/IR4212

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ALUMINA: SINTERING AND
OPTICAL PROPERTIES

PROEFSCHRIFT

TER VERKRlJGING VAN DE GRAAD VAN DOCTOR

IN DE TECHNISCHE WETENSCHAPPEN AAN DE
TECHNISCHE HOGESCHOOL EINDHOVEN, OP GEZAG
VAN DE RECTOR MAGNIFICUS, PROF. DR. P. VAN
DER LEEDEN, VQOR EEN COMMISSIE AANGEWEZEN
DOOR HET COLLEGE VAN DEKANEN IN HET OPEN·
BAAR TE VERDEDIGEN OP DINSDAG 17 MEl 1977
TE 16.00 UUR

DOOR

JAN GERARD JACOB PEELEN

GEBOREN TE RENKUM
Dl1' PROEPSCHRlFT IS GOEDGEKEURD DOOR DE PROMOTOREN
PROF. JR. A.L. STUIJTS EN DR. R. METSELAAR
Alln Beitsche
Aan Evelien, Marc en Janine
Aan mijn oudas
DANKWOORD

lIe! onderzoek beschreven in dit procfschrift is uitgevoerd op hct Natuurkundig

Laboratorium van de N.Y. Philips' Gioeibmpenfabrieken te Eindhoven. lk ben de
dirccti.;; van dit iabocatoriul1l erkentelijk voor de mij geboden gelegcnhcid om het
onder7.oek in dele vorm te publiceren,

Gaarne wil ik mijn dank betuigen aan allen, die bij de uitvocring van de experimcn-
ten betrokken zijn geweest en aan de lotstandkoming van dit procfschrift hebben
bijgcdragcn, Ecn belangrijk deel van het ondcrzock is geda~n in samenwcrking met
Dr. R. Metselaar. Yoor dCl.e samenwe!'king ben ik hem vcc1 dank verschuldigd.
MijI\ dank gaat verder uit naar mijn coHcga's, die het manuscript van dlt proefschrift
krilisch hcbbcn doorgelezen.
CONTENTS

I. INTRODUCTION
1.1 Properties of alumina . . . . . . .
1.2 Application of alumina as a lamp envelope 2
1.3 The present investigation 2
REFERENCES . . . . . . . . . . . 4

2. SINrERJNG OF ALUMlNA AND THE lNFLUENCE OF DOPES 5

2.1 Short introduction to the sintering process . 5
.2.2 Sintering of alumina, Review of the literature 8
2.2.1 lnfluence of impurities. . . . . . 8
2.2.2 Influence of grain boundaries. . 'I
2.2.3 Influence of additives on sintering. Defect structure. 11
2.2.4 Influence of additives on the microstructure. , . 12
2.2.5 Conclusion ............. 14
2,3 Influence of MgO on the evolution of the microstructure 14
2.3.1 Introduction . . . . 14
2.3.2 Experimental prooedures . . . . . . 16
2.3.3 ReSults . . . , . . . . , . . , 18
2.3.3.1 Influence of MgO on the dens.ity 18
2.3.3.2 lnfIuence of MgO on the grain size 19
2.3.3.3 lnl1uence of extra addition ofeaO and Y103 24
23.3.4 Auger spectroscopy 26
2.3.4 Discussion . 29
2.3,5 Conclusion. 31
REFERENCES . . . 32

3. HOT PRESSING OF ALUMINA 37

3.1 Introduction to hot pressing 37
3.2 Continuous hot pressing 38
3.3 Results and discussion 40
3.3.1 Influence of the atmosphere 41
3.3.2 Influence of the hot-pressing parameters 43
3.3.3 Influence of powder properties . . . 45
3.3.4 The mic\"ostructure of hot-pressed alumina 46
3.3.5 Crystallographic texture of the grains 49
3.4 Conclusion. 52
REFERENCES . . . . . . . . 53

4. OPTICAL PROPERTIES OF ALUMINA 55

4.1 General introduction . . . . 55
4.1.1 Review of the literature 56
4.1.2 Factors contributing to transmission losses 57
4.2 The in-ljne trans)ni~siQn 59
4.2.1 Scattering theory. 59
4.2.2 Calculation of the in-line tf<lmmission 63
4.2.2.1 Pores with a fixed radius 63
4.2.2.2 Porc siLC diSlribution 68
4.2.2.3 Inl1ucIlcc of the pore size distribution on the scattering
coefficient . 69
4.2.3 Measurements of the in-line transmission 71
4.2.3.1 IntlL!cnce ,)f the pore siLc . 73
4.2.3.2 Influence of the MgO content 75
4.2.3.3 Int1uence of extra addition of CaO and Y1 0 3 77
4.2.4 Dekrminalion of microstructural paramotcrs [rom the measured
transmission spectra. 78
4.2.5 Conclusion. 83
4.3 Transparent and lranslucent alumina 83
4.}.1 Introduction , 8}
4.3.2 Theoretical c()nsiderations 85
433 Experimental part 86
4.3.4 Rc~ults and disC\lssion 89
4.3.S Conclusion, 92
REFERENCES 94

SUMMARY 97
SAMENV ATTlN(~ 99
L INTRODUCTION

1.1 Properties of alumina

In ceramic literature the term "alumina" is used rather loosely to denote

L aluminous material of all types taken collectively;
2. the anhydrous and hydrous aluminium oxides taken indiscriminately;
3. the calcined or substantially water-free aluminium oxides, without distinguishing
the phases present, and
4. corundum Dr alpha alumina, specifically.
Gitzen I) in his standard review on alumina uses the term in the sense of the second
definition. In the present work we wHl use the term in the SenSe of the fourth defini·
tion. Many other phases like gamma, delta, cIa, kappa, chi, rho, theta alumina, all
corresponding to the molecular formula Al2 0 3 , are described in the literature. They
are all transition phases and some of them are of doubtful existence or the differences
are mainly baSed on somewhat subtle X-ray diffraction differences.
Beta alumina is not a monotropic form but it is a mixed oxide containing alkali or
alkaline earth atoms. More information on these compounds can be found in the
literature 1,2).

Alpha alumina, the only thermally stable oxide of aluminium, has the corundum
structure. This structure may be described as a slightly distorted hexagonal close-
packing of oxygen ions. The aluminium ions occupy two-thirds of the octahedral
inlerstices, while one third is empty. This structure is extremely stable. The formation
energy of alumina is about 400 kcal/mol, only exceeded by the oxides of some rarc
earth metals, like La.
Consequences are an extremely low vapour pressure and a high melting point
(2045 °C). The deviation from the stoichiometric composition of alumina at normal
atmospheric conditi(ms is < 5 x 10'$ even at 1600 °c ~).

Alumina has a unique combination of useful electrical, mechanical and chemical

jJroperties. Electrically it possesses high resistivity (around 10 17 nem at room
temperature), good dielectric strength and a low dielectriC loSS factor at high
frequencies. These electrical pr<Jpertjes were already applied early in the technical
development of sintered alumina as insulators for spark plugs. The electrical con-
ductivity is very sensitive to the purity of the oxide.

Mechanically, alumina possesses great hardness, resistan~e to abrasive wear and

dimensional stability. The strength properties of ~i!1tered alumina are strongly
influenced by the microstructure: porosity, grain size, pore size, second phases.
In the application of alumina as cutting tools use is made of its special mechanical
properties.

Finally, alumina i~ inert against attack from most chcmicals and can be used in severe
2

environments. Even sodium does not provoke any appreciable reaction. Alumina
maintains these characteristics to high temperatures: the working temperature can
be \lP to 1500 °c.

I.! Application of alumina as a lamp envelope

The combination of the above·mentioned properties makes sintered alumina a very

suitable material to be used as a lamp envelope in the high·pressure sodium lamp.
This lamp is based on the phenomenon that the n{)[mally narrow spectrum of sodium
light can be broadened to cover most of the visible spectrum, if the sodium pressure
and temperature inside the lamp are increased 4).The lamp produces a golden.white
light with a very high efficiency. The material of the discharge tube has to resist the
,mack from ~odium vapour at 1250 QC, and of course the light loss in the visible part
of the spectrum should be as low as possible.

To meet the latter requirement a material of very low porosity has to be used. In the
fifties t.he problem in sintcring alumina waS the effect. of discontinuous grain growth.
The somewhat larger grains with more strongly curved boundaries tend to grow very
fast, so that pores become enclosed in the grains and are unable to diffuse out. In
1960 Coble and Burke ., ,6) slIcceeded in suppressing discontinuous grain growth by
adding 0.25 wt % MgO to the alumina. This drastically reduces the numbet of pores
that Me trapped inside the grains and prolonged Sinterlng then produces a material
that transmits light. reasonably wdl, thoush very diffusely. The material is oalled
LucaloJ( (derived from translucent aluminium oxide) or DGA (derived from "door-
schijncnd gasdicht aluminiumoxidc") and has found wide application. The lamp
envelopes made with it proved to be capable of withstanding attack from the hot
sodium vapour for more than 20000 hours.

1.3 The present investigation

After this important. practical result a number of fundamental questions remained.

How MgO could suppress the discontinuous grain growth in alumina W<lS not under-
stood. In numerous publications many ideas about the- role of a sintering additive
were developed. A complication in the study of the sintering of alumina is the
important role th~t impurilies i.e. not intentionally added ~dditives rMy play. It is
very diftkult to prepare alumina on a largo soale with impurities in the ppm range,
and many sintering studies have been carried Ollt with impure powders, making the
results questionable to say the Iea~l.

Another unanswered question waS how the transmission of light through sintcrod
alumina is related \.0 tbe mi;;;rostrllcture. The material Lucalox was introdl\Ced as an
essentially pore-free material due to the action of MgO 7). A high density and a
large grain size were thought to be necessary for a high light transmission, while the
influence of the pore sile was not noticed. The lack of transparency of sintered
 3

alumina was ascribed to guin boundary scattering and the intrinsic birefringence of
alumina. Some recent developments point in another direction. It proved to be
possible by continuous hot pressing at a relatively low temperature to produce a
transparent material with a 25 times lower grain size than the normally sintered
alumina 8). This indicate~ that not the size of the grains but the size of the often
neglected pores determines the optical properties of dense alumina. Moreover,
application of the theory of light scattering showed that the transmission of
poly crystalline alumina could be described very well with the parameters pore size,
number of pOres and spread in the pore size distribu tion 9).

This thesis is the result of an investigation to answer the above-mentioned funda-

mental q\lestions. Dense alumina samples with micrustructures widely varying in
grain size and pore size have been prep;ned by normal sinteting and hot pressing.
nle~e samples have been used to verify the statement that pores mainly determine
the transmission of light through polycrystalline alumina 8,9). The in t1ucn~e of
MgO on the sintering behaviour of alumina was investigated by studying the
evolution of the microstructure for samples with increasing amounts of additive 10 ).

Chapter 2 of this thesis gives a survey of the intluence of impurities and additives
on the sintering behaviour of alumina. It also describes the influence of MgO on the
evolution of the microstructure of alumina.

Chapter 3 deals with the hot pressing of alumina powder. The microstructures of
normally Sinlercd and hot-pressed alumina are compared.

Chaptet 4 deals with the uptical properties of polycrystalline, dense alumina. Jt

gives relations between the light transmission and the microstructure of materials
sintered in the normal way as described in chapter 2, Or hot-pressed as described in
chapter 3. The questi(Jn whether a material should be called transparent Or trans·
lucent is also treated in chapter 4.
4

REFERENCES

I) W.H. Gitzen, AhLrnina as a Ceramic Material, Am. Ceram- Soc., 1970.

2) B.C. Lippens, Structure and Texture of Aluminas, Thesis, Delft, 1961.

3) R,W. Vest, citeda~privatecommunlcaticmin JJ. Mills, J.Phys.Chem_

Solids 31, 2577 (1970).

4) L.B. Beijer, H _1.1 _ van Boort and M. Ko~dam, Ughting Design &
Application, 4,15 (July 1974).

5) R.L Coble and I.E. Burke, Proc_4th Int. Symp. on the Rw;tivity of
Solids, Eds 1.11. de Boer et aI., Elsevier Pub!. Co., Amsterdam, 1961, p_38.

6) RL- Coble, 1. App!. Phys. 32, 793 (1961).

7) C.L brochure on Lucalox, Lamp Glass Department, General Flectri(; Co ..

Cleveland, Ohio, J 970_

8) 1 _G _1. Peden, Science of Ceramics 6, XVH (1973).

9) 1 _G.J. Peden and R- Metselaar, 1. App!. Phys_ 45,216 (1974).

10) J.C.J. Peelen, Mat. Sci. Res. to,443 (1975)-

 5

2. SINTERING OF ALUMINA AND THE INFLUENCE OF DOPES

2.1 Short introduction to the sintering process

The process to convert powder compacts into dense products is called ~intering. It
can be described as the thermally activated proce~s of densification of compacts at
temperatures below the melting point. During sintering many changes ()CCUL The
essential characteristics are tho increase in strength of the powder compact caused
by the formation of bonds between the particles and the shrinkage of the compact
as the void spaces between the particles decrease in size and are ultimately almost
completely eliminatcd.·Another characteristic is the increase in average grain size.
Sometimes very large grains can develop during sintering. This complex process of
sintcring is influenced by a variety of factors: the nature of the powder, impurities,
intentional additions, pressing conditions, sintering temperature, time and atmo·
sphere. Because of the complexities involved, it is impossible to fit the sintering
process in onc model.

Looking closer at the process of sintering, we can distinguish three different stages
of sintering:
1. DUring the initial stage particles begin to adhere together and necks grow
between the particles. At the end of this stage grain boundaries are established
and grain growth begin~ to occur. Shrinkage is only a few percent.
2. During the intermediate stage grain growth continues. Continuous pore channels
are formed along the grain edge~. The cross·section of these channels dCcreascs
gradually until at the end of this stage, at a relative density of about 95%, the
channels are pinched.
3. In the final stage dosed pores are formed at the grain boundaries and grain
COrnerS. This final stage m~y lead to an almost completely dense material by
removal of these pores, or, alternatively, the pores may be trapped inside the
grains when the boundaries break aWilY from them: the problem of pore·grain
boundary interaction becomes dominant. P(lre growth will occur as well.

Figure 2.1 illustrates the initial stage of the sintering of alumina. It shows the
original powder particles and the necks growing between them.

Sintcring requires displacement of atoms, of cations and anions, and this process is
determined by diffusion. Several mass transport mechanisms have been proposed as
contributing to sintering, some processes producing shrinkage and others producing
no shrinkage, In all cases matter flows into the neck between the powder particles.
The six mechanisms for this flow of matter, as ccmsidered by Ashby I), have been
Collected in table 2.1. In figure 2.2, which is a plane section through an assembly
of three spheres, the possible diffUSion paths are shown.
6

Fig. 2.1. Scanning electronmicrograph of the initial stage of sintering process, showing neck
growth between the particles. White bar is 1 lim.

GRAIN
\'BOUNDARY

Fig. 2.2. Three-sphere model showing the six transport paths from table 2.1 (page 7). In all
cases neck growth occurs, but only path 4 to 6 lead to densification (from ref. 1).
 7

Table 2.1

Mechanism No. Transport path Source of matter Sink of matter

I Surface diffusion Surface Neck
2 Lattice diffusion Surface Neck
3 Vapour transport Surface Neck
4 Boundary diffusion Grain boundary Neck
5 Lattice diffusion Grain boundary Neck
6 Lattice diffusion Dislocations Neck

Mechanisms only leading to rounding off of the pores without shrinkage include
evaporation of matter from the convex surface of the particles and condensation
in the neck between the particles. It is doubtful whether this method of mass trans-
port is very important in the sintering of an oxide with a low vapour preSSure such as
aiumina. Another mechanism by which matter can be transported without shrinkage
is surface diffusion. This can be a competitive process with other processes that
produce Shrinkage, especially at low sintering temperature.

The shrinkage of alumina can best be explained by assuming atomic diffusion along
two different paths of diffusion. Volume diffusion or lattice diffusion involves the
transport of material from the grain boundary tluough the lattice int(1 the neck
between the particles, while in grain boundary diffusion the grain boundary itself
might be the path along which the atoms move. Both transport mechanisms will
contribute simultaneollsly to the sintering process.
Johnson ~) has proposed sintering rate equations for conCUHent volume, grain
boundary and even surface diffusion.

The driving force for sintering is the excess free energy of a powder compared with
that of a dense material. The decrease in free energy occurring on sintering a powder
of 1 pm particle size is about 1 cal/g. Part of the initial surface energy is used to form
grain boundaries. This grain boundary energy delivers the driving force for grain growth.

The sintering process cannot be treated in all details here. Suffice it to remark that it
is a great step from a two or three particles model to the kinetics of densification of
real powders having a particle size distribution, no spherical shape, etc, Therefore,
discrepancies between theory and practice are often found. In ionic compounds effects
from a difference in diffusivity of cations and anions have to be considered. This
has often been underestimated in the ceramic literature. Ready 3) and Reynen ~)
have pointed to the effect of non "stoichiometry on sintering, which sometimes can
be very large. Review papers on sintering are included in the list of references S-s).
Some aspects of importance to an understanding of the sintering behaviour of
alumina are treated in the next section, These aspects include the influence of
impurities and grain boundaries on sintering, the defect structure of alumina and the
8

inl1ucncc of additives on the Il1icro~tructurc of alumina_ Section 23 is devoted

mainly to the ini1uence of magnesia on the ev()luti()n of the microstructl1[e of
alurnina.

2_2 Sintering of alumina. Review of the literature

2.2.1 In/luencro oIimpuritfes

Since sintcdng is dependent on diffusion processes, it is important to know what

kind of point defects are present in alumina and in what concentration, In the caSe of
intrinsic diffu~ion the fraction of point defects is determined only by the temperature
and the energy, hj; it costs to create the defects. Compared with NaCl, for instance,
alumina is a rather unknown material. In the case of alumina there is still doubt as
to whether a Schottky or a Frenkel type defect structure is present (see sec- 2_2_3)
and the energy for defect formation is unknown. Oishi and Kingery 9) measured
jS 0 diffusion both in poly crystalline arid in monocrystalline Alz 0 3 , It can be

deduced from their results that it costs an energy of 20.5 eV to create 2 Al vacancies
~nd 3 0 vacancies.
Fryer 10,1 t ) analyses his results on pressure sinlcring of undoped alumina in a
different way _He believes that the activation energy he observes can be ascribed to
intrinsic diffusioIl arid he arrives at a Schottky formation energy of 10 eV_ His
analysis taken over by others 12), however, is very doubtfuL It is unlikely that his
starting powder, Linde A, permits intrinsic behaviour at temperatures as low as
1200 - 1400 or- In a recent publication Dienes et aL 13) give a calculated value
of 28.5 eV necessary to create a Schottky quintuplet or 20 eV to Create a Frenkel
pair in the Allatlice_ B()(h values arc very high compared with ii/= 2.3 eV for NaC!.
As a conScqllcrlcc, tho concentration of intrinsic vacancies will be extremely low,
even at high temperatures. With the value of 20.5 eV the fraction of vacant calion
sites at 1600 °c can be estimated as 10- 10 , 1'his is much lower than the impurity
level of the purest alumina!

It is dear from this that only extrinsic diffusion behaviour carl b~ expected: the
vacancy conccntJ'ation will be controlled by the number and nature of impurities
present. ~nd will be independent of tempel'ature. Add to this that many impurities
have a very limited wlubilily in alumina Blld thet'efore, they will be present as a
dispersed second phase. The presence of these impurities in not well characterized
starting materials may explain the many contradictory reslllts, which typify the
investigations of diffusion in alumina, such as sintcring behaviour, electrical
conductivity etc, (see figure 23).
As a consequence, alumina is by no meanS a suitable model material for sintcring
research 8,14).
Anion impurities can be as effective as cation impurities 15), although they have
usually been neglected.
 2000 lOOQ 200

4 5 10 15 <0
10'{7'rK)

Fig. 2 .3. R~po,td lit¢,at"," data fOr tho electrical cunciuctivity of alumina (f,om ref. 16).

2.2.2 Influence oigrain boundaries

Sintering requires displacement of both cations and anions by diffusion. The main
diffusion paths lie in the volume of the grains and in the grain boundaries. The
relative effectiveness of both will be affected by the microstructure. It is very
difficult to assign an exact grain boundary width. Mistler and Coble 17), analysing
grain growth and sintering data, give a value of about 100 A.

At a grain boundary the atoms are less densely packed and this may result in a lower
activation energy for boundary diffusion and a greater atomic mobility.
Oishi and Kingery 9) demonstrated that the oxygen ion self-diffusion coefficient is
enhanced by the presence of grain boundaries. Paladino and Kingery 18) measured
the diffusion of 26 AI onJy in polycrystalline alumina and they state that diffusion
of AI is not influenced by the presence of grain boundaries. The combined results
are given in figure 2.4. Based on these results and on an analysis of the
apparent diffu~ion coefficient in sintering and creep experiments, Paladino and
Coble 19) conclude that volume diffusion of Al is the rate-controlling process in the
sintcring of fine.grained alumina, while 0 diffuses more rapidly along grain bound-
aries. For grain sizes larger than 20 p,m they expect the diffusion of oxygen to be
rate·controlling.
In a later analysis Mistler and ~oble 20) expect the change-over from Al to 0 rate
control to take place at a grain size of 5 .urn. It is very difficult to deduce the
10

Ternll"!"t'11.'r'$II.';'
19~O le.SCl liM 1650 I~~O 1450 13!:£1 1~'5O

Fig. 2.4. Combined ,osul" of the oxygen diffusion measurements of Oishi and Kin~ry·) and
[he aluminium diffusion measurements of Pa.Lldino and Kingt;;:t'y 11').

kinetics from calculated values of the diffUSion coefficient or activation energies

for a process such as sintering, because the values of Do and DAI are S() similar. This
may explain why the sintering mcchanism has been ascribed to volume diffusion and
grain-boundary diffusion 21). Enhanced oxygen diffusion along grain boundaries has
also been reported for other oxides, like MgO 2~), Fe203 23) and CoO 24). Enhanced
cation diffusion has been reported for U0 2 2S).

Grain boundaries may int1ucnce the diffusion ofions in another way. It has been
shown 26 ,l7) lhat the concentration of defects near vacancy sources and sinks like
grain boundaries differs from the bulk concentration.
The reasOn is that the energies needed to creat~ anion and cation vacancies or, in
the case of a Frenkel defect strllcture, vacancies and interstitials, are different. The
consequence is that the grain boundary may carry an electric charge resulting from
the presence of excess ions of one sign. This charge is compcnsated by a spacc-
charge cloud of the opposite sign adjacent to the boundary. The distance the space
charge region extends in to the crystal is assumed to be 20 to 100 A. The sign and
the magnitude of the electrostatic potential at the boundary are determincd by both
the solute concentration, if present, and the temperature 2~). This will be true
especially for alumina with its low concentration of thermally indl1ccd lattice defccts.
 11

lGngery 28) ha~ demon~trated the existence of a boundary charge in a number of

oxides by observing the bowing of grain boundaries in an electric field at 1650 °C.
He observed a positive sign of the boundary charge in an alumina sample containing
about 1000 ppm MgO. The charge of the grain boundaries may possibly explain the
preference for grain boundary diffusion of only oxygen 29) . However, as the con·
cent ration and valence of impurities affects the charge of the boundaries, one has
to be very careful with conclusions. There is hardly any knowledge of these effects
on grain-boundary diffusion.

2.2.1 Influence of additives on sintering. Defect strncture

Many investigators have studied the initial stage of sintering of deliberately and un·
intentionally doped alumina to see, what defect model might explain the sintering
data. Not only the sintering behaviour has been studied, also the steady state creep
behaviour, thermal grooving and electrical conductivity, which are all diffusion-
controlled processes. Failure to recogni~e the importance of purity, concentration
of additives, tho presence of second phases, the intemlation b"tween ~int"ring and
grain growth, and different sintering mechanisms like grain boundary and volume
diffusion, led to great confusion in the literature (see e.g. fig. 23).

Until 1971 the basis of every explanation was a Schottky defect structure, i.e. with
AI and 0 vacancies as the main native defects. Addition of 4+ or 5+ cations would
create AI vacandes, addition of 2+ cations 0 va~ancies. In 1970 Bagleyet a!. 30)
found an increase of the sintering rate of alumina, when doped with Ti0 2 • In 1972
McAllister and Cutler 31) reported that addition of both MnO and Ti01 to alumina
increased the rate of thermal grooving. In 1973 Rao and Cutler 32) also found that
addition of FeO increased the sintering rate of alumina.
These observations are difficult to explain with a Schottky type defect structure,
since the assumption of Schottky pairs as the predominant defects leads to the
conclusion that the sintering rate of Fe.dopcd alumina is controlled by the diffusion
of 0 vacancies, whereas the sintering rate of Ti-doped alumina is controlled by the
diffusion of A1 vacancies. It is diffucult to understand such a cnange in the rate·
controlling species. If a rapid diffusion path for the oxygen ions is assumed to
explain the sintcring data for Ti"doped alumina, it is difficult to explain why the
sintering rate of alumina is enhanced by the presence of divalent cations.

In 1971 Brook, Vee and Kroger Ja), in an investigation of the electrical conductivity
of doped and undored alumina, were the first to suggest the existence of a Frenkel·
type defect structure, that is to say AI interstitials and Al vacancies as the main
native defects. An A1 interstitial is a possible defect in view of the octahedral holes
in the oxygen sublattice, one third of which are empty. Rao and Cutler 32) tried to
verify this by measuring the power by which the volume diffusion coefficient
depends on the total Fe content. With the same intention Hollenberg and Gordon "")
studied to what power the creep rate of Fe-doped alumina depends on the oxygen
12

partial pressure. They all found that the scatter in their data did not enable them
to determine the rate-controlling species Al j .. or Vo _The calculations of Dienes
et a1. I') of the formation energy of defects in alumina favour the idea of a
Schottky defect structure. In another calculation thc formatioll energy or Schottky
defects is estimated t() be greater than that of Fre)l kel defects 35) The rapid ratc
of reduction of Mg-doped alumina compared with that of Ti-dopcd alumina led
Cox 36) to ~uggest the presence of the very mobile interstitial cation in Mg-doped
samples. Recently Dutt and Kroger }1) concluded fr<)m the oxygen pressure depen-
dence of the electrical condl1ctivity of Fc-doped alumina that AJ i - - must be the
majodty defect ~pecies_

The assumption of Frenkel defects is attractive, because it makes the sintcring and
creep data consistent. The sintering rate of Fe-doped alumina can then be explained
as being due to diffusion of Al by an interstitialcy medlanism. whereas the sintering
rate of Ti-dop~d alumina is controlled by the diffusion of Al through a vacancy
mechanism. ThllS in either case the sintering rate is contrulled by the djffu~ion of Al
ions with no chang~ in tbe rate-controlling species.
For MO the incorporation reaction becomes:

(2.1)

and hr MO z :

3(MO z )s ,., 3M Ai + V Ai' + 60 0 (2_2)

2.2.4 Injluem:f! o/addiliv&s all the microstmcture

Apart from the theoretical considerations of the previous section, another goal of
additives is to lower the sintering temperature or to produce a desired microstructure
by controlling the relative rates of the competitive reactions, which occur during the
h~ating of a powder compact. The critical stage during Sinlering is the final stage.
Sint~ril1g may thm lcadto an almost completely deme material, if the pores remain
on the grnin boundaries and are able to migrate with the grain boundaries_
Alternatively, grain boundary migration may proceed too rapidly, trapping the pores
inside the grains. This will never re~ult in a very dense materiaL
This so called discontinuous grain growth (fig. 2.5) occurs when undopcd alllInina is
sintered at high temperatures.

The migration rate of grain boundaries is strongly influenced by the number, size,
geometry, and mobility of the pores, which exert a drag on the boundaries.
A gimilar drag can be exerted by impurities or additives, and the presence of a sotid
or liquid phase ',t the boundaries has also a strong inf1llence ()O the grain boundary
mobility. A basis for an understanding of the conditions, which determine pore
migration and grain boundary impurity drag was bid by Brook 38) and extended
recently by Carpay 39)_
 13

.' "
,
. .: .. . .. . ,.
:
' ,"
- . ;,. !
.
:,' , , .... "

' ...
.. :~~ -: '..
, '.
, I .,

'. ,...'
-
. ~ . ....,.: ."
: .~ . ': .
"
' .
.'
: ~". ' - ', . ,
', .. . ..... .,
: '
,

... . .

Fig. 2.5. Undoped alumina sintered for 10 h at 1850 ° C, showing discontinuous grain growth.

The effect of many additives, such as oxides, fluorides, metals, has been investigated
to overcome the discontinuous grain growth in alumina. A summing up can be found
in ref. 40). In a very recent paper Kovatschev 41) describes the influence of 16 dif-
ferent additives. Cahoon and Christensen 42) and Coble and Burke 43,44) were the
first to demonstrate that discontinuous grain growth could be inhibited by adding
0.25 wt % MgO to the alumina powder, reSUlting in a densely sintered product.
Warman and Budworth 4S) even published criteria for the selection of additives to
enable the sintering of alumina to proceed to full density. Their two criteria are:
volatility of the additive to get a uniform distribution on the grain boundaries and
insolubility of the additive in alumina for it to remain on the grain boundaries . They
found that ZnO, NiO, CoO and Sn02 gave the same result as MgO.

Rossi 46) and Rossi and Burke 47), reporting their work on finding additives other
than MgO that would permit sintering of alumina to full density, were unable to
confirm earlier work, except for NiO . They observed that many additives like CaO,
SrO, BaO, Y203 and Zr02 when sintered at high temperatures, yielded a micro-
structure similar to that shown in figure 2.6.
This microstructure is characterized by clusters of fine pores at the centre of about
150 11m large grains . Surrounding each fine pore cluster is a region which is free of
fine pores, but it may contain very coarse pores, 10 - 20 11m in diameter. The struc-
ture also shows an intergranular phase which is presumed to have been liquid at the
sintering temperature . All these additives form eutectic compositions melting below
the sintering temperature. The authors make this structure plausible, proposing a
sequence of events leading to three generations of grains.
14

Fig. 2.6. Alumina doped with 0.3 wt % Y 20, sintered for 3 hat 1900 °e, showing pore
clusters in grain centres and pore-free regions with occasional large pores (from ref. 47).

The above illustrates the strong influence of the presence of a solid or liquid phase
at the grain boundaries on the evolution of the microstructure. Less work has been
done on the influence which powder characteristics have on the occurrence of dis-
continuous grain growth in alumina. Agglomerates in the powder and density
fluctuations in the powder compact can strongly influence the microstructure 48 -51).

2.2.5 Conclusion

Densification and grain growth during sintering of alumina are influenced by a

complexity of factors . Contradictory results reported in the literature are often
caused by using poorly characterized starting powders. The diffusion during sintering
is impurity-controlled . The kinetics of the sintering process are strongly influenced
by the presence and the charge of the grain boundaries. Sintering experiments with
deliberately doped alumina can be explained consistently, if a Frenkel type defect
structure is assumed. Impurities or additives play the leading part in the evolution
of the microstructure.

2.3 Influence of MgO on the evolution of the microstructure

2.3.1 Introduction

Without doubt MgO is the most intensively studied of the additives that promote
the sintering of alumina to high densities. The great improvement in the optical and
mechanical properties of the sintered material justifies all these investigations.
Ryshkewitch 52) was the first to suggest MgO as the ideal additive for the sintering
 15

of alumina, this system having a eutectic point at 1925 °C, well above the practical
sintering temperature of alumina.
His explanation is that a dispersed phase will form a system of barriers between the
oxide particles,inhibiting their mutual contact and coalescence_
Coble 4~,44) demonstrated that alumina could be sintered with the aid of 0.25 wt %
MgO to a nearly pore-free condition. Other necessary conditions are the Use of a
carefully selected powder and sintering in an atmosphere of a gas that can readily
diffuse out of closed pores in the partially sintered compact 53). Coble's result
marked thc first achievement of a nearly pore· free mlltedaL Since that time other
materials have been developed with extremely low porosities, e.g. MgO 54), La-
doped Ph (Zr .Ti)03 for opto-eiectronic devices '5), (Ni,Z)) )Fe~ 0 4 for recording
heads 56), garnets for magneto-optical applications 57), Th-doped Y Z 0 3 for poly-
crystalline laser rods ,8), MgAl2 0 4 ,9).

MgO is often said to play the role of grain growth inhibilor. However. it does not
inhibit normal grain growth, as will be shown in sec. 2.3-4, but it only inhibits the
discontinuous grain growth. The result is that pores are nOt trapped inside the grains,
but can disappear by diffusion of vacancies_ Several theories have been put forward
to explain the role of MgO, Ryshkewitch 52) mentioned the physical separation of
the alumina grains. The action of second-phase particles of spinel located preferen-
tially at grain boundaries in pinning these boundaries and decreasing the mobility
has generally been realized 60-63). Jorgensen and Westbrook <S4) assumed that MgO
dissolves preferentiaUy in the grain boundary region, called solute segregation_ This
would cause a decrease in the grain-boundary mobility. Although they could not
give convincing experimental evidence, this assumption has found the most wide-
spread belief. Haroun and Budworth 63,65) conclude that MgO distributes itself
throughout the specimen by vapour-phase transport and then remains at the grain
boundaries as a tUm around the grains. However, an additive in solid solution can
also suppress discontinuous grain growth by reduction of the grain-boundary mobility
or increase of the pore mobility_ This wM earlier pointed out by Coble 44), and later
by Rossi and Burke 4'), although they were unable to give the precise mechanism.

The goal of the investigation to be described in this chapter was to study the
evolution of the microstructure of alumina with increasing amounts of MgO, ~tarting
far below the solubility limit. This WOrk is only possible if the available alumina
powder has an impurity content in the ppm range. Up to now no work with such
low impurities has been published_ However, only then it is possible and significant
to use MgO as an additive in concentrations as small as 50 ppm. The density and
grain size of the sintered alumina will be given as a function of the MgO content.

Auger electwn spectroscopy (AES) is a very sensitive technique to see whether

different concentrations of additive are present in the boundary and bulk regions.
Marcus and Fine 66) in 1972, who were the tlrst to apply this technique to look for
an enrichment of MgO at the grain boundarie:j>, could not detect any MgO at all, but
to their surprise they found a strong Ca cnrichmenL Before them Tong and Williams 67)
 16

reported an increased Mg concentration at the grain boundaries_ They used the

technique of spark source mass spectrometry, which makes craters about 0.3 J.lm
deep at the (;;rain boundaries. Analyses of the data of ref. 66 yielded a rather high
detection limit for Mg, so it seemed worth while to repeat their experiments.
During this work Tayl(Jr et al. 68) reported that they found an enrichment of Mg
at the grain boundaries by a factor of Z- They used the technique of X-ray photo-
electron spectroscopy (XPS), which has a somewhat greater sensitivity than AES-

23.2 Experimental procedures

All experiments described in this chapter were carried out with an alumina powder,
obtained from Rubis SyntMtique des Alpes, code A 15 RZ. This powder, made by
calcination of alum, consists of 85% Ct-AI 2 0" with a mean particle si7.e of 0_3 pm
and 15% r-Ab 0 3 with a mean particle sir.e of 0_02 /lill. The decon1p()~iti()n
reaction during calcination is accompanied by sintering, in which process luge
agglomerates can grow_ Since these agglomerate~ can have an unfavourable influence
on the sintering process, we used a p()wder deagglomerated by the manu factureI',
which reduces the mean sizo of the ag(;;lomerates from 15 pm to 4 ).Im- Figure 2.7
is an eiect.ronphot.omicrograph of this powder, showing the particles of Ct- and r-
AI 2 0 3 - The specific surface of the powder determined by the BET adsorption
method is 15 m2 (g. The impurity content was analysed spectrochemically except
for the impurities Na, K and Ca, for which the spectrochemical method is wther
insensitive_ Their cuncentration was determined by atomic absorption analysis.
The results can be summarized as follows:
Fe 5, Ga 4, Mg 0.8, Si 30, Na 10, K 30, Ca .;;; IO ppm.

The additive MgO was added as a solution of Mg acetate- 4 H1 0 (Merck, reagent

grade) in absolute alcohol to a suspension of the alumina powder in the S'lme
alcohoL This suspension was dried while continuously stirring. After further drying
the powder was sioved and prepressed in a plexiglass die to avoid CQntamirl3tion into
pellet.s 20 mm in diameter and 10 mm thick. These pellets were then isost.atically
pressed at 100 MNhn 2 and preheated in oxygen at 700°C to decompose the acetate
to oxide. The sinr.ering took place in a high-purity ahlmina tube heated in a
molybdenum resistance furnace.

Great care was taken to measure the apparent densities of the sintered spc(;imcns
because of the small difference with the theoretical density of alumina. The X-ray
density was calculated frum our experiment;llly determinod lattice parameters
a'" 4_7585 ± 0.0002 A and c = 12_9942;1; 0.0005 A to be 3_9859 j; 0.0005 g/cm 3 •
The density was determined by the method of Prokic 69), which takes into aCl;()Unt
the counterbalancing force of the air. The density of the sarnple at temperature
r,D1, can be calculated from
Mt Di - Do
M~ ~M;- v-l-=- Do (2.3)
 17

"t

;,
0'

... .
O.llJ m

Fig, 2 ,7 . Elec[ronpho[omicrograph of alumina powder used in [he sinrering experimenrs, showing

panicles ot 0,- and ,),-Al. 0 3 '
18

where MI is the weighl of the sample in air, M2 is the wm of the weight of the
sample in air and the weight of .a thin nylon thread fixed to a hook of the balance
and submerged in distilled and boiled·out water of density DJ . M,ds the weight of
the sample tied to the nylon thread and submerged in the water, Do is the density
of the air, dependent on temperature, barometric pressure and relative air humidity-
The density of water was checked using the density of a highly perfect silicon single
crystal as a reference 10). An accuracy in the apparent density of ± 0_0005 gfcm'
can be achieved. This means an inaccuracy in the pOf()sity of ± 2.5 x 10. 4 .

The microstructure of the sintered samples was studied by microscopic observation

of polished and etched samples. Polishing was done on a vibratory poliShing machine
with diamond paste_ Etching was carried out by heating the polished samples at
1450 °c for 1.5 h (thermal etching). The mean grain size was calculated using the
relation 11): G"' 1.5 T, where Tis the mean grain intercept of random lines Dn photo-
graphs of the polished and etched cfoss-sections- The value obtained in this way is
a good approximation if the size distribution of the grains is not too wide, i_e_ if no
discontinuous grain growth has occurred_

For ttie Auger experiments a commercial Auger spCdrometer was used, consisting
of a Physical Electronics Cylindrical Mirror Analy:.:er and a standard Auger ultra-
high vacuum system (VItek-Perkin Elmer). To prevent charging effects ()n alumina
we used the grazing inddcncc electron gun, the diameter of the electron beam being
about 50 Mm- In-depth profiles could be measured by means ofaXe·ion gun. Rods
2 mm in diameter were prepared from the sample and fractured in a specially
constructed break apparatus under ultra-high vacuum (10'10 Iorr). The fresh sllrfacc
was then analysed with the Auger spectron1eler.

2.3.3 Results

2.3,3.1 Influence of MgO on the density

Sintering experiments were carried out on alumina powder compacts with increasing
amounts of MgO dope, starting with the undoped alumina fOf comparison_
Figure 2.8, Cllrve A, gives the density of the specimens after sintering at
1630"C for 1.5 h in a humid H2 atmosphere (dew point 20 ·C) to prevent
yolatilization of MgO. It is seen that doping with 50 ppm MgO is already sufficient
to increase the density of alumina substantially_ The density reaches a maximum at
300 ppm dope level; at larger dope concentrations a deCrease in density is found,
Second.phase particles can be detected in the specimens with 300 ppm MgO and
more with the optical microscope_ This is in agreement with the solubility data of
Roy and Coble 7 2 ), They found for the solubility of MgO in alumina in vacuum:

In X .. 8.1 - 30 706fT, (2.4)

 19

where Xis the atomic fraction Mg/Al and Tthe absolute temperature. According to
this equation the solubility of MgO in alumina at 1630 °c is 250 ppm.
The highest density is thu~ obtained when the amount of MgO corresponds to the
solubility limit in alumina. With electron microprobe analysis Mg and Al could be
detected in the second-phase particles. The MgfAl ratio in the spinel phase was about
20 % lower than in stoichiometric spinel. This corresponds to the high solubility of
Al103 in MgAl 2 0 4 at high temperatures 73).
,...
....
';j;
c L.OO
'"
-.::J

3.96

196

3.94

lS2
A: 1.5h 1630'C
3.90 B: 1.S h 1630'C
+'0 h ,850'C

o 50 100 300 1000 3000 ppm MgO

fig. 2.8 lnflu~no. of MgO content on the density of .inteNd alumina.

All specimens underwent a second heat treatment at 1850 °c for 10 h, This resulted
in an increase in the density of all samples; see figure 2.8, curve B. There is no distinct
peak now because all samples with a MgO content between )00 and 1000 ppm reach
nearly full density. Higher MgO contents result in a decrease of the density,
This decrease is greater than can be ex:plained by the slight decrease in theoretical
density due to the presence of the second phase. According to eq. (2.4) the solubility
limit at 1850 °c is 1350 ppm MgO,

2,3.3,2 Influence of MgO on the grain size

The microstructure of the speciJ1len~ was evaluated and the mean grain size deter-
mined for the various amounts of MgO dope. Figure 2.9 gives the result after the
sintering treatment at 1630 °c for 1,5 h, It appears that MgO promotes grain growth
until the solubility limit is reached. The mean grain siu decreases when more MgO
is present, probably because of the dragging effect of the second phase particles on
the grain boundaries. In the single-phase region we observe a distinct increase in
grain size with the MgO content together with an increase in density.
20

E
2,8
Il!)
QJ
N
' ;jj
c
nI
I-
7

6
/. /
./
l!)

t. 1.5 h 1630 ·C

~o,r'--~~~--~-------
50 100 300 1000 3000 ppm MgO

Fig. 2.9. Influence of MgO content on the mean grain size of alumina sintered for 1.S h at
1630°C .

Pores lying on a grain boundary obviously influence grain growth more or less like
a second phase . The fewer the pores, the more freely the grain boundaries can move.

Fig. 2.10. Undoped alumina sintered for 1.S h at 1630 °c.

Figure 2.10 is a photomicrograph of the microstructure of undoped alumina

specimen. No discontinuous grain growth has occurred at the temperature of
1630 °C, although some pores lie inside the grains.
 21

Fig. 2.11. Alumina doped with 300 ppm MgO sintered for 1.5 h at 1630 °e.

Figure 2.11 shows the microstructure of the sample doped with 300 ppm MgO, while
figure 2.12 gives the microstructure of the sample doped with 3000 ppm MgO. This
last picture shows the many second-phase particles present, mostly at the corners of
the grains.

Fig. 2.12. Alumina doped with 3000 ppm MgO sintered for 1.5 hat 1630 0c.

During the second sintering period at 1850 °c for 10 h discontinuous grain growth
occurs in the undoped alumina sample. This is illustrated in figure 2.13.
22

.. ' . . ', .
.. . .
•. / . ..../ . .:. . .
." ",

. . ,. , .' .
".
~,;.:; '. ~
(... ' .
: ' =/'
/
':
•
o

~.
' 0" ,
•

'.
' , ', ' 0

.'
•
' .. .. :' ,

... .. , .
' "0 • ~. O • • ' ...... .. .
"
..
Fig. 2.13 . Undoped alumina sintered for 10 h at 1850 cc.

The microstructure contains many large grains of 100,um and more, while most of
the pores are trapped inside the grains. The specimen doped with 50 ppm MgO
contains cracks and shows a non·uniform microstructure : many very large grains, even
larger than 100 ,urn, are visible within a matrix of much smaller grains. Grain growth
occurs in a stage at which most pores have disappeared . The large grains now are
essentially pore-free, in contrast to the case of undoped alumina . Large pores are
found between the large and the small grains. The same holds, but to a much lesser
extent, for the sample with 100 ppm MgO. This sample contains no cracks, however.
The non-uniform microstructure is illustrated in figure 2.14.
, "
" I, .
'\.. • . .J
~. \
. : r -~ '. 'j
. t:
" . \

,. ) / >-.... t

• •
-' . ,
-"
.r, ':. " . .n 1

~~~ - "~' ',1•. / '(

,.
50pm .( " -: . ~ .: ... ~ \ { .~
~ /.....-: .. . /1• .~ ..... "....
: - /\ ( '
r" .J
r~
".1; ..... .

Fig. 2.14. Alum ina doped with 100 ppm MgO sintered for 10 h at 1850 cc, showing non-
uniform grain growth.
 23

All samples with more MgO show a very regular distribution of grain sizes. Illustra-
tions are given in figure 2.15, which shows the microstructure of the sample with
300 ppm MgO, containing occasionally a second-phase particle, and in figure 2.16,
which shows the microstructure of the sample with 3000 ppm MgO, containing
large coarsened spinel particles.

Fig. 2.15 . Alumina doped with 300 ppm MgO sintered for 10 h at 1850 ° C.

Fig. 2.16 . Alumina doped with 3000 ppm MgO sintered for 10 hat 1850 ° C.
24

The mean grain size of these samples is given in figure 2.17. Essentially the Same
dependence on the MgO content is found as in the previous case after sintering at
1630 °C; increasing grain size in the singlo-phase region, decreasing grain size in the
second-phase region .

.------.
E
2:-
I~

<I>
N
25
III

c:
.§
(!)
20

15
15 h 1630·C
10 -10 h 18S0 'C

0 50 100 300 1000 3000 ppm MgO

fig. 2.17. Influence of MgO come", on th~ mo<ln grain size of alumina aft~r a seeond 5intering
period at 1850 °c for 10 h.

Although parI of the second phase can originate from precipitation during cooling,
the solubility rate of the spinel particles, present at lho grain corners, is apparently
very low.

2.3.3.3 Influence of extra addition of CaO and Y 2 O~

Many combinations of MgO and some other oxide as additive have been tried to ~ee
whdher the pwpertics of sintered alumina could be improved. The patenlliterature
in particular gives many examples of such investigations. Most attention has been
paid to the combinations MgO + CaO 14) and MgO + Y 203 75), To see whether the
extra addition of CaO or Y2 0] could enhance the transmission of alumina sintered
at relatively low temporatures, we carried out $inlcring experiments starting with
the alumina powder already doped with 300 ppm MgO, To this powder 0.1 wt %
Y2 0, was added as an emulsion of very pure Y1 O~ in absQlute alcohol. The SO ppm
extra CaO was added by immersion of a compact in a solution of Ca acetate. These
pellets were already isostatically pressed and presintercd at 1250 °c in oxygen.
This treatment increases the relative density tll 56 % and gives the necessary
mechanical strength, Knowing the constant amount of water these compacts
 25

absorb, one can calculate the required concentration of the Ca acetate solution to
add 50 ppm CaO.

Comparing the microstructure of the samples with and without Y2 0 3 , it can be

concluded that Y203 has an inhibiting effect on grain growth. But also the density
is lower after the same sintering treatment. The spread in grain size distribution is
larger without the occurrence of discontinuous grain growth. Electron microprobe
analysis reveals solid phases of two types: a phase containing only Mg and Al, often
in the form of needles, and a phase containing only Y and Al, probably Y 3 Als 0 12
particles with a diameter of 1· to 2 pm, lying on the grain boundaries. This phase
must be responsible for the decrease in grain size compared with the samples without
the extra Y 2 0 3 dope.

Addition of extra CaO causes a much more irregular microstructure (Figure 2.18).
Although the mean grain size is not much larger, the grain size distribution is very
wide. The same is true of the pore size distribution. The density is equal or stays a
little behind. The phase diagram of the system Al 2 0 3 -- CaO predicts low melting
eutectics. The straight grain boundaries in the microstructure point indeed to the
presence of a liquid phase 76). With electron microprobe analysis two phases can
again be distinguished: the well-known spinel phase with extra Alz 0 3 in solid
solution, and a more irregularly occurring phase containing Mg, Ca and AI,
presumably CaO . 6 AI 2 0 3 with part of the Ca atoms substituted for Mg atoms.
Both phases are clearly distinguishable by the different colour of the luminescence,

'..
\
/

, /"

."
~- \

Fig. 2.18. Alumina doped with 300 ppm MgO and 50 ppm CaO sintered for 10 h at 1850 °c,
showing a rather irregular microstructure.
26

which occurs when the sample is irradiated with a broad defocussed electron beam
(figure 2.19). The colour of the spinel phase is green, that of the Ca-containing
phase is black, while the main phase is violet-blue.

The results of the transmission measurements on these samples and on the samples
containing only MgO are given in section 4 .2.3.

Fig. 2.19. Luminescence of the same sample as in fig. 2.18 in the electron microprobe. The
colour of the spinel phase is green, that of the Ca-containing phase is black.

2.3.3 .4 Auger spectroscopy

Auger spectroscopy was used to investigate the possible grain boundary segregation
of MgO and CaO in alumina.
Samples containing 1000 ppm MgO and 45 ppm CaO were used for these experi-
ments. The bulk concentrations were verified by atomic absorption analysis. The
powder compacts were sintered at 1630 °c for 1.5 hand 1850 °c for 10 h in a
humid H2 atmosphere. Rods 2 mm in diameter were prepared from the sample.
Figure 2.20 is a scanning electronmicrograph of a fracture surface, which shows
that the fracture is mainly intergranular.

Other rods were fractured under high vacuum. The Auger spectrum of the fresh
fracture surface is shown in fig. 2.21. Besides the peaks of Al and 0, the Ca peak at
292 eV is very clear in the spectrum. The Ca concentration at the surface could
be fixed 77) at about 6 at %. This means an enrichtment of the surface by a
factor of 1000.

Signal averaging techniques were used to decrease the detection limit for Mg. A part
of the resulting spectrum is shown in figure 2.22.
 27

Fig. 2.20 . Scanning electronmicrograph of a fracture surface of an alumina sample with

1000 ppm MgO and 45 ppm CaO, showing mainly intergranular fracture. White bar is 10 /-1m.

Auger signal

i -3x

Cal2921
AI

AI

o
_ Energy I eV I
! I I I ,

o 200 400 600 800 1000 1200 1400 1600

Fig. 2.21. Auger electron spectrum of a fresh fracture surface of the sample in fig. 2.20.

Quantization of the Mg peak yields a Mg concentration of about 0 . 1 at %. This

agrees with the analysis of the original powder. No grain boundary enrichment
could thus be established. It should be remarked that the accuracy of the Auger
analysis is a factor of 2. A further remark should be that part of the MgO may
have evaporated during the sintering treatment. In fact, analysis of the sintered
piece showed that the MgO content had decreased by 20 %. A minor enrich-
ment of Mg at the grain boundaries is therefore still possible .
28

II ~

Port Cit tne group

~
of hnliJs, of AbO)
at ~ 1350 .v
_E~ergy I.vl
1040 1200 13S0

Fig. 2.22. Part of the A1)g~r el~c[rOIl spectrum of the ~<1.lYIplt!" in figure 2.20, obtl:iined by means
of .ign.l .v<rag;ng techni<jues.

By simultaneous sputtering of the fracture ~urfacc with Xe iom and measuring the
Auger spectra, the profile normal to the surface was investigated. The remlt, of

~ 5 sec sputter
line
..".,.., 30

-Iv-
~
1 min
1
~

~ 10 ..

~
40
C

Fig_ 2_23_ Behaviuur of the Auger 'ignal of <:. a. a functiOn of spYl!cring time_
 29

these experiments are shown in figure 2.23. The figure indicates that Ca is concen-
trated in a region nea, the intergranular f,acture surface. One has to be very careful
in translating the sputter time into a depth measured in Angstroms. The intergranular
surface is very rough and the Xe ion beam hit the surface at grazing incidence. The
sputtering of the surface can therefore be expected to be non-uniform.

2.3.4 Discussion

The results of sees 2.3.3 and 2.3.4 demonstrate that MgO influences both the
densification kinetics and grain growth of alumina in the same way. This suggests
that densification and grain growth are governed by the same mechanism. This
could also be concluded from intermediate stage sintering data of CoO ll).

Very small amounts of MgO promote the sintering of alumina. A second phase of
spinel is obviously not necessary. The experiments with Auger spectroscopy do not
point to an important grain boundary segregatiun uf MgO or tu its presence as a
mOl around the grains, which would decrease the grain boundary mobility. This is
contrary to the conclusion arrived at by Jorgensen and Westbrook (>l) and
Budworth 65). Our conclusions are supported by the work of Johnson and Stein 78).
With broad beam AES they observed Mg peaks representing not more than twice
the bulk level. With scanning Auger microprobe they were able to determine that
most of the Mg detected on the fracture surface is confined to discrete particles and
that the overall coverage between the particles corresponds to the bulk level in the
alumina. The overall increased concentration of Mg at the grain boundaries found
by Taylor et aI. 68, n) must be the result of precipitation rather than segregation.
It should be realized that the results of grain boundary analysis will be influenced
by the cooling rate after sintering. During slow cooling segregation and precipitation
may strongly increase.

Our eJ\periments and the eady eJ\perilnents of Marcus and Fine 66) show that ell is
a pronounced segregant. Since the size misfit for the Ca ion in alumina is large, it
may be that elastic strain energy makes an important contribution to its tendency
to segregate. The ionic radius of Ca is about 0.99 A, significantly larger than that
of Al, which is about 0.50 A and Mg, which is about 0.65 A. 1n spite of its strong
tendency to segregate, CaO as the only additive to alumina is not effective in pre-
venting discontinuous grain growth in alumina 45). Nor did the combination of
MgO and CaO in our experiments improve the density of the samples or their
transmission properties (section 4.2.3). The same holds for the combination MgO
and Y,O).-.

111ere is still another reasun for rejecting the idea of solute segregation of Mg.
Figure 2.9 (page 20) shows that in the single-phase region the grain size increases
with the MgO content. In the case of segregation of Mg to the grain boundaries
one would expect the reverse to occur. This reverse effect has been found in Y 203
containing various amounts of Th0 2 , and was ascribed to segregation of III 30).
30

Coble 44) already observed that addition of MgO to alumina did not irlhibit the rate
of normal grain growth, and Coble and Burke $) listed possiblo reasons for this.
However, they added 0.25 wt % MgO, which far e)(cecds the solubility limit. Our
results indicate that MgO even promotes normal grain growth as long as the
solubility limit has not bem reached.

II sCCms that the average grain growth rate is completely controlled by the volume
fraction and si<l:e of the pores. The more MgO is present (below the solubility limit)
the mOrC the sintering !"ate and thus the rate of pore removal is enhanced. This
means that there are fewer restraints on the grain boundaries and the grain boundary
velocity can more closely approach the velocity of a free boundary. The essential
action of MgO is then the enhancement of the densificatiOl\ rate of alumina and
nO! th", reduction of grain boundary mobility. Rao and Cutler 32) found that the
sintering rate of alumina doped with fe 2T ions increas~s with the total Fe (;On tent ,
and it seems that the same is tmc of alumina doped with Mg2 + ions. This makes
Ollr results consistent with t.he defect model for alumina diSC\lssed in sec. 2.2.3.

We must conclude that the inhibition of discontinous grain growth by MgO is not
caused by a considerable red\lction in grain boundary mobility due to ci ther a
soltltc segregation mechanism or to the presence of spinel a~ second-phase particle~.
More important is the enhancement of the sint.ering rate or rale of pON removal,
which averts the condilion for the occurrence of discontinu()l[s grain growth.
A second effect of MgO may be an increase of the pore mobility, so that the pore
can f·oUow the grain boundary more easily. Possibly both mechanisms contribllte
to the inhibition of discontinuous grain growth by MgO. The additive might also
change the poro geometry, i.e. the grain boundary angle of a pore situated on a
grain boundalY. This dihedral angle is determintd by the fa tio of the grain
boundary energy and the SIIrface energy. Jorgensen 51 ), trying to detect pos~ible
solute segregation, states that addition of 0.1 wt % MgO inGreases the angle by a
faGtor of 2. However, we were unable to observe this large increase in our samples.

Above the solubility limit scc()nd'phase particles are present and this changes the
situalion completely. The second·phase inclusions lie on grain edges and at grain
corners and influence the grain growth process,
An increase irl the MgO content corresponds to an increase in the average number
of second·phase part.icles per grain boundary and/or iln increase in their average size.
This results in an increasing drag on the grain bOllndaI'ies and e)(plains the decreasing
mean grain size found experimentally. MocelUn and Kingery ~2), who have annealed
samples of MgO-doped al\lmina, als(l find that second-phase draggjng probably con·
troIs the grain growth kinetics.

Another aspect of an increasing amount of second-phase particles is the decrease ill

sintering rate, which is expressed in lower densities (figure 2.S, page 19). The same
phenomenon has beon found in other systems. Rcijncn 4) has put forward the
 31

hypothesis that grain boundary sliding is essential for fast sintering, and suggests that
a dispersed second phase would suppress this grain boundary sliding for purely geo-
metrical reasons. If this hypothesis holds in this case, longer sintering times should
give higher densities. This has indeed been confirmed. Another explanation involves
an overall decrease of mobility in the boundary when the boundary is 'blocked' by
a dispersed phase.

Finally a remark on the non-uniform microstructure in the samples with 100 ppm
MgO and less, as illustrated in fig. 2.14 (page 22). It is possible that this is caused
by a non-uniform distribution of MgO. Locally mare MgO may be present and this
would then result in a higher rate of pore removal and more rapid grain growth.
These large grains oan then grow at the expense of others. This might explain why
the large grains are nearly pore-free (in contrast with the large grains in the case of
undoped alumina) and why large pores are often found between large and small
grains. A similar phenomenon has been found by Groscovkh 83) in the ThO~ "doped
YZ 0 3 system.

2.3.5 Conclusion

The addition of MgO promotes both the densification and grain growth of alumina
as long as the solubility limit has not been reached. The most effectIve dope level
corresponds to the amount that can be brought into solid solution. Auger spectro-
scopy shows no important enrichment of the grain boundary area with MgO.
These results do not support the theory of grain boundary segregation. The essential
action of MgO seems to be enhancement of the pore removal rate. At higher dope
levels, when seccmd·phase particles are present, grain growth is slowed down and
the densification is also negatively influenced.
32

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 33

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34

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 35

61) EV. Degtyareva, Inorg.Mat.l,25S(1965).

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(1970).

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65) D.W. Budw orth, Min. Mag. 37,833 (1970).

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67) S.S.C. Tong and J.P. Williams, J. Am. Ceram. Soc. 53, 58 (1970).

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69) D. Prokie, J. Phys. D(Appl. Phys.)7, 1873 (1974).

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74) B.J _ Hunting et aI., U.S. patent 3 846146.

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78) W.C. Johnson and D.P. Stein, J. Am. Ceram. Soc. 58,485 (1975)

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(1976).

80) P.J. Jorgensen. Defects and Transport in Oxides, Eds M.S. Seltzer and RI.
Jaffe, Plenum Press, New York, 1974, p. 379.
36

81) P.J. Jorgensen, Grain Boundaries in Engineering Materials, cds 1.L. Walter,
J.H. Westbrook and D.A. Woodford, Claitor's Publishing Division, Baton Rouge,
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83) C. Grescovich, private communication.

 37

3. HOT PRESSING OF ALUMINA

3.1 Introduction to hot pressing

Hot pressing Or pressure sintering is an alternative meanS of densifying a powder

compact. The process differs from sintering in that heat and pressure are applied at
the Same time. The additional pressure delivers an extra driving force for the
dcnsification process. Therefore, densification OCCurS al a much lower temperature
than in the normal sintering process. This low temperature and the relatively short
time cycle of the hot-pressing process make it possible to fabricate very fine-grained
alumina. If only sintering temperature and time can be varied a relationship exists
between density and grain size of the compact 1,2). This makes it practically im-
possible in normal sintering to combine a low POf()sity with a small grain si;[e. The
application of pressure enables extremely low porosities to be obtained combined
with a grain size below I Jll11, without the use of $intering additives. Hot pressing is
therefore an attractive method to obtain unusual microstructures possessing such
features as low porosities, very small grain sizes and very small pore sizes. The
method is applied mort in materials research than in industrial practice b CcauSC of
its high cost and poor shaping possibilities.

In spite of the importance of the hot-pressing process, fundamental knowledge

concerning the factors that affect the process is limited. The extra variable of
pressure leads t,) process mechanisms that are mOre complex than those occurring
in pressureless sintering. Just as in normal sintering, it has been recognized thar
generally several mechanisms contribute jointly to the densiflcation process 3,4).
During the early stages of densification particle rearrangement by particle sliding,
aided by fragmentation and possibly plastic flow, is an important mechanism,
especially at high pressure and lower temperatures. There is general agreement that
the final stage of deosiHcation of alumina occu,S by enh.anced diffusion under the
influence of stress or by Nabarro-Herring diffusional creep $-8). The measured
activiation energy agrees with that for the final stage of normal sintcring and for
the self-diffusion of Al ions in alumina 7,S). It should be noticed, that these
experiments were performed in graphite dies, which only allow pressures up to
70 MN/m 2 • At higher pressures plastic flow may be another important mechanism-
The recognition that several mechanisms contribute jointly to densification has led
to the development of pressure sintering maps, which visualize the mechanism
contributing mostly to densification under given conditions 9,10)_

As in normal sintering, impurities play an important roie in hot pressing, Gaseous

impurities are especially important because they do not get enough time to diffuse
Ollt and are trapped in the pores. These gaseous impurities may come from the
atmosphere or from gases adsorbed 00 the powder or from chemically bonded
anions, like H2 0, CO 2 and S 11,12). These impurities may inhibit further shrinkage
of the pores, they may discolour the alumina and they may have a negative influence
38

011 the physical and mechanical properties. On annealing they may cause bloating
of the hot-pressed alumina 13). Rossi and Fulrath 7) estimate that a monolayer of
Hz 0 is still covering 15 % of the surface of alumina at 1250 "c. Outgassing and
vacuum hOI-pressing helps, but not always suffjciently.

Additives have been used to enhance the dcnsification of alumina. Rice 11) reports
that LiP is successful, while MgO gives no significant difference. Use has been made
of the transition of 1'-AI 2 0 3 to o:-A1203 14), called reactive hot pressing. This was
only successful when high healing rates were used IS),

Although hot pressing is a costly procI>SS, it has great practical value in Ihat it
permits the densification of materials thaI show an intdnsic poor sinterability.
Moreover, there are special applications where c(lSI is not of primary importance.
Examples of materials where hot pressing has been successfully applied are~
optically transparent materials, MgO 16), Yz 0 3 17) and Sc~ 0 3 IS); low-loss
microwave ferrites 19); transparent piezoelectrics for electro-optical devices iO):
piewe1ectrics lor application at high frequencies 21). Rhodes et a!. 30) report
that they h<Ive made transparent alumina by hot forging of already densely
sintered alumina. However, transparent alurnina made by hot preSSing has never
been reported.

Much attention has been paid to the practical development of hot-pressing techniques
Some of these developments have recently been reviewed 22). Many aspects of h!)t-
pressing, which could not be dealt with i.1l. this short introduction, call. be f()und in a
review by Spriggs 23).

The present investigation describes the hot pressing of alumina by the technique of
continuous hot pressing, This technique was developed in our laboratory 24) and
will be described briefly in 8ec.3.2. The goal of the work reported in sec, 3.3 was to
eliminate lhe porosity as far as possible and to keep the remaining pores as small as
p()ssible, We hoped that this cumbination of properties would result in really
transparent alumina. Sin!ering of alumina powder in the normal way always results
in translucent alumina, The question of transparent versus translucent alumina is
discussed in sec" 4"3" The microstructure of hot-pressed alumina is described in
sec. 3.3.

3.2 Continuous hot pressing

The process of continuous hot pressing, as opposed to the l1()fmal single piece
process, allows the fabrication of solid rods of, in principle, infinite length. As the
cyclic heating and cooling uf tho die in the single-piece process is avoided, the die
Ufe is lung. Figure 3,1 gives a schematic view of the die during operation. The
cylindrical die D is heated by a resistance wire W, wound in a groove in the die,
The kmpcratIJre ls measured at different heights in the die by means of a number
 39

Fig. 3.1. S~hematic repro.ontation of tbe COn!inUOus hot-prossing process. Solid arrow,; indicate
pr~s5ure~, open arrows the: direction of motIon.

of thermocouples placed in small holes bored radially into the die as far as 1 to 2 mm
from the inner surface of the die. The powder P is compacted between an upper
punch U and a lower punch 1. The lower punch is continuously lowered by a spindle
mechanism. The upper pinch, which is watereooled, exerts a constant force on the
powder. In this way the matedal is pushed through the die, and while the upper
part P is still in powder form the lower part S is already a sintered rod an d can be
considered as an extension of the lower punch L.

When the upper punch reaches a preset lowest level, it is lifted to make rOOm for the
next batch of powder to be fed in, Careful choice of this level, with water-cooling of
the upper punch, allows this new batch of powder to be fed in before the top of the
powder layer starts to sinter. If the pressing conditions have been chosen properly,
the individual batches cannot be detected later in the hot-pressed rod. The sintering
takes place in the middle of the die in a zone of highest temperature of about I em.
The sintering powder mass passes through the hot zone by means of an audible slip'
stick mechanism. The velocity can be chosen between 5.0 mmlh and 1.5 mlh, which
means that the sintering timc can vary between 2 hours and 0.5 minute.

The die consists of fine-grained, dense alumina. To overcome the high tensile stresseS
which build up during pressing., the die is mQunted under a permanent compressive
stress. The compressive streSS is applied by pressing support blocks from six sides
40

against the die, which for this reason has the shape of a hexagonal prism (see figure
3.2). The practical advantage of this design is that the performance of the die remains
excellent even if the die is cracked due to thermal or mechanical shocks .

Fig.3.Z. Details of the die assembly.

The hot-press allows high temperatures and pressu res to be attained. A maximum
pressure on the upper punch of 200 MN/m 2 is possible . The maximum temperature
is higher than 1500 0c. Pressing rate, pressure and temperature are the parameters
that determine the hot-pressing process . It is remarkable that hot pressing of alumina
powder is possible in an alumina die without the powder sticking to the die wall. The
rods obtained have an extremely good finish, with shiny surfaces, as if the rods had
been polished after hot-pressing.

3.3 Results and discussion

Most experiments described in this section were carried out with a-Al2 0 3 powder
obtained from Rubis Synthetique des Alpes, code A6 . The specific surface of this
powder, determined by BET-analysis, is 6.3 m 2 /g. The impurity content was
analysed spectrochemically with the following semiquantitative result:
Si 200, Fe 100, Na";;; 100, Ga 20, Pb 3, Mg 7 ppm .
The average particle size of the powder is about 0.3 /-lm , but the powder contains
many large agglomerates of particles. The average size of the agglomerates is 20 /-lm.
For a comparison with the powder used in the sintering experiments, see sec. 2.3.2.
The difference in hot-pressing behaviour between these powders is discussed in
sec. 3.3 .3. Section 3.3.1 deals with the influence of the atmosphere on hot pressing,
while sec. 3.3.2 is devoted to the influence of the process parameters temperature,
 41

pressure and transit rate. In section 33_4 the microstructure of hot-pressed alumina
will be described and compared with the microstructure of normally sintered
alumina. Finally, section 33_5 discusses a possible crystallographic texture of the
grains.

3.3.1 Influence o/the atmosphere

The atmosphere in normal sintering experiments will influence their results.

According to Coble 2,) the gas molecules must be soluble in the solid; if not, they
exert an inhibiting effect on pore closure during the final stage of densification. This
is the case with nitrogen, argon and helium. The hot press is provided with gas-tight
seals, allowing hot preSSing to be cauied out in all kinds of atmosphere, including
vacuum. In this case 'vacuum' means a pressure of about O. I - 0.5 Torr.
This way of hot preSSing has been extended with an outgassing step by installing an
adjustable time switch: after the die has been fed with a new charge of powder, the
upper punch remains in the lifted position during an adjusted time allowing gaseous
impurities to diffuse out.
We carried out a series of experiments in different atmospheres but at the same
temperature of 1440 Dc, the same pressure of 120 MN/m 2 and the same transit rate
of 25 mm/h. The results are given in table 3, I.

Table 3_1

Influence of the atmosphere

-'"

Atmo sphere Density (g/cm 3 ) Colour

_... "
---
m _

3.980 white
3.979 grty
3.980 white
3.980 white
vacuu m 3.982 grey
id T I min. outgassing 3983 white
-"-'."-- -..>."..., .......--.

The table shows that the differences in density are slight. In all listed atmospheres a
high density can be achieved (the theoretical density is 3.986 g/cm 3 ). There arc
slight variations of the density along a hot-pressed rod- The values indicated in the
table are the lowest measured values. The density of the last pressed part of the rod
is often Significantly higher than the average density. The reason for this phenomenon
is not completely clear but may be related to the somewhat conical outlet of the die-

The outgassing step results in a slight improvement of the density. The colour change
from grey to white is striking. This may be caused by gaseous impurities which get
42

the opportunity to disappear. As the powder is made by calcining AlNH4 (S04)2 ,

sulphate impurity may be responsible for this effect. A chemical analysis indeed
showed the presence of 365 ppm S04 in the powder. Above 1100 °c in a reducing
atmosphere the expected Al2 S3 is a liquid and this may lead to some liquid-phase
sintering. This may very well explain the large grains that can be found in the
microstructure of vacuum hot-pressed alumina (figure 3.3).

Fig. 3.3. Undoped alumina hot pressed in vacuum at 1440 DC, 120 MN/m 2 and 25 mm/ h
showing large elongated grains.

The influence of gaseous impurities is also apparent from the behaviour of hot-
pressed rods on annealing. The dense hot-pressed bodies always undergo a decrease
in density . The decrease depends on the atmosphere during hot pressing. This may
be illustrated by the results of the following experiments:

vac. h .p. d = 3.982 } 120 h 1050 °c 1 d = 3.981 } 2 h 1400 DC d = 3.970

_ O2 _ O2
O2 h.p. d - 3.982 d - 3.980 d = 3.959

The decrease in density of the body hot pressed in O2 (A = 0.53%) is about twice
the decrease in density of the body hot pressed in vacuum (A = 0 .27%). Annealing
experiments were also carried out under an isostatic gas pressure :

vac. h .p.d: 3.981} 20 h 1360°

H2 h.p. d - 3.980 92
d =3.978 ; .1=0.08%
0 ~ d =3.975; .1=0.13 %
atm 2
O2 h.p . d = 3.983 d = 3.976 ; .1= 0.18 %
 43

We again find a decrease in density, even for the body hot pressed in vacuum. Assum·
ing that 1 % of the surface of the alumina powder is still covered with gas molecules
at 1440 °c (e.g. H~O molecules) and that this gas will be trapped inside the pores
during hot pressing, a gas pressure of 400 aim can be estimated in the pores. The
microstructure after annealing shows that considerable pore growth has taken place
without a large increase in grain sb:e. Very typical are also the many fissures and
broad grain boundaries, possibly formed by merging of small grain boundary pores_
This su pports the hypothesis that the decrease in density after annealing is caused
by bloating due to the high gas pressure inside the pores. Bloating of hot "pressed
alumina on annealing has also been described by Rice 11). The same phenomenon
has been found for hot"pressed Fe2 O~ Z6).

3.3.2 Influence of the hot'pressing parameters

The density of the hot-pressed products can be directly influenced by the parameters
transit rate, preSsure and temperature. Some experiment~ were carried out to estimate
the importance of each of these parameterS. Figure 3.4 gives the influence of the
transit rate on the density, the other parameters being held constant (temperature
1440 °Cand pres~u[e 120 MN/m 2 ).

4.00

S Il 50 m
vlmm/hl

Fig_ ~-4- Influence of the transit rat" during hot pr.ssing on the d"n.ity of alumina.
Temperature 1440 ·C, pressure 120 MN/m' iUld atmosphere 0,.

The atmosphere in all experiments was O2 , The hot zone in the die being about 1 em,
the transit rate can be transformed immediately in a sintering time. Under the chosen
conditions of temperature and pressure the optimum velocity is apparen tiy about
25 mm/h_ A transit rate of 5 mm/h proves to be too low: samples pressed under
44

these conditions show discontinuous grain growth (figure 3.5). This very low transit
rate requires much lower temperatures. Indeed, at 1300 °c the density was again
3.980 g/cm 3 and in vacuum at 1280 °c and a transit rate of 5 mm/n a rod could be
pressed to a density of 3 .984 g/cm 3 .

Fig. 3.5 . Undoped alumina hot pressed in 0, at 1440 cc, 120 MN/m 2 and 5 mm/h showing
discontinuous grain growth.

The influence of temperature and pressure appears from figure 3.6. All experiments
were performed with a transit rate of 25 mm/h and an O2 atmosphere. It can be seen
that a combination of high pressure and high temperature is not always favourable.
'00

196

194

150 200
-P[MN/m'l

Fig. 3.6. Influence of temperature and pressure during hot pressing on the density of alumina.
Transit ra te 25 mm/ h, atmosphere 0,.
 45

There are optimum conditions above which the density decreases again due to dis-
continuQus grain growth.

3J3 Influence of powder propertles

Some hot pressings were carried out with the same alumina powder as used for the
sintcring experiments and characteri~ed in sec. 2.3.2. The main differences between
this powder AIS RZ and the powder A6 with which all other hot-pressing experi-
ments were carried out ate: a higher specific surface, smaller average size of the
agglomerates and a higher I?urity. The conditions chosen for these experiments were:
transit rate 25 mm/h, pressure 120 MN/rn 1 and an O2 atmosphere. Figure 3.7 gives
the influence of the teml?erature on the density. Although the attainable densities
do not differ much from these shown in figure 3.4 and figure 3.6, the optimum
temperature is seen to be almost 100 6 C lower. The A15RZ powder can be
considered to be more reactive; this results in a higher densification rate but also
in a higher grain growth rate. Comparison of the microstructure confirms that the
discontinuous grain growth starts at a lower temperature. This results in trapping of
the pores inside the grains and a lower density at the temperature where the powder
A6 attains maximum density.

'300 1/;00 '500

rfel

Fig. 3.7. I"'fh,e ... ~e of temp.rat~r. during hot pro.. ing on the densit), of A15RZ alumina.
P(e~~"N 120 MNfm' , Iran.it rate 25 mm/h and atmo'phere 0,.

Limited trials of hot pressing alumina powder with 0.05 wt % and 0.2 wt % MgO
indicate no significant differences compared wlth the undoped alumina. The
distribution of grain sizes may be somewhat more hom(lgeneous and the average
grain size somewhat lower (figure 3.8).
 46

Fig. 3.8. Alumina doped with 0 .2 wt % MgO hot pressed in 0, at 1440 °e, 120 MN/ m 2 and
25 mm/h.

3.3.4 The microstructure of hot-pressed alumina

When we compare the microstructure of dense, hot-pressed alumina with that of

dense, but normaHy sintered alumina , we find a number of characteristic differences .
Due to the much lower densification temperature (1400 ue instead of 1850 °e in
normal sintering) we may expect a small average grain size. Figure 3.9 is a scanning
electron micrograph ofa dense sample, that was hot pressed at 1350 °e.
lt shows a uniform microstructure wi th an average grain size jj = 1.4 11m (obtained
by multiplying the average grain intercept by the geometrical factor 1.5 27). This is
still a factor of 5 larger than the average size of the particles in the starting powder.
Figure 3.l0 is also a scanning electronmicrograph of a sample that was hot pressed
at 1440 0c. It shows a less uniform microstructure with an average grain size
jj = 1.8 11m. These values are typical of hot-pressed alumina. All values measured on
hot-pressed samples lie between 1.0 and 2.0 11m.

In view of these small grain sizes we can also expect small pore sizes. Figures 3.9 and
3 .10 show that most pores are between 0.1 and 0.2 11m. These pores, which cannot
be detected with the optical microscope, are much smaller than those usually found
in normally sintered alumina. Grain growth is always accompanied by pore growth,
because pores may coalesce when small grains disappear 28). A typical value for the
average pore size in sintered alumina is 0.5 to 1.0 11m. Another difference between
the pores in hot-pressed and normally sintered alumina is their position: in hot-
pressed alumina all pores lie on the grain boundaries, while in sintered alumina
most pores lie inside the grains. This agrees with the much lower grain boundary
mobility at the hot-pressing temperature.
 47

Fig. 3.9 . Scanning electronmicrograph of alumina hot pressed at 13 50 0c.

Fig. 3.10. Scanning elecuonmicrograph of alumina hot pressed at 1440 c c.

48

The differences in microstructure and fabrication parameters are summarized in

table 3 .2 .

Table 3.2

Preparation conditions and microstructure of hot-pressed and sintered alumina

hot-pressed alumina sintered alumina

temperature 1400 °C 1850°C

time 0.5 h lOh
pressure 125 MN/m 2 0.1 MN/m 2
atmosphere not critical H2
additive - MgO
mean grain size 1.5 11m 25 11m
mean pore size 0.2 pm 1.0 11m
density ;;. 99.9 % ;;. 99.9 %
position of the pores in tergranular intragranular
I

Most hot-pressing experiments were carried out with a common , agglomerated

alumina powder. These agglomerates can be found again in the hot-pressed product.
Figure 3.11 is a dark field picture of the agglomerates, focussed 25 pm beneath the
surface . It shows that the agglomerates, which can be many tens of a micron , are
still intact after hot pressing.

Fig. 3.11. Agglomerates in hot-pressed alumina seen under dark field illumination a nd focuss ed
2S /-Lm beneath the surface.
 49

5 j.lm

Fig. 3.12. Transmission photomicrograph of an agglomerate in hot-pressed alumina.

Figure 3.12, taken in transmitted light, shows an agglomerate in higher magnification .

It demonstrates that a significant part of the end porosity after hot pressing is caused
by the presence of these agglomerates in the starting powder. These agglomerates,
often appearing as white spots and containing more impurities than the bulk, have
sometimes been called the measles in alumina.

3.3.5 Crystallographic texture of the grains

A preferred orientation of the grains may be expected if plastic flow contributes

considerably to densification during hot pressing 3). A strong texture could
influence the optical properties of hot-pressed alumina (sec. 4.3.4). Therefore we
investigated the possible crystallographic texture by looking at polished and etched
sections perpendicular and parallel to the pressing direction and by using X-ray
diffraction techniques. Investigation with the optical microscope and with the
scanning electronmicroscope gave no indication of any preferred orientation of the
grains, nor did we find any such indication in the case of the large elongated grains
in figure 3.3.

The degree of crystallographic texture is best determined by X-ray diffraction.

Table 3.3 lists the intensities of a great number of reflections for samples parallel
and perpendicular to the pressing direction and for a normally sintered sample, the
grains of which are randomly oriented. The reflections from the basal plane viz.
(0006) and (000.12) are only weak. More suitable for investigation are the strong
reflections (10 1.l 0) and (1129), which are very close to (0001) and nearly in-
distinguishable. The angle between (101.10) and (0001) is only 15°, the angle
50

between (1129) and (0001) is ISo. The reflection~ (0330) and (1120) correspond
to prism planes.

Table 3.3
r------ .. _-,,_ .. ~~

X·ray refleclion intensities from indicated planes in hot-pri;'ssed and

normally sintered alumina

angle sample and orientation

with
plane (0001 )
in sintered h.p. alumina h_p_ alumina
degree~ alumina 1 h.p_ direction II h.p.direction

(0112) 57_6 22.5 23 24

(1014) 38.2 49.S 58 20
(1120) 90 18 11.5 32.5
(0006) 0 0.5 I 0
int. x 10 7 11 2.5
(l1~3) 61.2 6l.S 39 49
(0224) 45 2L5 19 19
(II ~6) 80 43.5 55 23
(1232) 76.5 3 7 3
(1234) 30 15 14_5 20
(0330) 50 8 15.5 43
(000.12) 0 0.8 2 0.5
int. x 10 8 24 5_5
(I Q1_10) I (1129) 17.5 6 15 2
, ........ """ ...._-_. -_._".'"'",', ... ,'-.....

Table 3.3 shows that most reflection intensities are dependent on the pressing direc-
tion. Ret1cctions from the basal planes are increased in sections perpendicular to
the pressing direction, and reflections of the prism planes are increased in sections
parallel to the pressing direction. The ret1ectians of the planes in normally sintcrcd
alumina are often in between the two others. These results lead to the qualitative
cunclusion that hot pressing introduces a certain preferred orientation uf the
crystallites.

A more quantitative indication of the distribution of the ('-axes can be obtained

by rotating the specimen about the normal to the plane of the incident and reo
tlected beam. The X-ray counter is fixed in position to receive a chosen reflection.
BCC3llSC the (0006) and the (000.12) relkctions aro both vcry weak, we choose
the (I 0 1_"10) or (ll 29) reflection, which makes only a small angle with th~ c-axis.
0
In the case of a perfect alignment of the grains we expect two peaks at :18
(l1gure 3_13A), in the case of a random distribution we expect the rotation to have
 51

no influence (figure 3.13B). In the intermediate case we expect two overlapping

peaks or one broad peak. The result for a section perpendicula, to the hot-
presSing direction is given in figure 3.13C. The ordinate gives the ratio of the
intensities of the hot.pressed sample and alumina powder. According to the
figure, the volume of material with ,,·axes (or better the normal on the (101.10)
planes) in the direction of the pressing direction is increased by a factor of 1_66
compared with the random distribution of a powder. This means that there is
only a slight preferred orientation of the grains in hot-pressed alumina_ It con·
firms the result of the previously mentioned investigation with the scanning
electronmicroscope.

1Id9Q.~
"
I)ri9ntt;l.lon

-so
II
om; o.m; "90 e
r<mdom orient-ation

2
r
-90
\
+90

-~
i
.!1
-~
¢

~
.90 0 .90
(lnglo from ba$Ol pig""

Fig. 3.13. Intensity of the (101.10) rdlection in hot.pressed alumina as a function of

the angle with the b • .al plane_ (A) In the "as. of • perfect orientation. (8) in the C's<
of a random distribution. (e) measured for a sample pe~peJ)di(oula~ to the hot-p~essing
direction.

Hamano ct aI. 29) report on alumina hot pressed at much higher temperatu,es:
1600 °c to 1900 °e. They find an orientation 3 to 5 times normal with the coaxes
tending to parallel the compression direction. Rhodes et aI. 30) have studied the hot
forging of dense alumina samples at 1750 °e to 1950 °c. They find a strong
cry~tallographic {OOOI ~ texture normal to the pressing direotion. The texture was
attributed to the dominance of basal slip during deformation: the basal planes
rotate into a stable position normal to the compressive force. They 31) alSo
determined the ratio of the relative intensity of the (0006) reflection for two samples
52

and obtained values of II and 17 respectively. Compared with (,I1.lr value of 1,66 it
means that hot pressing causes a much lower degree of preferred orientation than
hot forging.

3.4 Conclusion

Continuous hot pressing allows alumina to be densificd to nearly full density. This
hot-pressed alumina is further chiHacteri~cd by a very small size of the grains and
the pores. The optim\lm processing parameters arc strongly infl\lenced by the
powder characteristics. Gaseo\ls impurities and agglomerates in the powder determine
the rest porosity. C~mtinuous hot pressing (,Inly causes a slight degrc0 of preferred
orientation of the grains.
 53

REFERENCES

I) G.C. Kuczynski, Mat. Sci. Res. 6,217 (1973).

2) T.K. Gupta, J. Am. Ceram. Soc. 55,276 (1972).

3) R.M. Spriggs and L. Atteraas, Ceramic Microstructures, Eds R.M. Fulrath

and J .A. Pask, J. Wiley & Sons, New York, 1968, p. 70 I.

4) R.M. Spriggs and S.K. Dutta, Mat. Sci. Res. 6,369 {l973).

5) R.L.Coble and J.S.Ellis, J.Am.Ccram.Soc.46,438(1963).

6) T. Vasilos and R.M. Spriggs, J. Am. Ceram. Soc. 46, 493 (1963).

7) R.C. Rossi and R.M. Fulrath,J.Am.Ceram.Soc.48,558(1965).

8) R.C. Rossi, J.D. Buch and R.M. Fultath, J. Am. Ceram. Soc. 53,629
(l970).

9) D.S. Wilkinson and M.F. Ashby, Mat. Sci. Res. 10,473 (1975).

to) M.R Notis, R.B, Smoak and V. Krishnamachari, Mat. Sci. Res. 10,
493 (1975).

II) R.W. Rice, Fabdcation and Characterization of Hot-Pressed AI~ 0;), Naval
Research Lab., Washington, D.C., AD 709 556, 1970.

12) M .H. Leipold and C.M. Kapadia, J. Am. Ceram. Soc. 56,200 (1973).

13) R.W. Rice, Proc. Brit. Ceram. Soc. n, 99 (1969).

14) DJ. Matkin, W. Munro and T.M. Valentine, J. Mat. Sci. 6,974(1971).

15) C.J.P. Steiner, R.M. Spriggs and D.P.H. Hasselman, J. Am. Ceram.
Soc. 55, 115 (1972).

16) R.W. Rice, Am. Ceram. Soc. Bull. 41, 271,586 (1962).

17) S.K. Dutta and G.E. Gazza, Mat. Res. Bull.4, 791 (1969).

18) G.E. Gazza, D. Roderick and B. Levine, J. Mat. Sci. 6, 1137 (1971).

19) J.G.M. de Lau, Proc. Brit. Ceram. Soc. 10,275 (1968).

54

20) C.H. Haertling and C.E. Land, J. Am. Ceram. Soc. 54, 1 (1971).

21) D. Pcrdllijn, R.R.P. Varekamp and H.C. Vorjans, PrOG. Brit. Ceram.
Soc. 18,239 (1970).

22) A.L. Stuijrs and J.G.M. de Lau, to be published in Ceramurgia Int.

23) R.M. Spriggs, High Temperature Oxides, part Ill, Ed. A.M. Alper, Academic
Press, New York, 1970, p. 183.

24) G.1- Oudemans, Proc. Brit. Ceram. Soc. 12,83 (1969).

25) R.L. Coble, J. Am, Ceram. Soc. 45.123 (1962).

26) A.C. Crouch and R.T. Pascoe, Proc. Brit_ Ceram. Soc, 20,189 (1972).

27) M.r. Mendelson, J. Am. Cefam, Soc 52,443 (1969),

28) W _D. Kingery and E. Francois, Proe. 2nd Conf. on Sintering and Related
Phenomena, Eds C. KLlczynski et aL, Gordon and Breach, New York, 1967,
p,471.

29) y, Hamano, M_ Kinoshita and Y.Oishi, YogyoKyokaiShi70,165

(1962), cited by R.M. Spriggs and L. Attoraas, ref- 3.

30) W,H, Rhodes, DJ. Sellers, A.H_ Heuer and T. Vasilos, Development
and evaluation of transparent A12 0 3 , AVCO Corporation, Lowell, Ma.,
AD 661487,1967.

31) W.H. Rhodes, D.L Sellers and T. Vasnos, J. Am. Ceram. Soc. 58,31
(1975),
 55

4. OPTICAL PROPERTIES OF ALUMINA

4.1 General introduction

Interest in the optical properties of alumina will depend on the different applications.
Once alumina has been chosen for use as a lamp envelope material, its optical proper·
ties are of the utmost importance, since they then belong to the primary function of
the material. In this chapter we will mainly be concerned with those optical properties
which are influenced by the ceramic microstructme and the chemical composition,
and so. indirectly by the fabrication process of the material. The function of a lamp
envelope is to transmit the light prOduced by the gas discharge. For this application
only the total transmission is of importance. However, the in,line transmission (the
light transmitted in the direction of the incident light, see figure 4.1) is a much more
sensitive property to study the relation with the microstructure.

incident
light

in -line
transmission

Fig.4.1. When a narrow beam of light pass.. tl)rough a slice of porous polycrystallille alumina,
tho/;; tran.smlssion in the jncid~nt direoction is r~duc;-~d and a diffuse reflection and a diffusoe trans-
mission ar,= gc-neratc:d.

In sec. 4.2 we will describe how the in·line transmission can be calculated and how
thi$ property depends on the microstructure. In sec. 4_3 we will consider the
diffusivity of the transmitted light- The main reason for this investigation is the
striking difference between polycrystalline alumina sintered in the normal way, as
described in chapter 2, and hot-pressed alumina, described in chapter 3. In common
parlance hot-pressed alumina can be described as 'transparent', while normally
sintered alumina is, at best, 'translucent'.
56

This introductory section gives a short historical review of the literature on the
optical properties of alurnina (sec. 4.1.1), followed by a discussion of the various
factors responsible for the loss of light, like refloction, absorption, birefringence and
scattering (sec. 4.1.2)_

4_1_1 ReJ!iew of the literature

Various f~ctors arC responsible for the loss of light when a narrow beam of light
passes through a plane-parallel slice of a ceramic material. The situation is shown in
figure 4.1 _At each change of refractive index a certain amount of scattering occurs.
Moreover the passing light is attenuated by the intrinsic absorption of the materiaL
Inhomogcneilies in the refractive index inside the material include grain boundaries,
second-phase particles and pores. 'The intrinsic birefringence of alumina also in-
fluences the transmission of light.

No quantitative theory exists that. describes the influence of all microstructural

parameters. The interest in the ()ptical properties of polycrystalline materials like
alumina, magnesia etc_ can be related to the progress made in sintering technology.
In 1960 Coble and Burke)) announced the sintering of alumina to a high density
(Lucal(lx)_ At the same time Lee and Kingery 1) reported on the infrared tranS-
mission properties of polycrystallinc alumina- They conduded that scattering by
pores was the major factor limiting infrared transmission, because the wavelength
dependence of the transmission resembled the transmission curves of fine particle
suspensions.

Bowever, in later publications 3,4) the influence of grain boundaries was pointed
Ollt as welL The manufacturer of Lucalox S) states that a high density and large
grains are necessary due LO the strong dependence of in-line transmission on the
density and grain size. The lack of transparency of Lucalox is stated to be another
consequence of the presence of grain boundaries- For the question of translucent
or transparent alumina, ~ee section 4_3_ The overemphasis given in the literature
on the role of grain boundaries can be traced back til the missing of a quantitative
theory describing the influence of the different microstructural parametMs.
It also results from the belief that aU pores are eliminated in the magnesia-doped,
high temperature"fired alumina. However, the material is to be described as
essentially pore-free. A material with a relat.ive dlm~ity of99.9 % and uniform
pores of 0_5 pm diameter, still contains 10 10 pores per cm 3 , too many to simply
neglect!

Budwort.h 6) considers Lhe scattering of light by both pores and grain boundaries.
Bis conclusion is that the limited transparency of sintered alumina is due to residual
porosity and grain growth control addit.ive rather than to optical anistllropy. Be
introduces a grain boundary scattering coefficient to describe the inl1ucllce of the
grain si:cc. According to him it is probable that l'esidual additive at the grain bound-
aries is responsible for a grain size effcct.
 57

Kahan et al. 7) describe a completely different scattering modeL The parameters in

their model are grain size, birefringence and porosity, not the pore size. For a given
birefringence and ~ero porosity the model predicts a rapid decrease of transmission
as the grain size increases. This is hardly to understand. The int1uence of porosity is
greatly underemphasi~ed in their model.

Bondar et al. 8) have studied the effect of annealing of polycrystallinc hot"pressed

magnesia. They found a decrease in IR transmission. This was ascribed to pore
growth during heat treatment by pore coalescence.

Crimm et al. 9) presented empirical relations between the IR transmittance of poly-

crystalline alumina and density, grain size, sample thickness and surface finish. They
found that variations in density were the major contributors to the variations in
transmission. The relative contribution of grain size was of minOr signiflcance in the
grain size region of 20 to 60 11m. However, this minor contribution can also be
explained by minor variations in the density of the samples. They consider the
effect of grain size as a result of the birefringence of alumina and estimated that the
fraction of light deviating from its original path for a thickness of SO grains is only
2.5 x 10'3.

In contradiction with this estimation of the effect of birefringence Rhodes et al. 10,11)
ascribe the improved transmission of hot-forged alumina to reduction of the optical
anisotropy and birefringent scattering due to the presence of a strong crystallographic
texture (see sec· 3.3.5).

4.1.2 Factors contributing t(J transmission losses

We will now discuss successively the factors influencing the transmission of light
through a slice of polycrystalline alumina. These factors !He, as already mentioned in
the prevjous section, absorption, reflection at the surface, birefringence and
scattering by inhomogeneities inside the material like grain boundaries, second.phase
particles resulting from sjntering aids or impurities and pores.

Due to the high value of its electronic energy gap AI:. OJ is transparent in a wide
rang~ of wavelengths. Between 0.2 and 7 11m the transmission of a :2 mm thick
sample of sapphire exceeds 10 % lZ). At short wavelengths the transmission is
terminated by electronic transitions, at long wavelengths the ela~tic vibration of
ions is responsible for absorption. The intrinsic absorption of alumina in the visible
and near IR range is negligible. However, absorption losses may increase due to the
presence of impurities, especially transition metal ions.

Inevitable is the light loss due to reflection at the surface of the material. Provided
there is no absorption, the fraction of light reflected at normal incidence is given
by Fresnel's formula:
58

(4.1)

where n is the refractive index of the rna terial.

The reflection losses are higher because multiple reflection occurs at the front and
back of the slice- Therefore the total reflection loss!?'t is 13)
2R
Rt = 1+1<- (4,2)

In the region of visible light alumina has a refractive index of 1.77, which means
that the reflection loss is 14 %, at normal incidence and for perfectly polished
surfaces_ The importance of a good surface finish appears from the wOrk of
Grimm et aL9 )_ The dispersion of the refractive index of synthetic sapphire between
0.26 and S.6/.!m has been determined by Malitson 14)

All inhomogeneities inside the material wnt give rise to scattering of light. The grain
boundaries come into the picture for two reasons: firstly, alumina has a hexagonal
crystal stwcture and possesses an optical anisotropy; secondly, the grain boundary
itself may be considered as an inhomogeneity _Jeppcsen 15) has measured the
birefringence: at 5890 fJ... he finds for the ordinary ray flO = 1.768 and for the extra-
ordinary ray fle '" 1.760. The extent to which the transrnission is affected by this
birefringence at the grain interfaces will depend on the value of 6.n '" flo - fie and
the number of interfaces, thus on the grain size,
An exact calculation of the int1uence of the birefringence is difficult. A model has
been proposed by Dalisa and Seymour 1~) tor ferroelectric ceramics, but this model
gives too high values for polycrystaJline alumina. (The modd predicts a width of the
0
scattering profile of 4 for .::l.n = 0,008 and 500 grain interfaces, whereas the
experimental value is less than 0,8°; see section 4.3). Budworth 6) and Johnson 17)
both give an estimation of the birefringence contribution. They me eg_ (4.1) and
assume that all grains arc perfectly misoriented, which. means that at all boundaries
the relative refractive index m = 1_760/1_768.

For a sample thickness of 0.5 mm and a mean grain size of 25 I1Il1 (20 grains) the
fraction oflighl deviating from its original path is then 10'4, for a mean grain sile
of I J-lm al the same sample thickness (500 grains) this fraction is 2.5 x 10- 3 , This
simple estimation points to a negligible contribution of the birefringence to the
light IOS5, except for very small grain sizes, e,g. less than 0.1 /1m. Besides these
theoretical considerations ther~ are two experimental justifications for neglecting
the birefringence, First, hot.presscd alumina with its very small grain size of I /-1m
can be made transparent (see sec. 3.3 and 4.3); second, the in·line transmission
of hOI.prcssed alumina approximates to the transmission of sapphire in the infrared
region of the spectrum (see sec- 4_2),
 59

The other reason why we have to consider the role of grain boundaries in scattering
i~ that impurities or additives can precipitate or segregate at the boundarie~_ Clean
boundaries represent regions of atomic disorder only some tens of A wide 18). This
is too small to hinder the light appreciably in passing the grain boundary. Indeed, no
difference in transmission has been found in poly crystalline and single crystaJljne
alkali halides 19). Fmm an optical point of view a polycrystalline material without
birefringence and without pores or precipitates can be considered as a single crystal.
To be sure that the effect of grain boundaries can be neglected one has to use
starting powders of high purity and to minimize the amount of additive.

This leaves us with the pores as the principal scattering centres. Pores are very
efficient scatterers because of the great difference in refractive index, At a porosity
of 0.5 % pOlycrystalHne alumina is still completely opaque. Scattering of light results
in the generation of a diffuse transmission and also of a diffuse reflection due to
ba~kward scattering (figure 4.1, page 54).

4.2 The in-line transmission

The in-line transmission, defined as the fraction of the original intensity that emerges
from the material in the direction of incidence, is very sensitive to changes in the
microstructure, much more than the total transmission, which also includes the
diffuse transmission, The relevant parameters in the micro~tructure are the porosity,
the pore size and the pore size distribution, In this section we will first outline the
general scattering theory (section 4.2.1), which we need to calculate the in-line tranS-
mission as a function of the above mentioned parameters (section 4_2,2). Then we
will present our measurements of the in-line transmission of samples with different
microstructures (section 4.2_3). Finally we will show how the same microstructural
parameters can be calculated from the measured transmission spectra (section 4.2.4).

4.2.1 Scattering theory

Studies of light scattering go back to Tyndall's experiments with aerosols (1869)

followed by the theoretical contributions of Lord Rayleigh (from 1871)_ The
problem generally is to relate the properties of the scatterers - shape, size, size
distribution and refractive index - to the unperturbed, transmitted light or the
angular distribution of the scattered light_ Scattering theory is widely used by
astronomers and metercologists. but also by chemists and phySicists in the study of
colloidal solutions, supcnsions, glasses and polymers. The feature common to these
problems is that the scatterers have a larger refractive index than the medium.
Pores in a ceramic material represent an example of scatterers with a (much) smaller
refractive index than the medium.

The complexity of scattering problems depends on the ratio of the si7.e of the
scatterer to the wavelength. The Rayleigh scattering theory is applicable to particles,
60

that are no larger than one tenth of the wavelength. This implies that we may
consider the particle to be placed in a homogeneous electric field of the light wave.
This Held will induce a synchronously oscillating dipole that radiates in all. directions.
Rayleigh sca!!ering is characterized by the fact that the scattered intensity is inversel:
proportional to the fourth power of the wavelength and the fact that the ilngular
distribution of the scattered light is symmetric with respect to the axis of the in-
cident light and to an axis normal 10 this direction.

If the scattering centres are much larger. the lighl scatlered from one portion of a
particle may be out of phase with thaI coming from another portion. The scattering
intensity in a given direction is now the result of a superposition of contribution$
C(lming fr(lm different p(lints of the particle. With incI'easing particle sb::e the
scattered light becomes more concentrated in the forward direction and the
sco.ttering lnten~jty becomes less and less dependent on wavelength. In 1908
Mic 10) gave the full solution of the problem of the scattering of light by a homo·
geneous sphere of arbitrary sil.e. It can be shown 22) that Mie's theory C(lntains
Rayleigh scattel'ing as a special case. For increasing particle sizes the calculations
become increasingly complex, and require the LIse of a high·speed computer-

The scattering treatment for very large particles (particle size larger than ten times
the wavelength) can be greatly simplifIed by the theory of diffraction. The diffracted
light is spread over a small angular zone.

In oU!' treatment of the scattering of light by pores in a Geramic material we have t.o
use the rig(l(()US Mie theory _Theref(lre, a brief outline will be given of that part (If
the Mie theory that we need to calculate the scattered light intensity. The complete
theory can be found in the standard books on scattering by Van de Hulst 21) or by
Kerker 22).

The scattering in any direction is described by a complex amplitude fundion S (0, '-PJ
which gives the amplitllde and phase of the ~cattered wave. 0 is the anglc between
the forward and the scattered direction Or scattering angle and I{J is an a7,imuth angle.
111c general formulation involves four amplitude functiom S I - S4. but in the ease
of homogeneous spherical particles S3 and S4 ar., ~_ef(l_ Fw scattering in the forward
direction also holds SI (0,0) = S, (0,0)-

The scattered wave is calculated frum Maxwell's equations by requiring that the wave
al the surface of the sphere satisfies certain boundary condltiol1$- The soil! lion
contains the wavelength Ain the medium surrounding the sphere, the normaliz-ed
radius, x = 27rr/A, and the relativc refractive index, ttl =II~Pb~r<lnmcdium. The
amplitude functions of the scattered waves, S] and S2' are found to be
 61

~ 2n+1 { }
fi(n+TJ "/j1l/j(coSO)+b/j1/j(COSO) ,
n=1 (4.3)

The components SI and S2 are perpendicular and parallel, respectively, to the

scattering plane. This plane contains the incident direction and the direction of the
scattered wave (0, <p).

The coefficients a/j and b n are given by

1/I n (m;x;) -.JJn(x) - m I#n (mx) 1#;" (x)
an '"
I#n(mx) tn(x) - m -.JJn(mx) ~rdx)
(4.4)
m-.JJ';(mx) I#n(x) - I/In(mx) I/In.(x)
bn ;; m-.JJ'lmx) t/j(x) - I#n(mx) tnjx)

where I#n and t n are Riccati-Bessel functions.

The addition of a prime to the functions denotes diffe,entiation with respect to their
arguments. The Riccati-Bessel functions are defined as

'/Inft) = Z in(z) ,
(4.5)
In(z) = Z {infz) - iYn(z)} ,

where in andYn are spherical)3essel functions of the first anq second kind :13).

1n cq. (4.3) the coefficients an and b n are multiplied by the angular functions 7fn (cos e)
and 1n(eos e), which express the direction dependence of the solution. These functions
can be exprEssed in the Legendre polynomial Pn(cos (}) by
dPn (cos e)
11n (cos /J)= --d·co-sir·~

The intensity of the scattered radiation is given by the intensity functions i! and i~
defined as
62

(4.7)
i~ = IS~ F,

where i 1 is again the component polarized perpendicular to the scattering plane and
i~ the component polarized parallel to this plane. If natural light of intensity 10 is
incident on a sphere the intensity of the scattered light at the distance d in any
direction is

(4.8)

with k .. 21T/A .

To be able to cakul!ite the in-line transmission, we consider the total energy

abstracted from the beam of light by a particle. When we neglect absorp lion by the
particle, the total extinction cross·secti()fi Cext equals the scattering cross-section
Csca . This is the total energy scattered by a particle in all directions.
Each particle forms a geometric obstacle of cross·section G '" Tft2 • However, its
capability for scattering differs from its geometric cross-section by a factor Q. The
scattering cross-section is therefore defined as

(4.9)

where Qsca is called the efficiency factor for scattoring.

Mit's evaluation led to expressions for CSCQ and Cext. For Csca the expression reads
A2 GO
Csca = 21f L (2n+l) {ianl~ + Ibnl~}. (4.10)
n"'l

The efficiency factor fQ( ~catt.,dng can be found by dividing by Tfr2, So that

')
Qsca '" 71: (2n+1) jlanl" + Ib n I2 }. (4.11)
n=l

The dimensionless quantity Qsca depends on m and x, thus on the relative refractive
index, the wavelength and the size of the spheres.

In a medium containing Nindependent particles per unit vQlume the intensity of a

pT()ceeding beam decreases in a distance [by the fraction e· rl r is the cx tinction
coefficient or scattering coefficient if absorption is absent. It is computed from

r;;; Nnr2 Qsca (4.12)

independently of the state of polarization of the incid'~nt light.
 63

A final remark: the A used in scattering theory is the wavelength in the suspending
medium. This means that Ar= Ao/nmedium where AO is the wavelength in vacuum
and nmedium in our case is the refractive index of the ceramic containing the pores.

4.2.2 Calculation of the in-line tr(lnsmission

4.2.2.1 Pores with a fixed radius

After this introduction to scattering theory we can calculate the in-line transmission
of light passing through a slice of polycrystalline alumina. As a first approximation
we assume that the pores are homogeneously distributed and can be thought of as
spheres with a fixed radius r. The refractive index of the gas in the pores is set equal
to 1. The refractive index of alumina has been determined for the complete rangc
of transparency by Malitson 14). He found the following dispersion equation:

I 1.023798 A~ 1.058264 Ag 5.280792 ;>"5 ) lh (4.13)

n "" ( +;>"3 - 0.00377588 ... A~ + 0,0122544 + "At - 321.3616'

where AO is the wavelength in vacuum. This equation gives us the relative refractive
index m .. 1in as a function of the wavelength. Figure 4.2 gives a graphical repre-
sentation of eq, (4,13).

&55
100
o.~

~~,
1.7'>

().~

1:J!l
0.59

0.60
\ll!j
0.61

062
1~O
M~

0.2

Fig. 4.2. Ordinary refractive inde~ n and relative refractive i!>dex m = Un as a function of wave·
length A. according to mea.uroment. repotted by M.lit.an I.) On sapphire at 24 • c.

The main problem of calculating the in-line transmission is the calculation of the
scattering coefficient Qsca as a function of m and x. According to eq. (4.11) Qsca is
64

a SIJnlluation of terms containing the coefficients an and b n . These coefficients

contain spherical Bessel functions with complex argument The number of terms
required for evaluating thc series is proportional to,x. Hence, reliable Mie scattering
computations for large spheres arc tedious and time consuming. Tables have been
published wich give Qsca for many values of m and x. However most values of Qsca
have been computed fm m > I. Exceptions are the tables given by Boll et aJ. 24, 2S)
for m" 0.60, 0.70,0.80 and 0.90 and Chimey 26) for m =0.50 and 0.75. Inter-
polation of these data for the desired values of m is dangerous because of the
complex character of Qsca.

fo'or the exact calculation of Qsca we used the numerical procedure outlined by
Dave 27) and the recurrence rdations he gives for the Bessel functions. To test the
reliability of the calculations we compared the value of these Bessel functions with
tho~e tabulated in the Handbook of Mathematical Functions ~;)). This showed an
increasing deviation for the higher order functions due to aooumulated rounding
errors. Therefore we changed the forward reourrence relation for a backward
recurrence (sec Ross 18). The improved program has been tested for very large
values of x. Ref. 21 gives a ~imple formula for m '" 1.342 and x > 5 :

2 3
Q = 2.0-7.680 X-I sirl (0.684 x) T 1.84 X- / + 'ripple' . (4.14)

The result of the test is given in table 4.1 which gives the calculated value of Q,
the value of Q obtained from this formula, and the number of calculated Bessel
functions N

Table 4.1

x Q (calc) Q (form) N

5011 2.0305 2.0345 168

10071 2.0180 2.0165 326
20011 2.0198 2.0178 647
30071 2.0240 2.0239 959

The table shows good agreement, even for extreme values of x. Therefore, the
calculation procedure can be considered to be reliable.

The calculated efficiency factor can be represented in several ways. Figure 4.3 gives
Qsca as a function of the pore radius r for three different values of the wavelength.
A generali,.ed representation of QSCIl is given in figure 4.4, where this quantity is
plotted against the function p defined by
41TY
P '" 2x I m-l I = },,~- II-/! I . (4.15)
 65

(The physical meaning of p is the difference between the phase shift which a central
light ray experiences upon travelling thwugh the sphere and that obtained in the
absence of the particle).

if".(U, I m. 0,56
~.1.0, ... 0.57
btl:), mz 0.'58

OJ.

QO~~~~~------~~~----~t~5~----~W~------~~~
rlJ.lml_

Fig. 4.3. The t:!:f:fici~n(:y f,actot for S~Qttt'tin~ by pores in alumina as a function of th~ pore
radius" (or thr¢~ "alu~s of the wavelength A•.

fig. 4.4. ·rh. effi(;ien.:l' fa(;tor for scattering as a function of p" 2"x I »1-1 I willi m - 0.S65.
66

The curve in figure 4.4 is calculated for m '" 0.565. All curves have in common a
rapid increase to Qsca ~ 2.16 and then a damped oscillation about the limiting value
Qsca = 2. Superimposed upon this main oscillation is a ripple structure which is not
shown he,e and which can only be found ifvery small increments of x are selected
in computing Qsca . The limiting value Qsca'" 2 follows from the theory of diffraction
by a circular disk.

For comparison with the experimentally determined transmiss\(m curves a plot of

the transmission T against the wavelength 71.(1 is more suited. For a sample thickness
t we have

(4.16)

where R t takes into account the tolal reflection losses as defined in eq. (4.2), and
'Y is the ~cattering coefficient defined in eq. (4.12). The notation of Tin cq. (4.16)
implies that the scattering is due to independent ~cattering cclltres and that we
exclude mult1ple SC;lttering_ The exponential thickness dependence of the trans-
mission in alumina has been experimentally verified by Grimm et al. 9). The total
geometrical cross-section G = Nrrr2 can be expressed in the experimentally more
accessible quantity Vp, the volume fraction of porosity, by G' = 3 Vp/4 r. This gives
fm the scattering coefi1cient
3Vp Qsca
'Y '" --4r- . (4.17)

Wilh equations (4.16) and (4.17) the in-line transmission can be calculated.
{n tlgure 4_5 results arc shown for three different values of the pore radius r, with
a porosity Vp '" 0_002 and a ~ample thickness t =0.5 mm. The great influence of
the pore si~-e is very clear: at short wavelengths large pores 3rc necessary for a high
transmission, at longer wavelengths the reverse is true.

60

r=l0f-l m
40

20

°O~~~~----~----~----~4------.5~

"ol~rnl-
Fig. 4.5. Cakulatc::u tranS.I'lliSSlOn c.:llI:'V("S;)8;.1. function of wavelength for n fix.~d I)(ll'( raulu:!i r.
P",o,ity V f' = 0,002, ;ample ,hickn .. ' t = 0_5 mm,
 67

The pronounced influence of the pore size can also be seen in figure 4.6, which gives
the transmission as a function of pore size for two wavelengths, Ao '" 0.5 Mm and
A¢ =2 pm, porosity Vp" 0.001. and thickness t .. 0.5 mm.

100

80

~
o
'';

'~ 60
.
<=
i'
:E"
i:.

20

3.0
pore di~meter (Mm)

Fig. 4.6. Calculated ttal1lmissj')n as a f\lnction of the pore radius r for twO v.lues of the wave-
1~IlgJ;h
)..•. porosiw Vp ~ 0.001, sample ~bickness t = 0.5 mm. No corro~tion has b.on mad. for
'et1ec~io~ lm~~'.

In figure 4.6 the reflection losses have not been taken into account for simplicity. It
follows from figure 4.6 that the curves have their minimum value if 2r/'t.. '" 0.73; then
the interaction between light and pores is strongest. Fot smaller pores the scattering
behaviour goes into the direction of Rayleigh scattering, revealing a very strong
dependence on wavelength and pore size. FOr pores larger than the critical size the
tnlnsmi$sion increases with size, but less drastically, and the transmission hardly
depends on wavelength.

The oscillations in Qsca of figure 4.3 and figure 4.4 are also present in figure 4.5.
The fact that we never observe such oscillations in experimental transmission curves
suggests that the assumption of uniform pore size is not realistic. In fact Van de
Hulst 21) has shown for the limiting case of Rayleigh-Gans scattering (lm-l HI),
that the amplitude of the osdllations in Qsca deCreases if we no longer assume the
68
presence of scattering centres with a fixed radius, but instead introduce a site
distribution.

4.2.2.2 Pore sh::e distribution

The assumption of uniform pore size is not realistic in actual ceramic materials; there
is always a spread in pore size, just as there is always a spread in grain size.
Determination of the pore size distribution is very laborious: many measurements
of generally very small pOres are necessary to estimate the distribution with any
accuracy. It is understandable from this argument that hardly any results on pore
size distribution have been published. Moreover, the derivation of the true si;-:e
distribution from the observed distribution in a polished section is a complex
problem 29). An approximate method for this conversion, valid for spherical pores,
has been givGn by Tornandl 30).

For grain size and powder particle size distributions a logarithmic Gallssian distri-
bution is often assumed 3l). This lognormal distribution applies exactly for
quantities that are the result of a process involving steps where the probability of a
change is proportional to the instantaneous value of the quantity. Many growth and
breakdown processes belong lo this category :12). We do not know of any data
published on the nature of pore size distribution functions. Only few measurements
of pore size distribution~ have been reported in literature. However, figures shown
by Oel 33) can be fitted reasonably well with a lognormal distribution.

We have tested in two differenl ways the assumption of a lognormal pore site
distribution in several highly sintered ailunina specimens with large pores. One
method was to determine pore sizes with a planimeter from photographs of a
polished section. The other method made use of an image analyser 34): the picture
of a TV camera was converted into sixtoen grey levels; the black spots from a
certain grey level (the pores) could then be counted automalically. Neithct method
is very accurate and the tesults proved \0 bo very sensitive to sample pr~para!ion
and sample magnification. The resulting two-dimensional distribution was then
converted into a three-dimensional one ~o). A lognormal distribution fitted the
experimental distributions reasonably welL St.andard deviations were found with
a bet.ween 0.25 and 0.35.

For the representatiOl\ of the logarithmic distribution we used the so·called ZOLD
function (zeroth order logarithmic distribution function), described by Espenscheid
ct aL ~$, 22). This function is given by

f(t} =(2~fi~-~~e~·p(f-;;2) cxp [~(ln r 2~}n-~Ill)~-J (4.18)

dei1ned by two parameters rm , which is the modal value of r (the value of the rtidills
r for which the functionf(r) reaches its maximum value) and u, which is a measure
 69

of the width and also of the skewness of the distribution (the skewness of the dis-
tribution increases with its width). A property of this ZOLD function is that the
mOdal value of r remains constant as the value of 0 is varied. The relation between
rm and i, the mean pore radius, is

r'" f r f(r) dr"" rm exp dol). (4.19)

o

The pre"exponential factor in (4.18) is the normalizing factor to ensure

ff(r)dr"'l. (4.20)
o

4.2.2.3 In fluence of pore size distribu lion on the scattering coefficien t

Afte, the introduction of a pore size distributionj{r} we have to reformulate the

expressions of section 4.2.2.). For convenience we introduce the dimensionless
parameter U "" rlrm. If r is normalized with respect to rm, then f(u) does not widen
with time, but remains COnstant during normal growth 36).

We define an effective porc radius reffas the radius that identical pores should have
to cause the same light scattering as the whole of lognormally distributed pores.
For each sphere holds: volume/geOmetric cro$s-$ection;;; 4r13. The effective pore
radius may now be written: "'"
f u 3 f(u} du
3 total volume '" r 0 (4.21)
reff=- "4 total geom. cross-section m
00

f u2 f(uj du
o

Substituting eq. (4.18) we have

reff"" rm exp (fOl j. (4.22)

Thi$ expression already indicates the importance of the width of the pore size distri·
bubon. Table 4.2 gives some values:

Table 4.2
a reff/rm
0 I
0.2 1.15
0.4 1.75
0.6 3.53
0.8 9.39
70

We further define an effective efficlency factor for scattering Qeffby

. . Qsca (u) f(uJ u~ du

j
total scattenng cross-sectIOn _ 0
Qeff = total geometrical cross7eciion- - jf(u) u 2 du
(4.23)
o
With eg. (4.18):

J"'" Qsca (u) f(u} u 2 du

I)
(4.24)
0"(21l-)~ exp (~)-)-

Finally we introduce the generalized parameter Pelf-

With eg. (4.15) and eg. (4.22) we can write:

41frm 2
Pefr ----x;- (n-I) cxp (#;O" ;. (4.25)

Using the ZOLD distribution eg_ (4.18) with parameters a and rm and using the Mic
expressions to calculate Qsca (u), we can numerically integrate eg. (4.24) to obtain
Qeif The results of the calculation of Oef! as a function of Peff are shown in
figure 4.7 for m '" 0.565. The figure indicates that the oscillations in Qeffare damped
out with increasing values of the parameter u. For u> 0.3 no oscillations are observed.

lS

1.0

10 1,
p ~j I ---------

Fig. 4.7. The df~ct;v~ dfici~ncy fa"Wt for s~atlering by porcs in .lumina with a lognormal
pore ~i.c .;I;.tribution as a function of Peff = 4tr'eff Im--·ll/11. with m = 0.565. The width of
the disr;::ribt..l'don jt')c;-rea~es. with incr~a5in8 0 values,
 71

The influence of the spread in pore sizes on the transmission is illustrated in figure
4.8, where the calculated in-line transmission is given as a function of wavelength.
T.1tI%]

r 80

60

0"
40 06
05
20 Q4
03

0 02
0 2 3
Aol!.Im)-" 5
Fig. 4.8. Calculated transmission cutv.s for .lumin. with a lognormal pore size distributiOn
as. function of wavelength. The width of the distribution inc~••s¢s with inc~easing u valuos.
Th. maximum <;If tll. distribution rm " 0.5 I'm, porosity Vp ~ 0,002, and sampl~ thii;kness
t =0.5 mm_

The transmission Teffis obtained from eq, (4.16) after substitution of

_ 3Vp Qeff _ 3Vp Qeff
"1---- - -' (4.26)
4reff 4rm exp (tcr 2 )

The curves in figure 4,8 have been calculated for'm =0_5 Mm, Vp =0,002 and
t =0.5 mm. The figure shows that with increasing values of a the curves are
flattened out more and more, while the over-ali transmission increases in the visible
part of the spectrum and decreases at longer wavelengths, The influence of a on the
in-line transmission is expressed by Qeffand reff Eq. (4.26) shows that with the
assumptions made the in-line transmission of polycrystaIline alumina is a function of
three parameters of the micro ~tructure: the value of the pore radius where the
distribution function assumes its maximum, 'm; the width of this distribution, 0-;
and the porosity, Vp_ For each set of these parameters it is possible to calculate the
transmission as a function of wavelength.

4.23 Measurements 0/ the in "line tmnsmission

All samples used for the transmission measurementS were plane-parallel slices with a
thickness of 0,5 ± 0.01 mm. These slices were made from the sintered pellets
(chapter 2) Or the hot-pressed rods (chapter 3) by sawing, grinding and polishing.
The grinding of hot-pressed alumina proved to be much more time-consuming than
72

the grinding of sintered alumina. The slices were given a final polishing on both sides
with 0 - 2 I_UTI diamond paste to obtain a good surface finish. The importance of
surface finish on transmittance has been demonstrated by Grimm et a1. 0:>). Scratches
and so on will greatly affect the back.scattering of light.

Transmission measurements were carried out in the wavelength range from 0..4 .
2.5 11m with a Beckman DK 2 spectrophotometer. This apparatus could be oquipped
with an integrating sphero to measure the total transmission, I.e. the sum of the
diffuse transmission and in·line transmission. For measurements of the in-line trans-
[11ission the apparatus could be provided with a special transmission unit with the
detector situated 25 em behind the sample ({) minimi;1;e the measurement of
scattered light. As the light.sensitive surface area of the detector waS 7.2 mm 1 , only
light scattered in a <;:(me of a half-angle less than 0-0 I rad (about 0.5°) could inter-
fere with the transmission measurement. This means that only a small <;:onection
has to be applied to the measured SC<lttering coefficient. This point will be discussed
in more detail in ~ection4.2.4. The same spe<;:tluphotorneter equipped with the
integrating sphere was used to meaSllre the diffuse reflection due to backward
scattering. The principles of the measurements arc schematically shown in figure 4.9.

r~~---"t-T-F!e!-- -- '1'
< t " , <:>
Dol
A

~~f
C

Fig. 4.9. Pos.ition of thl:: Sctr):~pk in the BcckIno,o !'.pcctrQphct0m~~a uscd for me~l,.~\.J.rcment of
the in-line n.n.mi»io'l (A), enrol transmission (B) and tot "I r~t1oction (C).

The transmitt;mce m~aSll(ements at higher wavelengths (2.5· 7 pm) were !llade

using a Hit.achi double-beam Speet(ophotometer. The position of the sample irl this
apparatus is shown schematically in figure 4.10. Much mure scattered Ught will be
0
measured. The aperture angle of the Hitachi can be calculated and is about 4 • This
)11eanS that the transmission at 2,5 I.UTI measured with th~ Beckman will differ from
that measured with the Hitachi.
 73

t ---- ~G': - ------ ---,..-/.,,\

I ~,..
I "

, ~
s
Fig. 4.10. Posi[jon of the sample;n the Hitachi spectrophotometer.

4.2.3.1 Influence of the pore size

The two techniques for fabricating dense, polycrystalline alumina, vb;_ normal
Mntcring described in chapter 2 and hot pressing described in chapter 3, provide
materials with very diverse microstructures. A comparison of the microstructure
of hot-pressed alumina and sintered alumina has already been made in chapter 3.
At about equal porosities the mean grain size differs by a factor of twenty and
the mean pore sb;e by a factor of five. We expect therefore a ~reat influence on the
optical properties. Figure 4.1 I gives the in-line tranSmission of a hot-pressed sample
and a sintered sample, both dcnsified to about the same relative density of 99.95 %
(porosity Vp = 5 x 10-4 ). The transmission of sapphire is also shown for comparison.
100r------------------,

'-Sapphira
80

0.4 0.6 O,S 1.0 2.0

-- ,--_ W.volongth ~ [urn]

Fig, 4.11. Measured in-line transmission of a sample of hot-pressed alumina (KG 15 3-HU) and
norm.lly Sintcrcd .lumin. (0176-S6) meaSured with the Beckman spectrophotometer.
Porosity V -p .. 5 X 10-4 , sample thickness t ~ 0.$ mm for both samples_ The figure .lso shows
[he m~nsmlssion of sapphire.
74

As can be seen, the in-line tranSmission of the hot-pressed sample is strongly

dependent on wavelength: it is very low at the shorter wavelengths but approximates
to the transmission of sapphire in the infrared_ This is in agreement with a Rayleigh
type of scattering and points indeed to the presence ofvery small pores_ It also
provides experimental evidence of the minor importance of the birefringence, The
value of ton is 8,5 x 10-3 at Ao "0.4 !.1m 1,) and i'in is 7.5 x 10"3 at Ao = 1.0 !.1m 14),
In spite ()f this small change in the birefriIlgcnce there is a very significant change
in the in-line transmission. Normally sintered alumina has a higher in-line trans-
mission at the shorter wavelengths, but the dependence on wavelength is weak, Thi$
is in agreement with a Mie type of scattering and points to larger pore sizes,
The increase in transmission is continuous without oscillations, indicating a spread
in the pore sile distribution of (};.. 0.3 (see section 4.2,2.3)_

The complete transmission curve is shown in figure 4.12.

T,r._,,"'~
80

70

60

60

.0

JO

zo
10

Fig. 4.12. Complete tt"",smi;;i"" curve. of tho ~an\e samp! .. a; in figure 4,11, HI' means hot·
pr~!i~d alumina f S meuns n.ormally sintert:d alumina,

The discontinuity at Ao '" 2.5 11m is the result of the difference in aperture between
the two spectrophotometers, reflecting the fact that the Hitachi is not a suitable
apparatus to measure the in-line transmission. The decrease in transmission above
4.5 Mn1 is probably due to true absorption ~7) and not to scattering. The figure
shows that the influence of light scattering by the pores in hot-pressed alumina at
the longer wavelengths is greatly reduced, This ()pens the possibility of using hot-
pressed alumina as an LR. window.

Figure 4.13 gives the total transmission and the total reflection (normal reflection +
diffuse ret1ection) of the same samples as measured with the Beckman spectro·
photometer, Although the in-line transmission of hot-pressed and sintered alumina
 75

90
~ppni~

Tmtol

l!;,;r~1
eo ::::=====
~
Mh::tl tl"Cll""I5mi5~ion
';11

60
50

<0

~
:ll

20 toto.l rtH.~;i(Jr.

"'0

O~ DB O~ I, .S
2 '.[~ml

FiS.4.13. Total transmission and total rcfl~ctk>n of tbe same samples as in fi(1ure 4.11 measured
with th~ B~ckman sp~ctrophotometer.

are very different (figure 4.12), the total transmission does not differ very much. AI
the shorter wavelengths the total transmission of sintered alumina is even higher.
At these wavelengths hot-pressed alumina is seen to have a strong diffuse reflection.
This is to be expected when the scattering behaviour more and more resembles
Rayleigh scattering.

From figure 4.6 we have seen that transmission is lowest for some critical pore size,
this pore size being of the same order of magnitude as the wavelength used. At
smaller pore sizes pore growth will have a detrimental effect on the transmission
and this can be demonstrated by annealing hot-pressed alumina samples. At larger
pore sizes pore growth will enhance transmission. This is illustrated in figure 4.14.
It gives the in-line transmission and total transmissiOn of two identical samples, one
sintered for 2 hours at 1800 °c, the other sintered for 24 hours at 1800 °c. At this
high temperature there is hardly any inCrease in density by prolonging the sintering
time from 2 to 24 hours. However, there is a considerable increase in mean grain
size from 17 pm to 32 pm and this is accompanied by a conSiderable increase in pore
size. The mean pore size as determined with the method outlined by Fullman 3S)
has increased from 0.33 pm to 0.46 pm.

4.2.3.2 Influ ence of the M gO con ten t

In chapter 2 we have described the influence of the amount of MgO On the evolution
of the microstructure. As both the porosity and the pore size are affected the amount
of MgO Can be expected to have a great influence on the in-line transmission.
76

0.5 to 2(1 2.5

WAVel."NGTH ",,,,I

fig. 4.14. M!;':.j\$u .. ~d 1;t'.&flsmission curves of two samples of alumina $intlt:I'~d ;).[ 1800 ~ C fur 2. h
and 24 h [esp~c(iv~Jy. I'O(o<it)l Vp ~ 0.001, >ample thickness t ~ 0.5 mm for both "'''plcs.

The same samples 1I~ de~cribed in section 2.3.3 and d(lped with 50 ppm to 3000
ppm MgO as a ~intering aid were used for the transmission measurements. All
samples received the same sintering treatment: first, l.S hours at 1630 °c and
second, 10 hours at 1850 °e. The microstructures and the densities (If these
specimens can be found in section 2.3.3. From the sample with 50 ppm MgO
containing some cracks no sljce~ for the transmission measu)'em~nts Gould be
prepared. Results for the other specimens are given in table 4.3. The trammissiml
values have been taken from the transmission spectra at the wavelength of 0.5 pm.

Table 4.3

Measured in-line transmission and MgO content

ppm MgO transmission (%)

100 29
200 25
300 18
1000 12
3000 4

The data of the table can be understood 4ualitatively a, follows. The samples with
300 ppm MgO and more contain an increasing amounl of second-phase pllrtidcs.
These particles result from the undissolved additive or result from precipitation
during cooling, 01' both. These particles act as scattering centres; lhe: rcrractly~ index
of stoichiometric spinel MgAl;l 0 4 is 1.72 at th~ wavelength of 0.5 Prll. The low
transmission of the last sample is of course also cau~ed by its lower density (fig.2.8).
 77

Although the samples with 100 and 200 ppm MgO have about the same total volume
fraction of pores, the former has the highest transmission. The reaSon must be the
larger mean pore size which is found in this s<lmple with its non-uniform microstruc"
ture (section 2.3.3.2).

The composition with 300 ppm MgO was chosen to investigate the influence of the
sintcring temperature on the in·line transmission, bdng very sensitive to differences
in pore density and pore size. All samples were sintered for 10 hours at the
temperature indicated in table 4.4, except the last two samples, which were sintered
for 24 hOurS. Transmission values are again those at 0.5 ,urn wavelength.

'fable 4.4

Influence of sintering temperatur~

on in·line transmission

temp. ("C) transmission (%)

~--

1850 19
1800 21
1750 21
1700 12
1650 13
1600 iO

The table shows that the sintering temperature can be lowered to 1750 0 C without
any significant change taking place in the in-line transmission. Samples sintered at
lower temperatures have lower transmission values, not only because of their higher
porosity but also because of their smaller mean pore size.

4,2.3-3 Influence of extra addition of Y203 and CaO

Sintering experiments were carried out to see if small additions of Y20; or CaO
could enhance the transmission of alumina sintered at relatively low t~mperatures.
These experiments and the influence of the additives on the micro~tructUIe were
described in section 2.3.3.3. Here we only give the results of the in-line transmission
measurements. Only one composition with extra Y1 0 3 and one with extra CaO was
studied: 300 ppm MgO + 1000 ppm YlO~ and 300 ppm MgO + 50 ppm CaO.
Table 4.5 gives again the transmission at 0.5 Mm of samples sintered for 10 hours at
the indicated temperature. An exception is again the sample sintered at 1650 °c,
which was sintered for 24 hours.

From the data of this table it Can be concluded that addition of extra Y20 3 has
an adverse effect on the in-line transmission. The effect of addition of extra CaO
on the in-line transmission is negligible.
78

Table 4.5

Inf1uence of sintering temperature on in-line transmission

.,,' ... .. _.
Temp. (C) transmission (%) transmission (%) transmission (%)
MgO only ,. extra Y20J + extra CaD
.... .. _-----
1800 21 - 22
1750 21 II 20
1700 12 9 12
1650 13 6 13
, ...

4.2.4 Determinl1tion of microstlUctural parameters from the measured trans-

mission spectra

In this section we shall compare the calculated results and the experimental results
for in-line tranSmission. Wilh the assumptions made in section 4.2.2 we have seen
that the in-line transmission of polycrystaIline alumina is a function of three para-
meters of the microstructure: tht porosity Vp. the spread in the pore size distri-
bution (} and the value of the pore radius, where this distribution is maximum rm·
Generally we must treat Vp as a free parameter and not as a known quantity. It is
derived as a small value from a difference, which makes it relatively uncertain at
very high densities. With much CarC it is possible to determine the density with an
~ccuracy of ± 0.0005 g/tm 3 (sec section 2.3.2). This means an inaccuracy in the
porosity of ± 0.25 x IO-~. For each parameter set (rm, 0, Vp ) it. i~ possible to
calculate the transmission a~ a function of wavelength. Conversely, we can try to
determine these parameters from the measured tranSmission curve. In fig\lfe~ 4.15,
4..J 6,4.17 and 4.18 the calculated effective transmission, corrected for rcl1ection
losses. has been plotted against the pore radius rm at three different wavelengths.
0.5,2 and S 11m. The parameter a has the values 0.3, 0.4, 0.5 and 0.6 and the
parameter Vp has the values 0.0005, 0.001,0.002 and 0.003.

It is advantageolls, when trying to determine the parameters rm. 0, Vp from the

measured transmission, to plot the scattering coefficient 'r instead of the trans-
mission against the wavelength. According to eq. (4.19) '}' is directly proportional
to the porosity Vp. Moreover, 'r is a material property, while the transmission T
is a sample property.

In comparing the calculated scattering coefficient with the experimental one, we

have to realiLc that Qsca is based on the total amount of light scattered by a
particle in all directions. However, it is impossible to m~asure only the intenSity
of the undisturbed light, with the complete exclusi(ln of light scattered in the
 79
90r---~--------~
1..W.l V.=01l00S
60

70

o 0.1 0.2 o.J O~ as

-----400 r,....I..I.i m]

Fig. 4.15. C,..lc"'at~d. transmission cQrrecteo for reflection 10515~5 35 a function of th~ modal
value of 1;h~ por~ radius 'Ym for different vah,Ics of the width of the distribution a and th~
wavelength ),.. ' Porosi~y Vp = $ II 10" , sample thicknoss t .. 0,5 moo.

Hg. 4.16. The Same as in figure 4,15, Vp = 10"

forward direction. Therefore Qsca must be corrected for the light scattered in a cone
of half. angle 8 determined by the detector in the spectrophotometer. Gurnprecht and
Sliepcevich ~9) define a correction factor F as

(4.27)
80

where Qa stands for the actual scattering coefficient and Qt for total ~cattering co·
efficient. it and i2 are the intensity functions of the scattered wave introduced in
eq. (4.7).

~o
T.,.I%I \.:.'5 ~rr.
~o

'ro
50

50

'U

20

1D

O~ 06 0" as O~ ;0
- r.. [)Jrr l ]

Fig. 4.17. Th~ same as in fih'ure 4.15, VP = 2 )( 10".

':II)

eo
7(1

50

,0
02
u:l
a'.
0,
~5
i-'5)Jr T1
-:i
,0

01 07 O~ Og ;0

Fig. 4.18. The .ame as in figure 4.15, Vp = 3 " 10-'.

 81

Assuming that i = (i l + i1.)/2 is independent of e for small values of e, eq. (4.27)

reduces to

(4.28)

The value of i can be approximated in several ways. Gumprecht 39) demonstrates

that for large spheres (x ~ 20) and small angles (8 .;;; 1.5") the exact value of I is in
good agreement with the value calculated from the much simpler diffraction theory.
Penndorf 40) proves that for x > 5 the value of i can be approximated by (Y4X 2Qt)2 .
We tlnd that F decreases with the size parameter x. In our experiments the highest
value of x is about 20. This gives I - F = 3.9 x 10'3 according to the method of
Gumprecht and I _. F'" 4.3 X 10-' according to the method proposed by Penndorf.
The agreement is very satisfactory and it means that the correction upon Qsca is
only 0.4 %. For smaller values of;x this correction is even less, for which reason
we have neglected it in the following.

We return now to the tlgures 4.15 to 4.18. These curves also give the scattering co-
efficient at a given wavelength as a function of pore radius 'm ,
with 0 and Vp as
parameters. Comparison with the experimentally obtained,), at some discrete wave-
lengths gives generally a number ofpossib1c combinations of 'm ,
r:J and Vp. For
each of these combinations we can calculate the scatterin(l coefficient as a function
of wavelength. By repeated comparison with the experimentally determined
scatterin(l coefficient at twelve wavelengths one can find the parameter set that
gjves the best fit Over the whole wavelength region.

This procedure was applied to normally sintered and hot-pressed alumina. As an

example figure 4.19 gives a plot or the experimental and calculated 'Y versus \0 of
a sintcrcd alumina. The curve shown was obtained by using a least-squares opti-
mization in the choice of rm, r:J and Vp " The points were obtained from the trans-
mission measurements. The measured density of the sample i~ 3.978 g/cm~, which
gives Vp -- (2 ± 0.25) x 10- 3 . The best tit with the experimental trammission was
obtained with the parameters Vp "' 1.9 x 10-3 , (J '" OA and rm " 0.34 Mm "for the
mean pore radius (this gives r "0.43 Mm). The va.lue found for the porosity in this
way is in good agreement with the experimental Vp. The values of (] and rm are
also very reasonable.

The same calculations Wl>fl> made for samples of hot-prossed alumina. Figure 4.20
is an example and gives the experimental and calculated scattering coefficient of a
hot-pressed specimen. The measured denSity of this transparent material is
=
),984 g/cm', which means a pc)rosity Vp (5 ± 2.5) x 10"4. For several values of
(J a combination of Vp and 'm can be found that (lives a reasonable agreement

between calculated and measured transmission curveS. In figure 4.20 the calculated
curve belongs to the set (] =OJ, Vp '" 4.9 X 10- 4 and rm = 0.11 pm. However, the
standard deviation of a least-squares fit for this curve is only slightly lower than the
82

50

r 30

0.5 to 1.5 2.0

Aol jJm ]
Fig, 4,19. Scattering coefficients a. a function of wavelength. Dot., measured on a oormally
sintcrcd s.ample of alumina. Solid line; calculated as::iuming a lognormal pOt{!' si;!.e di').J;:rtbllJ;:ion
with 'm = 0.34 1'''', <, m 0.4 ond Vp < 1.9 x 10".

20

15

10

o~~~~~~~~~~~~L-L-~~
05 10 1.5 2,0
'ol\J m! -

Fig. 4.20. Scattering co<fficieOfs as a function of wavelength. Dots: mc ..urc~ on. a hot:pressed
sample of alumIna. Sohd Itne; oalculated assumtng a lognormal pore OlZC dl<mbutlon wIth
Tm = 0.11 I'm, <"1 0.3 and Vp = 4.9 X 10"'.
g
 83

standard deviation for a curve with the parameter set (J '" 0.6, Vp " 6.6 x 10-4 and
'm '" 0.03 Ilffi· A comparison of these values of'm with the value estimated from
the micrstructure shows that the value of'm " 0.11 /-1m is to be preferred. The
porosity is again in good agreement with the experimentally found porosity.

4.2.5 Conclusion

The light transmission of polycrystalline alumina is governed by the scattering of

light by the residual porosity. The Mie theory allows a calculation of the trans-
mission losses due to scattering by pores. The experimental data can only be
described by this theory, if we assume a spread in pore size. We have calculated
transmission spectra for alumina with a given value of the po\Osity Vp , assuming
a lognormal pore size distribution with a modal value of the pore radius rm and
width of the distribution u. The measured in-line transmission spectra of
normally sintered and hot·pressed alumina samples with widely differing micro-
structures can be well described by this theory. We have determined the micro-
structural parameters Vp , rm and (J from the measured transmission spectra.
Very reasonable values for rm and (I are obtained, while the calculated and
experimental values of Vp are in good agreement. This good agreement supports our
assumption that in this approximation we can neglect the influence of birefringence
on the transmission loss in alumina.

4.3 TranSp!lfent !lnd t~!ln$lucent alumina

4.3.1 Introduction

In chapter 3 we mentioned a striking difference between hot-pressed and normally

sintered alumina. Even after alumina has been sintered to nearly theoretical density
at high temperatures, the material is translucent. It looks, at best, like ground glass.
A slice of hot-pressed alumina, on the other hand, can be seen through very well,
and in common parlance this material would be described as transparent. The
difference is j)Iustrated in figure 4.21, which shows two discs of alumina held
10 em above a printed page. The text remains readable only in the case of hot-
pressed alumina, although there is considerable loss in contrast.

There is much confusion in the literature in descriptions of a densely sintered

ceramic material. Words like 'transparent', 'nearly transparent' and 'translucent'
are often used inaccurately. The definition of the word transparent given in
Webster's dictionary 41) is: 'having the property of transmitting light without
appreciable scattering so that bodies lying beyond are entirely visible'. In this sense
sintered alumina is not transparent. This definition also indicates that the difference
between translucency and transparency is rather subjective: it leaves the judgement
to the human eye. We shall return to this point in the next section.
84

grain size of about

Th~ pores are
inside the grains. The m
specimen shows a ~ess h
magnesia present) of about
.•. " 1 j and h'
redomi

HOT-PRESSED DENSE SINTERED

ALUMINA ALUMINA
0)'.-

TRANSPARENT TRANSLUCENT

Fig. 4.21. Photograph showing twO di~c~ of polycry'talline alumina "hour 10 <m ahove a print«l
pa.ge. Only th~ tt.:xt urJl..k~· I;hf~ hOI:"-prc.'l.5Cddisc is. readable.

The lack of tr~nsparency of ~intcrcd alumina has been ascribed to grain boundary
~catteriIlg and birefringence s, 10, II). This underestimates the infhlence of porosity
and pore size. Because of its v~ry small grain size (Jess than I }.lIn is pussible) it is
precisely the hot-pressed alumina that should suffer frum a relatively high contributiun
of grain boundary scattering and double refractiun. Nevertheles~, this material is the
more transparent one.

In the following the dtfferenc~ between transparent and translucent alumina is

described in terms of the width of the forward lobe in the angular s(anel'ing dia-
gram and in terms of the blur both rnateJ'iais cause in imaging a test object.
A di~cussi()n is also devoted to the relationship between these properties and the
microstructure of the material and its preparatioll method.
 85

4.3.2 Theoretical considerations

In section 4.2 we focussed OUr attention on the in-line tra.nsmissiOn. This quantity
could be calculated with the three parameten: pore size, spread in the pore size and
porosity. The same three parameters determine the angular distribution of the
scattered light. This distribution can be calculated from eq. (4.3), which gives the
amplitude functions of the scattered wave as a function of the scattering angle ().
The variation of the angular scattering with the size of the scatterers and with the
scattering angle is quite complicated ::). For particles an order of magnitude
smaller than the wavelength the scattering diagram is calculable from the Rayleigh
scattering. The diagram is characterized by the symmetric forward and backward
scattering. With increasing particle size forward scattering dominates more and
more (the Mie effect), very complex oscillations with the scattering angle develop
and the forward scattering lobe becomes increaSingly narrow. FOr large particles
nearly all the scattered light is concentrated in a very small angular zone (diffraction).
The width of the forward scattering lobe and the position of the maxima and minima
can be used to determine the particle size in a monodispe)"se or nearly mono disperse
system 42). However, no oscillations are found in the scattering profiles of our
alumina samples (figure 4.22),

100

0,010 10 ;;0 3(l 40 so 60 70 60 90

scattoring angle B

Fig. 4.22. Angular disrribucion of tile scattered light intensiry on a logoarithmic scale (),.o =
0_546 I'm), mcasur~d on a sinr~red and hot-prossed samp!. of alumina.
86

The extent to which a sample of densely sintered alumina is translucent, or possibly

transparent, can be characteri7eed by the width at half height of the small scattering
profile. The light respoP$ible fDr this scattering profile consists of two parts. The
first part is the transmitted beam, which is unperturbed by the presence of the
scattering centres. Sinoe its phase is solely determined by the optical path through
the medium, this beam is coherent with the incident light. This light contributes to
the image formation. Tho second part consists of the radiation, which is scattered
in the forward direction and very close to that direction. This light has suffered a
phase delay due to the scattering process and is not coherent with the incident
light. Its contribution to the image formation will strongly depend on the distance
bClwecn the ceramic slice and the object we are looking at. At sufficiently high
density of the ceramic the contribution of the unperturbed light to the total trans-
mitted light will be relatively large and in that case we can expect transparent
alumina.

Although the mea~urement of the width of the diffusely transmitted light gives
information about the degree of translucency of II oeramic sample, it does not give
a definite answer to the question whether a ~pecimen is really transparent. The
reason is the difficulty of measuring the light intensity at very smail scattering angles.
A more adequate method is to measure the distortion of the image that arises when
we look through a slice of alumina at a test object at a certain distance behind the
alumina. Then we have to give a better definition of the concept of transparency.
For II material to be transparent we now require that the distortion of the image
does not affect the limit of resolution of the eye- This definition corresponds very
well with that given by Webster (previous section), but it is also more quantitative.
The limit of resolution of the human eye is about I minute of arc 43). Thi~ means
that the eye resolves details of 1 mm at 3.5 m. For imaging pictures it is more
customary to express the resolution in the number of lines per miJIimetre that can
be resolved. At a distance 0[25 em the eye resolve~ about 18 lines or 9 black and
white line-pairs per millimetre.

A photographic technique can be used to measure the resolution by photographing

a test chart through a slice of alumina. Generally, the diffusely transmitted light
will caUSE image blur. This blur is a convolution of the scattering profile and the
light source. The distortion of the image is proportional to the distance between
object and ceramic, and to the width of the forward scattering lobe. In the case of
transparency the distortion must be so slight that at a distance of about 25 em
from the test chart 18 lines per mm can be resolved, irrespective of the distanoe
between te~t object and ceramic.

4.3.3 Experimental part

The same samples whose in-line transmission was measured were used for the
measurements of the angular distribution of forward scattered light and the photo"
 87

graphic measurements. All these samples had a thickness of 0.5 mm. The measure·
ment of the angular distribution was carried out with a modified Zeiss Gonio·
photometer GP2. A schematic representation of the experimental set·up is given in
figure 4.23.

Iv= 0.54 jJm

Fig. 4.23. Sch<matic ~~p~esenwtion of the position of the satnpl~ in the goniophotomot~r ~sed
for th< m<asur"m~lIt of {he angular distribution of SC3tfered light.

The light source was a mercury lamp. A parallel beam of monochromatic light wilh
a wavelength of 0.546 /.1m was used. The aperture of the photomultiplier was 0.25°.
Measurement without a sample of the beam width at half intensity w, gave
w =0.65°.

The microscopy resolution test chart of the National Bureau of Standards (figure
4.24) was used to determine the resolution a$ a function of the distance between
the object and the alumina platelets. Photographs were made with a Leitz
Aristophot for photomacrography equipped with a 120 mm lens. The position of the
lens and the image plane could be adjusted $0 that the magnification of the test
chart was exactly one (see figure 4.25). The sample could be moved up and down
between the test chart and the Ions. The number of lines per mm resolved at a
certain distance could be determined visually or with a densitometer.
88

111;l,i
W..l.2
IIIII~ IIIF5
111111.0 ~ ::~: 11111,U
L""'~ IIIII~
111111.1
I L8
2
111111. 5 IIIII \. 4 111111. 6

MICROCOPY P[SOWTlON TEST CHAlrr

NfiYlONAL BU~E.AU OF :;IANLlIII~D'3-196J-A

Fig. 4.24. Micro;copy r<<olution te.t ch"r~ of the National Bureau of Standards.

image

I",ns
f=120mm

240 mm

----'----'---'-- test chart

light
tt t ~aurce

Fig. 4.25. Schematic rcprC5~ntati"n of the po,ition of the s.mpl. in the oct·up for (h. phOlD·
graphic me.~iU~n'lMtS. The sample can be mov~d between test chart ~nd lens over a di~tancc
of 24 em.
 89

4.3.4 Results and discussion

The angular distribution of transmitted light measured On the same representative

specimens for sintered and hot-pressed alumina as in the figures 4.11 to 4.13 is
given in figure 4.26. The intensity of light at 0° has been put at 100 % for both
samples. As expected, hot -pressed alumina has a very sh~rp peak round the in· line
0
transmission, The width at half height, w, for the best samples is 0_8 , only little
more than is measured for the blank. There is little spread in the measured values
of w for hot-pressed specimens with small differences in density and pore size.
All values lie between O.S" and 15°. From one hot"pressed sample slices were
made perperulicular and parallel to the pressing direction (sample KG 153-HIS),
The measured values of ware: w1 '" 1_0° and wIi = 1.5 • The difference has to be
0

attributed to the slight crystallographic texture accomplished by the hot-pressing

technique_ This point has already been discussed in section 3.3.5. Rhodes et al. II ),
who have a pronounced texture in their hot-forged alumina, also find a difference
in transmission for specimens taken parallel and perpendicular to the forging
direction_

100

80

i': 60

20

4 16
scatleri n9 angle e
Fig_ 4.26. Scattering profile of tran.mitted light 0,. = 0.546 I'm) measured on a normally
Sintcrcd and a hOI-pressed sample of alumina. The rdative light intenSity is plotlod as a function
e_
of the scattering anglo l'h~ imensity in th. direction of incideoco is arbitrarily assumed to be
100 in both cases_
90

The normally sintered alumina specimens all have a much broader peak at half height.
Values between 4° and 8° are found. This confirms that light passes through sintered
alumina much more diffusely. The degree of translucency is determined by the
number and size of the pores and the presence of second-phase particles. The data
of some specimens have been collected in table 4.6 (which will be discussed below),
together with the preparation conditions, the measured in-line transmission at the
same wavelength (0.546 11m), T, and the sharpness of the image at a distance of
3 mm expressed as the number of lines per mm resolved at that distance, N.

The difference in width of the scattering profile found for hot-pressed and normally
sintered alumina (figure 4.26) results in a sharp difference in the optical resolution .
Figure 4.27 shows the test chart seen through the same slices of hot-pressed and
sintered alumina at a distance of 3 mm above the test chart.

Fig. 4 .27 . Test chart seen through the same alumina samples as in figure 4 .26 at ad istance of
3 mm between test chart and ceramic. 5 line pairs per mm can be resolved through the normally
sintered sample, 18 line pairs per mm throught the hot-pressed sample. Magnification 4x.

In the former case there is no visible loss in sharpness at this distance : the 18 black
and white lines per mm are clearly distinguishable . On the contrary in the case of
sintered alumina the diffusely transmitted light already causes at this small distance
considerable blurring of the image . The limit of what can be resolved at 3 mm is
five line pairs per mm.

The data of five sintered samples and two hot-pressed samples are summarized in
table 4 .6.
 91

Table 4.6

Relation between preparation conditions, microstructure and optical properties

...,'-,'., ...... -
.-~,

MgO
sintering Vp T w Nom'"
Sample cont. Nw
conditions (%) (%) (") (mm- I )
(ppm)

a 500 2h1800°C 0.1 8.4 5.3 4.0 21.1

b 500 24 h 1800 °c 0.1 22.0 4.1 5.6 23.0
c 100 10 h 1850 °c 0.025 29_5 3_6 63 22.7
d 200 to h 1850 °c 0.025 25.0 4.0 5.6 22.4
e 300 10 h 1850 °c 0_025 18.5 4.9 4.5 22.1
f 0 25m 1440 °c 0.05 7.7 1.0 tranS· -
p= l20MPa parent
g 0 40m 1440 °c 0.025 18.1 0.8 trans· -
p", 120MPa parent
------- .. . " ...-

The sample~ a to e are all translucent but to a different degree. The first two
samples do not differ in porosity, but they differ considerably in mean pore size_
Due to the long sintering time considerable grain growth and pore growth has
occurred in ~ample b. The mean pore size as determined with the method outlined
by Fullman 3$) has increased from 0.33 pm to 0.46 Jlm (see also section 4.2.3.1).
This larger mean pore size is respon~jble for a much higher transmission, 1; a smaller
half·height width of the scattering profile, w, and a better resolution limit at the
test distance of 3 mm, N

The samples c, d and e differ in MgO content. Thi~ has only a minor influence on
the density after the indicated ~intering treatment, but it certainly influences the
concentration of second-phase particles and the pore size. As already discussed in
section 2_3_4 non-uniform grain growth occurs in the sample with 100 ppm MgO,
due to an irregular distribution of MgO- This results in a large mean pore sh;e and
thus in a high transmission and small half.height width. The sample with 300 ppm
MgO contains second.phase particles, which are extra scattering centres.

For small distances between ceramic and test chart the limit of resolution defined
as the number of lines per mm that can just be resolved, N, should be proportional
to the reciprocal of the product of this distance and the width of the scattering
profile, w. This means that at a constant distance the product N w must be a
constant too. This is shown in the last column of table 4.6.

The samples f and g listed in table 4.6 were prepared by hot pressing without
addition of MgO. They differ mainly in porosity due to the longer hot pressing
time of the last sample. This results in a higher in-line transmission, but the
92

difference in width of the scattering profile is smaiL In contraSl with the samples
a to e it turns out thal the sharpness of the image of the test chart is independent
of the distanoe for both samples. Even at the largest possible distance of 24 om
(see figure 4.25) the 18 black and white lines are cleady resolved. This resolutjon
corresponds with the resolving power of the eye. The hot-pressed samples with a
thickness of 0.5 mm thus behave in accordance with the definition of transparency
given above and they can be called transparent. This is illustrated in figure 4.28.

.··IIIII~ ·11111&i 11111

63
.
'! 7 I
Ill II '~J~C 1111171; I 7.1 'I 7.1
11111~ IIIII~ 1111~ 1 1 1 8 .0
lllll~
.IIIII~·:
IIIII~
•IIIII"!£'
'i~I.:.·,·....I,i IIIII~ t;J;. .
19.0
-
1.Iit
~ I.:&.
11111

IIIII~
IIIII~
90
.

I~~
:111~n~'.~ IOO~ I~I~ 1,,:.<;. l:i.i ~ ~ III!~ III~ II~

Fig. 4.28. To« ohart seen through a ,lice of hot-pr~ss~d ~l"mi"a at distance, of 8. 16 and 24 ~m.
The last picture tak~n without the ceramic lllusct'.a.tes tl)(" equality in sharpness but thte lQ~!l. of
contrast, Magnification 4 x.

It shows the test chart seen through sample g at distances of 8, 16 and 24 em,
followed by a picture of the test chart without the ceramic slice at 24 em. With
increasing distance only the contrast decreases. This is more serious for samples
with a low in-line transmission, where the intensity of the unperturbed radiation is
low 44). The hot-pressed sample will ultimately loose its transparency, if the in·line
transmission decreases further due to a too large number of small pores.

4.3.5 Conclusion

The striking difference in transparency betwccn hot-pressed and normally sintered

alumina can be described in terms of the width of the diffusoly transmitted light.

The normally sintered, translucent alumina is characterized by the blur it cauSes in

imaging a test object, This blur is proportional to the distance between object and
ceramic, and to the width of the angular distribution curve. The degree of trans-
lucency depends on the number and size of the pores and second·phase particles.
 93

For a material to be really transj>arent we require that the distortion of the image
does not affect the limit of resolution of the eye. This is realized in a material with
very few and very small pores. Samples of hot.pressed alumina satisfy these con-
ditions. Transparent alumina is characterized by the fact that the sharpness of the
image is independent of the distanCe between object and ceramic. Wilh increasing
distance only the contrast decreases.
94

REFERENCES

I, R.L. Coble and J ,E. Burke, Proc. 4th Int. Symp, on the ReactivHy of
Solids, Eds J.H. de Boer et al., Elsevier, Amstordam, 1960, p. 38.

2. D.W, Lee and W ,D, Kingery, ], Am. Ceram, SO(;, 43, 594 (1960).

3, R. Hanna, J. Am. Ceram. Soc. 48, 376 (1965).

4. II. Lange and R, Skib be, Technisch.wissenschaft.liche Abhandlungen der

Osram·GesellschaJt 9, 203 (I967),

5. G.E. br(lchure on Lucalox, Lamp Glass Department, General Electric Co,

Cleveland, Ohio, 1970,

(i. D.W. fludworth, Special Ceramics 5,185 (1972).

7, H,M.Kahan, D,P.Swbbs and R.V.Jones, lnt. Symp.on Optical and

Acoustical Microeleclrunics, Polytechnic ln~titute of New York, 1974.

8. LA, Bondar, F.K. Volynets, L.V. Udalova and V.p. Usachcv,

Inorg. Mat. 7, 553 (1971).

9, N.Grimm, G,B, Scott and LD.Sibold, Bull. Am.Ceram. Soc. SO,

962 (1971),

10. W.H, Rhodes, D.L Sellers, A.H. Heuer and 1'. Vasilos, Final Repl.
for C(lntract AVSSD·0415.67 RR, Aveo Corp" Lowell, Mass., 1967.

11. W.H.Rhodes, D.J.Seller~ and T.Vasilos,J,Am.Ceram.Soc.S8,31

(1975).

12, W.D, Kingery, H,K. Bowen and D.R. Uhlmann, Introduction to

ceramics, 2nd Edition, John Wiley & Sons, New York, 1976, p. 648.

13. G, Kortlim, Rcl1oxionsspektroskopie, Springer Verlag, Berlin, 1969.

14. l.B, Malitson, J. Opt. Soc. Am. 52,1377 (1962).

15. M ,A. Jeppesen, J, Opt. Soc. Am. 48, 629 (1958).

16. A.LDulisa and RJ,Scynl0uI, Proc,oftheIEEE61,981 (1973).

17. P.O. J(lhnsol1 cited as private communication in ref- 9.

 95

18. W .D. Kingery, J. Am. CeraIn. Soc. 57, I (1974).

19. M.A. Ford and G.R. Wilkinson, J. ScL Instr. 3l, 338 (1954).

20. G, Mie, Ann. Physik 25, 377 (1908).

21. H.C. van de Huist, Light Scattering by Small Particles, John Wiley & Sons,
New York, 1957.

22. M. Kerker, The Scattering of Light and other Electromagnetic Radiation,

Academic Press, New York, 1969.

23. Handbook of Mathematical Functions, Ed. by M. Abram owitz and

LA. Stegun, National Bureau of Standards, 1964.

24. R.H. Boll, R.O. Gumprecht and C.M. Sliepcevich, J. Opt. Soc. Am.
44,18 (1954).

25. R.H. Boll, LA. Leacock, G.C. Clark and S.W. Churchill, Tables of
Light Scattering Functions, Univ. af Michigan Press, Ann Arbor, Michigan,
1958.

26. F.C. Chromey, J. Opt. Soc. Am. 50, 730 (1960).

27. J.V. Dave, IBM J. Res. Dev. n, 302 (1969).

28. W.D Ross, App!. Opt. U, 1919 (l972).

29. E.E. Underwood, Quantitative Microscopy, Ed. by R.T. DeHoff and

F.N. Rhines, McGraw-Hill Book Co, New York, 1968, p. 149.

30. G. Tomandl, Ber. Dtsch. Keram. Ges. 48, 222 (I 97l).

31. F. Schuckher, Quantitative Microscopy (see ref. 29), p. 201.

32. 1. Aitchison and l.A.C. Brown, The Lognormal Distribution, Cambridge

Univ. Press, 1957.

33. H.1. Oel, BeI. Dtsch. Keram. Gcs. 43, 624 (1966).

34. CE. Peterson, Tijdschrift v.h. Ned. Electronica· en Radiagenootschap 39,87

(1974).

35. W.F. Espenscheid, M. Kerker and E. Matijevic, J.Phys.Chem.68,

3093 (1964).
96

36, M,I. Mendelson, J, Am, Ccram, Soc, 25, 4J3 (1969),

37, D ,A. G ryvn ak and D ,E, Burch, J, Opt, Soc, Am, 55,625 (1965),

38. R -L FuUm an, Trans. AIME J. of Metals S, 447 (1953),

39, R,O, Gumprecht and C,M, Slicpcevich, J,Phys,Chem, 57,90 (1953),

40. R.B. Penndorf, J. OpLSoc. Am. 52, 797 (I 962),

41. Webster's Third New Int. Dictionary of the English Language, Bell & Sons,
London, 1966,

42, J ,R, Hodkinson, App!. Opt. 5, 839 (1966).

43, 1 ,P.C. Sou thall, Introduction to Physiotogkal Optics, bover Publications,

New York, 1961.

44, KJ, Rosenbruth, Optik 16, 135 (I959).

 97

SUMMARY

Ceramic materials are used in widely diverging applications. This holds for aluminium
oxide Or alUmina (All 0 3 ) in particular. The field of application has brO<idened con-
~iderably, since it became possible to sinte. alumina to such a high density that it could
transmit light. For more than 10 years this translucent alumina has been u~ed as the
envelope of the very efficient high-pressure sodium lamp. This application is success-
ful because the ceramic material is capable of resisting the highly aggressive sodium
vapour.

The transmission of light through sintered alumina is determined by the micro-

structure, bec<iuse the intrinsic absorption is negligible. Therefore, it is necessary to
investigate the relationship between the optical properties and the parameters of
the microstructure. The sintering behaviour of alumina has to be investigated in
order to realize the desired microstructure. These are the two main lines of the
research described in this thesis.

The properties of alumina are discussed briefly in chapter 1. The application of

sintercd alumina as a lamp envelope is also treated briefly in this chapter.

Chapter 2 deals with the sintering process. In subsequent sections the influence of
impurities and grain boundaries on sintering is discussed. Additions of divalent and
tetravalent oxides can strongly influence the sintering rate. A survey is given of these
experiments and of their interpretations which, cQmbiqed with the results of measure-
ments of the electrical conductivity, have led to the model of a Frenkel.type defect
structure in the cation sublattice of alumina.

In the final stage of the sintering process of alumina very rapid grain growth generally
occurs. As a result the pores, which were at first located on the grain boundaries_
become trapped inside the grains from where they can hardly disappear by diffusion.
This so·called discontinuous grain growth is responsible for a relatively high residual
porosity, but can be prevented by the addition of a small amount of magnesia (MgO).
There is no agreement in the literature about the role of MgO. The leading opinion
is that MgO segregates on the grain boundaries, thereby decreasing the mobility of
the grain boundaries. The second part of chapter 2 describes the author's work
directed towards elucidating the role of MgO. This work was carried out by ~tudying
the evolution of the microstructure of alumina with increasing amounts of MgO. As
the solubility of MgO is small (about 250 ppm at 1600 °C), very pure alumina
powder has to be used if additions below the solubility limit are stilI to be significant.
Auger electron spectroscopy was used to see whether indeed an important enrich-
ment of the grain boundaries with MgO occurs. This could not be detected. The
experiments show that MgO in solid solution already prevents discontinuous grain
growth, so that this phenomenon cannot be ascribed to a reduction of the mobility
of the grain boundaries by a segregation mechanism or by the presence of a second
98

phase on the bO\lOdari~s_ A better explanation is given by the fact that MgO enhances
the ratc of pore removal, resulting in a decrease in the number and Silt of the pores
on the grain boundaries. MgO may also increase the mObility of the pores.

Chapter 3 deals with hot pressing of All 0 3 powder. Application of preswre delivers
an extra driving force for sintcring, resulting in densificatio[] at much lower
temperatures thall arC possible with normal sintering_ Due to this low temperature
hot pressing gives a dense material with a much smaller grain size and pore si~e-
·A striking characteristic of hot-pressed alumina is ilS transparency, whereas normally
sintered al\lmina is "only" translucent.

Chapter 4 deals with the optical properties of densely sintered alumina_ First, a
survey is given of the factors that may influence the transmission of light through
polycrystalline alumina_ It is concluded that it is not the intrinsic birefringence of
alumina Or the presence of grain boundaries that determine the loss of light, but
mainly the residual porosity.

The sec~)[]d part of chapter 4 outlines the general Mic scattering theory. A model is
developed that permits calculation of the in-line transmission, deflned as the trans-
mitted light in the diredion of the incident light. This ill-line transmission, being
much more sensitive to changes in the microstructure than the [Olal transmission,
is determined by the volume fraction ()f porosity, the mean pore size and the spread
in the pore size distribution. The measured traI18mission spectra agree very well with
this model. Reason~ble values for the three microstructural parameters mentioned
can be deduced from lhe expcrimen tal traI18mission spectra.

The third part of chapler 4 goes into the difference between the transparent hot-
pressed AI; O~ and the translucent sintered Al2 0 3 , This is descdbed in terms of the
width of the angular distribution of the diffusely transmitted light. This light causes
a certain blur in an imaged test object. To meet our transparency criterion this
distortion or the image caused by thc materia! mllst not affect the limit of resolution
of the eye. Samples of hot-pressed alumina satj~fy this c()[]dition for lransparency.
Only the CCll1trast decreases_
 99

SAMENVA TrING

Keramische materialen worden VOOr zeer uiteenJopende toepassingen gebruikt. Oit

geldt men name ook voor aluminium oxide (Ah 0 3 ), He! toepassingsgebied werd
belangrijk verruimd sinds men er in slaagde aluminium oxide zo dieht te sinteren,
dat het Iichtdoorlatend werd. Seder! ruim 10 jaar wordt dit doorschijnende alumi-
nium oxide gebruikt als omhulling voor de zeer efficientc hoge druk natrium lamp.
Deze toepassing is mede succesvol geworden omdat het keramische materia-al be-
stand bleek tegen de zeer agressieve natrium damp.

De lichtdoorlaatbaarheid van gesinterd A1~ 0 3 wordt bepaald door de microstructuur,

Omdat de intrinsieke absorptie van zichtbaar licht verwaarloosbaar klein is. Het is
daarom van belang de samenhang te kennen tussen de optische eigenschappen en de
parameters van de microstructuur. Een onderzoek naar het sintergedrag van All 0 3
isnodig om de gewenste microstructuur te kunnen realiseren. Oit zljn de twee hoofd-
lijnen van het onderzoek, dat in dit proefschrift beschreven is_

In hct inleidende hoofdstuk 1 worden de eigenschappen van AI:! 0; beknopt bespro-

ken_ Tevens wordt kort ingegaan op de toepassing van gesinterd A1.0 3 a)s lampom-
huliingsmateriaaL

Het sinterproccs word! bchande1d in hoofdstuk 2. Ingegaan wordt op de invloed

die verontreinigingen en korrolgrcnzcn kunnen hebben op het sinteren_ Toevoegingen
van tweewaardige en vierwaardige oxiden kunnen de sintersnelheid sterk beinvloeden_
Een overzicht wordt gcgeven hoe deze experim"nten, gecombineerd met de uitkorn-
sten van de metingen van het electrisch geleidingsvermogcn, hebben geleid tot het
model van een Frenkel defect structuur in htt kationen rooster van Al~ 0 3 -

In het laatste stadium van het sinterproces van Ah 03 treedt doorgaans cen zeer
snelle korrelgroei op, waardoor de porien, die aanvankclijk op de korrelgrenzen lagen,
ingesloten Taken in de krista11en en niet of nauwelijks meer door diffusie kunnen VeI-
dwijnen, Deze zogenaamde discontinue korrelgroei, die verantwoordelijk is voor een
betrekkelijk hoge rcstporositeit, kan voorkomen worden door het toevoegen van
magnesium oxide (MgO)- In de Iiteratuur bestaat geen overeenstemming over de wer-
king van het MgO. De mening die men het meest aantreft is, dat het MgO segrcgeert
op de korrelgrenzen en daardoor de mobiliteit van de korrelgrenzcn remt. In het
tweede deel van hoofdstuk 2 wordt het eigen werk beschreven, dat gericht is gcwcest
op he! vcrhelderen van de rol van het MgO_ Dil is gebeurd door de ontwlkkeling van
de microstructuur met toenemende hoeveeiheden MgO te volgen. Doordat de oplos-
baarheid van MgO zo klein is, (ongcveer 250 ppm bij 1600 °C), moest met zeer zui-
ver Al~ 0 3 gewerkt worden om toevoegingen beneden de oplosbaarhcidsgrens nog
zinvol te laten zijn. Met bchuJp van Auger electronenspectroscopie is ondcrzocht
of inderdaad een belangrijke verrijking van de korrelgrenzen met MgO plaats vindt.
Oit kon echter niet worden aangetoond. Vi! hel onderzoek voIgt, dat MgO in vaste
100

oplossing reeds discontinue korrelgroei voorkomt, zodat dit effect niet toegeschreven
kan worden aan verlaging van de mobiliteit van de korrelgrenzen door een segregatie
mechanisme of de aanwezigheid van een tweede fase op de korrelgrens. De oor~aak
moet gewcht worden in het feit, dat het MgO de snelheid waarmee de porien verdwij-
n~n blijkt te verhagen, waardoor er minder paden in aantal en grootte op de korrel-
grens zitten dan zonder MgO het geval zou zijn. MogeJijk neemt ook de mobiliteit van
de porien toe.

In hoofdstuk 3 word! het ondorzoek aan het hoctperscn van All 0] poeder beschre-
Yen. De bij het heetpersen toegepaste druk levert een extra drijvende Kracht voor het
sinteren, waardoor verdichtjng bjj lagere ternperaturen magelijk is.
Het gevolg is een dieht matcriaal met cen veel k1cincre korrelgrootte en poriegrootte
dan met normaal sinteren mogelijk is. Ben opvallende karakteristiek van heetgeperst
Al 2 0 3 is, dat het doorzichtig is, terwijl normaal gesinterd Ah 0 3 "Slechts" doorschij.
nend is.

Hoofdstuk 4 behandelt de optische cigenschappen van dieht gesinterd AI2 0 3 , Nage~.

gaan wordt eerst welke factoren de transmissie van licht door gesinterd Al~ 0" be-
invloeden. Geconcludeerd wordt dan, dat niet de intrinsieke dubbele breking van
Al z 0 3 of de aanwezighcid van korrdgrcnzen in de ecrstc plaats bepalend is voor
het Iichtverlies, maar dat de restporositcit hiervoor in hoofdzaak ycrantwoordelijk
gesteld moet wOrden.

In het tweede dec! van hoofdstuk 4 wordt de algemene verstrooiingsthcorie van Mie
uiteenge7.et. Tevens wordt een model ontwikkeld om de rechtlijnige transmissie, ge-
deflnieerd als het lieht dat doorgelaten wordt in de richting van het opvalJende licht,
te kUrlnen herekenen. De~e rechtJijnige transmissie, die veel gevoeliger vOur verandc-
ringen in de mierostructmu is dan de totale transmissic, wordt bepaald door de
volumefractie porositeit, de gemiddelde poriegrootte en de spreiding in de porie-
grootteverdeling. De gemeten transmissiespectra blijken goed met dit model overeen
te kOmen. Zelfs kunnen redeli.lke waarden voor de drie genoemde parameters uH de
experimerltc/c transmissiespectra worden afgeleid.

In het derde ded van hoofdstuk 4 wordt ingegaan op het ondcrscheid tllsscn het
door~ichtige heetgeperste AI. O~ en het doorschijnende gesinterde AI. 0,. Dit haudt
verband met de brecdte van de ho~kverdding van het diffuus doorgclalcnlicht.
Bij het afbcelden van een te~tobject veroorzaakt dit licht een bepaalde onscherpte.
Heetgeperst AI~ 0 3 blijkt te voldoen aan de eis, die men aan een transparant mated-
aal moet stdlen, nl. dat deze onsGherpte beneden het oplossend vermogen van he!
oog blijft. Wcl blijkt he! contrast te verminderen.
 101

LEVENSBERICHT

De schrijver van dit proefschrift werd op 16 april 1941 te Renkum geboren.

Zijn middelbare schoolopleiding ontving hij aan het Christelijk Lyceum te Arnhem,
waar hij in 1959 het diploma Gymnasium ~ behaaJde. In datzelfde jaar begon hij
zijn Scheikunde stu die aan de Vrije Universiteit te Amsterdam. Na een afstudeer·
onder1loek onder leiding van Prof. Dr. C. Maclean legde hij in mel 1967 het docto,
raal examen in de Physische Chernie af.
De militaire dienstplicht vervulde hij op de ontwikkelingsafdeling van de Artillerie
Inrichtingen te Zaandarn. Inmiddcls in dienst getreden van de N.Y. Philips' Gloei·
lampenfabrieken te Eindhoven begon hij in mei 1969 zijn werkzaarnheden als
wetenschappelijk medewerker op het Natuurkundig Laboratorium in de groep
onder leiding van Prof. Ir. A.L. Stuijts.
 STELLINGEN

J, G. J. Peclen 17 mei 1977

Bij het zoeken naar cen verklaring vOOr het verschi! ill rechtHjnige lran~mi~sie van
heetgesmede preparaten van A!203 in richtingcn loodrecbt op en evenwijdig aan de
smeedrichting wordt door Rhodes e.a. ten onrechte gecn rckening gehouden met
de mogelijkheid, dat de porien tussen de kristallieten cen langgerektc ¥orm
gekregen hebben.
W. II. Rhode., D. J, Sellers en T. Vasilos, J. Am. Cetam. So~. 51!,
31 (1975).

II
Het vcrstrooiingsmodel van Kahan e.a. dal als parameters de korrelgrootte, de
dubbe\e brcking en de porositeit bevat, maar niet de poricgrootte, leidl tot
onrealistische rcsultaten.
H. M. Kahan, D. P. S(ubbscll R. V. JOnes, Int. Symp. on Optjc~1 and
AcoustiQal Mimoelecttonics, Polytechnic ln~tjtute of New York, 1974.
Dit proof.ehlift, hoofd,tuk 4.2.

III

Het door MarCus e.a. uit Augcr onderzoek aan breukvlakken van Al 2 0 3 afgeleide
model, waarmce zij de inboud van Ca op het sintergedrag van Al 2 0 3 willen ver-
klaren, wordt onvoldoende door de experimcnten Qnderstcund.
H. L. Marcus, J. M. Harris en F. J. :-;,.Ikuwski, Fr~clure Mechanic., of
CermTlics, vol. L, f·:d, R. C. Bradt e.,., Plenum Pre", New YOlk, 1974,
p.387.

IV
Dc argulll<;>nten, waarnlec Jorgensen en Westbrook de segregatie van loegevoegd
MgO op de korrelgrenzen van Al~03 verdedigen, zijn of specu!aticf of indirect.
1'. J. Jorgensen en J. R Westbrook, J. Am. Cemm. Suc. 47, 332 (1964).
Ed. 1. L
1'. J. Jorgensen, Grain Boundaries in ~:n~nc"Ting Materials,
Walter e.a., ClaitN\ Pub!. Div" Baton Rouge, 1975, p. 205.
nit proefschrift., h""fd.(uk 2.3.

v
De hegrippen "translucenl" en "transpanlnt" worden in de keramischc lilemt\lur
onzorgvlI!dig gcbruikt.
Oil p[oefschrift, houfdstuk 4.3.
 VI
A1s men, zoals in de engeistalige literatuur vaak gebeurt, toevoegingen "impurities"
noemt, betekent dit nog niet dat er zonder toevoegingen geen "impurities" zijn.

VII
Het vaststellen van concentratieprofielen d.m.v. het sputteren van een breukopper-
vlak, lOa Is dit gebruikelijk is in de Auger clektronenspectroscopie, dient met grate
vOQfzichtigheid te gebeuren.
H. L. Marcus, J. M, Harri;; en F. J. Snlkowski. Fracture Me"hanic~ of
Ceramics, vol. I, flds R. C. Bradt e..." Plenum Press, New York, 1974,
p.387.
R. L T.ylor, 1- 1'. Coad en A. E. Hughes, 1. Am. Ccram. Soc. 59,374
(1976).

VIII
De bewering van Takagi c.a., dat het sinteren van ZrO~ gestabiliseerd met CaO
aanzienlijk versneld wordt door hel toevoegen van Ah03 I is in zijn algemeenheid
onjuist.
H. Takagi, S. Kuwabara en H. MalSumoto, Sprechsaal107, 584 (1974).
M. J. Bannister cn W. G. Garrett, Ceramurgia Irtt. 1, 127 (1975).

IX
De bekende uitspraak "Meten is Weten" dient wat betreft het karakteriseren van
keramische poeders met de nodige terughoudendheid te worden gehanteerd.

x
De regcl van Burton en Machlin om segrcgatie in het opperviak van legeringen te
voofspellen m.b.v. het fasendiagram is aanvechtbaar.
J. J. Burton en E. S. Machlirt, Phys. Rev. lett"rs 37, 1433 (1976).

XI
De theotie van Hench, die zegt dat een ideaal implantatie materiaai geen histo-
logische veranderingen aan het grensvlak mag verOOfzaken, is moeilijk toe te passcn
op de door hem zelf ontwikkelde bioglas coatingen.
L. L. Hench en E. C. Ethridge, Adv. in Biomedical Eng. S, 36 (1975).

Xli
Het verwijzen naar eigen niet gepuhliceerd werk voor essentWle informatie onder-
graaft de betrouwbaarheid van het artikel.
 XIII
Voor het besturen van gcrneenschappen die cen bepaald doel nastreven is het
principe van "one man, one vote" niet altijd het moest geschikte.

XIV

Achter het verschil in visie op de toelating van kinderen tot het Avondmaal in de
Protestantse Kerken ligt een verschil in beleving van het Avondmaal bij de ouderen.