Environmental Effects On The Fracture of Oxide Ceramics: Uitnodiging

UITNODIGING
U bent van harte welkom

bij de openbare
verdeding van mijn
Environmental effects on the fracture of oxide ceramics

Environmental effects proefschrift
Environmental
on the fracture of oxide ceramics effects on the
fracture of oxide
ceramics
De promotieplechtigheid
zal plaatshebben op
woensdag
18 december 2002
om 16.00 uur
in het Auditorium van de

Technische Universiteit
Eindhoven.
Aansluitend aan deze

plechtigheid zal een
receptie plaatsvinden
waarvoor U ook van
harte bent uitgenodigd.
Niels van der Laag Niels van der Laag

Niels van der Laag
F.D. Rooseveltlaan 239

5625 AZ Eindhoven
040-2486540
N.J.vanderLaag@tiscali.nl
± 170 pag. = 11mm rug

f.c.
glanslaminaat
Environmental effects
on the
fracture of oxide ceramics
PROEFSCHRIFT
ter verkrijging van de graad van doctor aan de

Technische Universiteit Eindhoven, op gezag van
de Rector Magnificus, prof.dr. R.A. van Santen,
voor een commissie aangewezen door het College
voor Promoties in het openbaar te verdedigen op
woensdag 18 december 2002 om 16.00 uur
door
Niels Johan van der Laag
geboren te Boxmeer
Dit proefschrift is goedgekeurd door de promotoren:
prof.dr. G. de With
en
prof.dr. R.C. Bradt
Copromotor:
dr.ir. L.J.M.G. Dortmans
Druk: Universiteitsdrukkerij, Technische Universiteit Eindhoven
CIP-DATA LIBRARY TECHNISCHE UNIVERSITEIT EINDHOVEN
Laag, Niels J. van der
Environmental effects on the fracture of oxide ceramics / by Niels J. van der Laag.
Eindhoven : Technische Universiteit Eindhoven, 2002.
Proefschrift. ISBN 90-386-2754-8
NUR 913
Trefwoorden: keramische materialen; breuk / vastestofchemie / spinel; magnesium

aluminaat / gahniet / zink aluminaat / breukmechanica / fysisch-chemische simulatie en
modellering; thermische eigenschappen
Subject headings: ceramics; fracture / solid state chemistry / spinel; magnesium
aluminate / gahnite / zinc aluminate / fracture mechanics / physicochemical simulation
and modeling; thermal properties
Aan mijn ouders
Table of Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Galloping Gertie . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Ceramics and failure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Aim and lay-out of this thesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2 Theoretical and computational background . . . . . . . . . . . . . . . . . . 7

2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Fracture mechanics: Stress intensity approach. . . . . . . . . . . . . . . . . . . . . . . . 8
2.2.1 Stress concentrators
2.2.2 Stress intensity factor
2.3 Fracture mechanics: Energy approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.1 Griffith energy balance
2.3.2 Mechanical energy release rate
2.3.3 Intrinsic work of fracture
2.3.4 Failure criterion
2.4 Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.4.1 Adsorption isotherm
2.4.2 Adsorption and fracture energy
2.4.3 Adsorption and fracture toughness
2.5 Subcritical crack growth. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.5.1 General
2.5.2 Constitutive model
2.5.3 Empirical power law
2.5.4 Combined kinetic and adsorption model
v
Table of contents
2.6 Experimental mechanical tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

2.6.1 Fracture toughness: SENB
2.6.2 Effect SCG in SENB test
2.6.3 Strength: Three-point bending
2.6.4 Fracture toughness - strength ratio
2.7 Computer simulations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.7.1 General
2.7.2 Bulk and surface properties
2.7.3 Potentials
2.7.3.1 Pair potentials (PP)
2.7.3.2 Density Functional Theory
2.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3 Water vapour influence on the fracture of commercially applied

oxide ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.2.1 Materials and specimens
3.2.2 Fracture toughness and strength
3.2.3 Measurement
3.3 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.3.1 Fractography
3.3.2 Fracture toughness
3.3.3 Relation between fracture strength and fracture toughness for Wesgo995
3.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.5 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4 Subcritical crack growth in calcium hydroxyapatite . . . . . . . . . . . 51

4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.2.1 Synthesis
4.2.2 Characterisation
4.2.3 Fracture
4.3.1 Synthesis and characterisation
4.3.2 Fractography
4.3.4 Analysis
vi
Table of contents
4.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5 Fracture of magnesium aluminate spinel (MgAl2O4) . . . . . . . . . . . 63

5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
5.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
5.2.1 Material preparation and characterisation
5.2.2 Mechanical testing
5.2.3 Surface investigation preparation
5.3 Results and discussion of bulk properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.3.2 Mechanical characterisation
5.4 Results and discussion of surface properties . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.4.1 EBSD
5.4.2 LEIS
5.4.3 DRIFTS
5.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.6 Appendix: Fracture and EBSD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
6 Structural, mechanical, thermophysical and dielectric properties

of zinc aluminate (ZnAl2O4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
6.2 Crystallographic aspects of zinc aluminate . . . . . . . . . . . . . . . . . . . . . . . . . . 86
6.3 Instrumentation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
6.4 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
6.4.1 Powder synthesis
6.4.2 Compaction and sintering
6.5.1 Structural properties
6.5.1.1 XRD
6.5.1.2 Composition
6.5.1.3 MAS-NMR
6.5.2 Mechanical properties
vii
Table of contents
6.5.3 Thermophysical properties

6.5.3.1 Heat capacity
6.5.3.2 Thermal diffusivity
6.5.3.3 Thermal conductivity
6.5.4 Dielectric properties
6.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
6.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
7 Computational investigation of bulk and surface properties of

zinc aluminate (ZnAl2O4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
7.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
7.3 Computational methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
7.3.1 Potentials
7.3.2 Surface energy
7.4.1 Structural and bulk properties
7.4.2 Surfaces (simulation)
7.4.3 Surfaces (experimental)
7.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
7.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
8 Predictive calculation of intrinsic thermophysical properties

from ab-initio phonon density of states: a case study for oxide
ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
8.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
8.2.1 Phonons
8.2.3 Debye model
8.2.4 Moment representation of phonon density of states
8.3 Criteria for comparison . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
8.4 Computer simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
viii
Table of contents

8.5.1 Density of states
8.5.2 Heat capacity
8.5.3 Entropy
8.5.4 Debye temperature
8.5.5 Moments of density of states
8.5.6 Debye temperature from elastic constants
8.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
8.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
9 Epilogue: overview, conclusions & future work . . . . . . . . . . . . . . . 133

9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
9.2 Overview and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
9.2.1 Fracture and adsorption
9.2.2 Surface and computer modelling
9.3 Thoughts for future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
9.3.1 Toughening
9.3.2 Wake field
9.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
Samenvatting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
Samenvatting voor niet-wetenschappers . . . . . . . . . . . . . . . . . . . . . 147
Dankwoord . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
Curriculum Vitae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
ix
Table of contents
x
-1-
Introduction
1.1 Galloping Gertie

Large man-made structures like dykes, bridges and buildings catch the people’s imagination for
its shear intransigence and are therefore symbols of eternity. An important point for all such
large and costly constructions is its (economical) lifespan, which is for modern bridges at least
50 years and for the Delta Project (improvement of the dutch coastal defence systems) at least
200 years. The construction has to be designed by engineers in a way preventing early collapse.
Therefore, they have to understand how the constructions will behave under all applied external
and internal forces under extreme local conditions.
However, sometimes engineers are facing the unpleasant sight of a collapsing construction as
e.g. the spectacular collapse of the 1800 m long suspension bridge over the Tacoma Narrows on
7 november 1940, see figure 1.1. This bridge was meant to be used for over 50 years, but already
collapsed within 19 weeks after its opening and within two years after the start of its construc-
tion. The suspension bridge was nicknamed Galloping Gertie after the unusual large undulation
of 1.5 m of the central span, which increased prior to the collapse to 8.4 m with an addition of
a twist.
The video images of the collapsing Galloping Gertie are widely used in science classes to show
the possible devastating effects of the resonance principle. The engineers of Galloping Gertie
were not unaware of these devastating effects since they knew all about the resonance principle,
but they were simply unaware of the impact of the wind on the bridge which causes turbulence
1
Chapter 1
Figure 1.1: Collapsing Tacoma Narrows Bridge (Galloping Gertie).
leading to the resonance. The failure of Galloping Gertie initiated the research to the aerody-
namic effects on constructions resulting in the present standard procedure to check the effects
of the wind on constructions as bridges and large buildings during the design phase. Galloping
Gertie showed dramatically that failure is actually a good teacher and a very important source
of knowledge.
1.2 Ceramics and failure

Ceramics are made by firing inorganic non-metallic-metallic compounds, such as carbides, ni-
trides and oxides in consolidated powder form explaining the greek origin of the name, kera-
mos, meaning "burned stuff". Ceramics have several favourable properties as e.g. chemical
stability, wear resistance, thermal and electrical insulation and thermal shock resistance. In gen-
eral, ceramics are divided in two major groups: traditional and advanced (or technical) ceram-
ics. Traditional ceramics are materials like bricks, roof tiles and china, which have easy-
quarrable (clay-) minerals as their source. Advanced ceramics like e.g. light-bulbs in cars or
magnetic cores in transformers are high-tech products, where the special properties of ceramics
are being enhanced by means of special processing. Advanced ceramics are less visible to the
general public than traditional ceramics, but are widely present in many applications as e.g. in
a Nokia mobile phone (without battery), where 16 % is made of ceramics or glass [1]. The total
ceramic industry in the United States alone has a market worth over $35 billion [2] of which
10 % are advanced ceramics [3].
Ceramics have very favourable mechanical properties as, in general, high Young’s modulus,
strength, fracture toughness and hardness. However, ceramic components can fail, like Gallop-
ing Gertie did. Moreover, if they fail then they do it in a brittle way showing hardly any defor-
2
Introduction
mation, which could act as a warning. Therefore, it is required for ceramic components prior to
application to have an idea of its mechanical reliability or, in other words, to predict when they
will fail.
The primary requirement for mechanical reliability is that already in the design phase the com-
ponent is designed so that it will not be subjected to applied stresses higher than the strength of
the ceramic. The mechanical reliability of future components can be further improved by a care-
ful examination of components which have failed revealing the origin of their fracture. Since
the fracture originates generally on microstructural imperfections as e.g. pores or inclusions, the
mechanical reliability can then be improved by improving processing as e.g. better mixing of
raw materials.
Another aspect influencing the mechanical reliability is the decrease in strength and fracture
toughness due to application conditions limiting the lifespan of the components. Ceramics are
vulnerable to the process of subcritical crack growth, where reactive molecules from the envi-
ronment enter the (always present) cracks and react with the stretched bonds at the crack tip re-
sulting in crack growth below the critical applied stress for fracture. The extent of subcritical
crack growth is dependent on the susceptibility of the material towards subcritical crack growth
and the partial pressure of the gaseous molecules.
However, reactive molecules do not only interact with the ceramic in a reaction with the
stretched bonds at the crack tip. The molecules can also adsorb on the newly formed surfaces
by the extension of the crack and lower the surface energy and with that also the strength and
fracture toughness, since surface energy is an opposing force to crack extension. This decrease
in strength and fracture toughness limits the life span and the mechanical reliability.
Although, the adsorption of molecules must be taken into account, this is hardly done in contrast
to subcritical crack growth despite the known role of adsorption in the decrease of fracture
toughness of hexaferrites [4] and MnZn ferrites [5]. The question is raised whether this adsorp-
tion is in general unimportant so that it not necessary be taken into account, or that it is an un-
known important factor like e.g. the wind factor in the Galloping Gertie case.
1.3 Aim and lay-out of this thesis

The fracture process is a complex phenomenon where among others intrinsic material proper-
ties, environment and microstructure interact in an unrevealed manner. Present theoretical ap-
proaches generally ignore several aspects and include only the crack tip itself [6], but can not
3
Chapter 1
explain significantly the influence of phenomena as e.g. adsorption and microstructure. A better
understanding of the mechanisms involved in the process zone in brittle (e.g. ceramics) and qua-
si-brittle (ceramic refractories) materials is therefore required.
The aim of this thesis is to understand the role of adsorption in the fracture process of brittle
materials. A better understanding of the associated chemomechanical processes would enable
material improvement by e.g. chemical composition changes. Therefore, a three-way approach
was followed: general survey, model material experiments and computational simulations.
Firstly, the influence of water vapour on the fracture of several oxide ceramics is investigated
in order to find out whether the adsorption is a general influencing feature or that it is only lim-
ited to the iron oxides as hexaferrite and MnZn ferrites. Subsequently, a model oxide ceramic
is used for an experimental and computational investigation on an atomistic level of the influ-
ence of adsorption. Spinel (magnesium aluminate, MgAl2O4) was chosen since it is a prototype
of the ternary oxides class. It does not show plasticity and has a much less complex stoichiom-
etry than the spinel-type MnZn ferrites (Mn2+Fe2+Zn2+, Mn3+Fe3+O4). However, it still exhib-
its cation inversion, which is difficult to simulate in structural computational investigations.
Therefore, it is attempted to eliminate this inversion by synthesizing ceramics of spinels with
just a small inversion naturally present. Zinc aluminate (ZnAl2O4), manganese aluminate
(MnAl2O4) and cobalt aluminate (CoAl2O4) are suitable candidates, but the latter two show also
oxidative transfer of Mn2+ and Co2+ to Mn3+ and Co3+, respectively. Accordingly, zinc alumi-
nate ceramics have been made for further experiments and validation of computational investi-
gations. Finally, computers simulations have been performed to investigate bulk and surface
properties of zinc aluminate.
Furthermore, as fracture is often treated on an atomistic (micro-)level, a number of phenomena,

as e.g. microstructure, are generally not taken into account. Therefore, the process-zone must
be scaled up from this level to a meso-level requiring, among others, thermophysical properties
to be taken into account. As a first attempt, a comparison was made between thermophysical
properties determined from phonon spectra calculated using density functional theory methods,
from the Debye model and from experimental data. In later work, this should be incorporated
into process zone processes.
The set-up of this thesis is aimed to facilitate the reader to read it in sections. Therefore, the re-
quired background is brought together in a single chapter and the other chapters can be read in-
4
Introduction
dividually. As a consequence, repetitions of some parts (notably descriptions of experimental

set-ups) is unavoidable.
In chapter 2, some theoretical background is treated. Firstly, fracture mechanics is dealt with
using the works of Inglis, Irwin and Griffith. Subsequently, the role of adsorption in fracture
mechanics is introduced and incorporated in a combined kinetic-adsorption model for subcriti-
cal crack growth. Finally, the theoretical (quantum mechanical) background of the used com-
puter simulations is explained briefly.
In chapters 3, 4 and 5, the influence of adsorption on the fracture of several commercially ap-
plied oxide ceramics, a calcium hydroxyapatite ceramic and magnesium aluminate ceramics
(porous and dense), respectively, is investigated. Additionally, the synthesis of the calcium hy-
droxyapatite ceramic is also described. Furthermore in chapter 5, the influence of water vapour
on the fracture of single crystal spinel is investigated. The resulting fracture surfaces of single
crystals are studied by Low Energy Ion Scattering (LEIS) to obtain information about the ato-
mistic composition of the fracture planes for comparison with computer simulation results. Fi-
nally, the orientations of the grains on and next to fracture path in a magnesium aluminate
ceramic are investigated using Electron Backscattering Diffraction (EBSD).
In chapter 6, three different synthesis routes of zinc aluminate powder are described and its ef-
fect of the inversion of zinc and aluminium cations. Furthermore, zinc aluminate ceramics are
made in order to find out whether inversion and atom type also have an influence on the adsorp-
tion effect during fracture. Although fully dense zinc aluminate ceramics could not be generat-
ed, several mechanical, thermophysical and dielectric properties are characterised and,
subsequently, extrapolated to fully dense values.
In chapter 7, the bulk and surface properties of zinc aluminate are investigated. The bulk prop-
erties obtained using computer simulations are compared to literature and experimental data.
Furthermore, the possible fracture surfaces along several low-index planes are simulated for lat-
er verification with experiments. Finally, experimental surface investigation of hydroxyl groups
on zinc aluminate using Diffuse Reflectance Infrared Fourier Transform Spectroscopy
(DRIFTS) are performed to gather information about their location on the surface.
In chapter 8, the predictions of thermophysical properties of ceramics in general by the Debye

model and from the phonon spectra, calculated using density functional theory (DFT), are com-
pared to experimental data.
5
Chapter 1
Finally, the epilogue contains some general considerations and ideas about the effect of adsorp-
tion on the fracture of oxide ceramics. Furthermore, some ideas are presented for future work.
1.4 References
[1] Website of Nokia, www.nokia.com
[2] Website of the American Ceramic Society, www.ceramics.org
[3] Critical Technology Assessment of the U.S. Advanced Ceramics Industry (003-009-
00687-2), Bureau of Industry and Security, USA (1993)
[4] G. de With, Anisotropy in mechanical properties of sintered Sr-hexaferrite, Silicates
Industrielles, 295 (1984), 185-189
[5] M.A.H. Donners, L.J.M.G. Dortmans and G. de With, Adsorption and kinetic effects on
MnZn ferrites, J. Mater. Res., 15 (2000), 1377-1388
[6] G. de With, Environment induced failure of brittle and quasi-brittle materials, Mat.
Chem. Phys., 75 (2002), 229-234
6
-2-
Theoretical and computational background
2.1 Introduction
The failure of ceramic materials typically originates at defects as large grains, inclusions, pores
and (micro) cracks, which can be formed during the synthesis of the material (e.g. pores) or
formed during processing and storing (e.g. surface scratches). This requires the understanding
of the role of defects in the fracture process. However, also reactive gaseous molecules take part
in the fracture process via e.g. subcritical crack growth and adsorption phenomena. Therefore,
they must also be incorporated into the theoretical treatise.
This chapter is devoted to the theoretical background required in the following chapters and can
be divided in two parts: fracture mechanics and computational methods. The first paragraphs
will be dealing with the concepts of stress concentrations leading to stress intensity factors. The
next paragraphs will focus on the energies involved in the crack extension. Subsequently, ad-
sorption is treated since it affects the energy balance in the fracture process. Next, after an in-
troduction of subcritical crack growth due to reactive gaseous molecules kinetically interacting
with the crack, a combined model of kinetic and adsorption effects is derived [1,2]. Finally, this
combined model is applied in single edge notched beam (SENB) and three-point bending ex-
periments for the influence of reactive gaseous molecules on the fracture toughness and
strength, respectively.
In the second part, computational methods are treated, which provide insight into and predict
mechanical parameters involved in the fracture process. Firstly, some compact theoretical back-
7
Chapter 2
x
2b
2c
σA
Figure 2.1: Plate containing an elliptical cavity with semi-axes b and c, subjected to an
applied uniform stress (σA). C denotes the crack tip.
ground of several mechanical properties is provided, but the thermophysical properties are ex-
plained in more detail in chapter 8. Finally, the potentials and their theoretical backgrounds of
the pair-potential and density functional theory methods are briefly discussed.
2.2 Fracture mechanics: Stress intensity approach
2.2.1 Stress concentrators

The stress distribution in a plate with an elliptical cavity when subjected to an uniform applied
stress (σA) was studied by Inglis [3]. The elliptical cavity in the plate, with semi-axes b and c
as shown in figure 2.1, can be described by:
2 2
y
x----- + ----
- = 1. (2.1)
2 2
c b
The cavity has a minimum radius of curvature ρ at point C (assuming b < c):
2
b
ρ = ----- , (2.2)
c
which is also the location of the maximum stress σC, given by:
8
Theory
c
σ C = σ A  1 + 2 --- = σ A  1 + 2 --c- . (2.3)
b ρ
The analysis of Inglis showed that a stress concentration of several times the applied stress oc-
curs in the plate. The stress-concentration factor (σC / σA) is dependent on both the size and
shape of the cavity.
2.2.2 Stress intensity factor

Inglis showed that stress concentrations occur at the sharp end of the cavity. Therefore, the
stress (σij) and displacement (uj) fields around the crack tip are analysed by several scientists
with linear elastic continuum approaches using Griffith’s idea to represent the crack as a infi-
nitely sharp end of a cavity. The fields around the crack tip are described in closed analytical
functions using polar coordinates with the assumption that the crack walls behind the tip are and
remain traction free. These analytical functions are known as the Irwin "near-field" solutions (in
general form):
1
σ ij = K ------------- f ij ( θ ) and (2.4)
2πr
K r
u j = ------- -----
-g ( θ ) , (2.5)
2E 2π j
where K is the stress intensity factor, E is the Young’s modulus, r and θ are the polar coordinates
with the crack tip as origin and the functions fij(θ) and gj(θ) describe the angular part of the
stress field and displacement field, respectively. It is important to realise that several cardinal
components appear as separable factors in equation 2.4: the applied stress, size of the crack and
specimen geometry are solely incorporated in the stress intensity factor K and the remaining fac-
tors only in the spatial distribution of the fields.
An (edge) crack can be loaded in three different ways known as the modes of loading as shown
in figure 2.2: opening mode, sliding mode and tearing mode. Only mode I loading is used in this
thesis1 and the entire set of expressions of equations 2.4 and 2.5 for mode I loading are given by:
1. Mode II and III loading will not be further discussed. For an extensive treatise see [2].
9
Chapter 2
I II III
Figure 2.2: The three modes of loading/fracture: I opening mode; II sliding mode and III tar-
ing mode.
 σ xx   cos ( θ ⁄ 2 ) [ 1 – sin ( θ ⁄ 2 ) sin ( 3θ ⁄ 2 ) ] 

  KI  
 σ yy  = -------------  cos ( θ ⁄ 2 ) [ 1 + sin ( θ ⁄ 2 ) sin ( 3θ ⁄ 2 ) ] 
  2πr  
 σ xy   sin ( θ ⁄ 2 ) cos ( θ ⁄ 2 ) cos ( 3θ ⁄ 2 )  and (2.6)
σ zz = ν′ ( σ xx + σ yy )
σ xz = σ yz = 0
 ux  K I r  ( 1 + ν ) [ ( 2κ – 1 ) cos ( ( θ ⁄ 2 ) – cos ( 3θ ⁄ 2 ) ) ] 
  = ------
2E
- ------  
 uy  2π  ( 1 + ν ) [ ( 2κ + 1 ) sin ( ( θ ⁄ 2 ) – sin ( 3θ ⁄ 2 ) ) ] 
with (2.7)
ν″z
u z = –  -------- ( σ xx + σ yy )
 E 
κ = (3 – ν) ⁄ (1 + ν) ν′ = 0 ν″ = ν (plane stress)
, (2.8)
κ = ( 3 – 4ν ) ν′ = ν ν″ = 0 (plane strain)
where ν is the Poisson’s ratio. For completeness, it must be noted that the various stress inten-
sities are additive, i.e.:
K tot = K I + K II + K III . (2.9)
The stress intensity factor in mode I with a uniform applied stress in mode I is given by:
K I = Yσ A c , (2.10)
where c is the crack length and Y is the dimensionless geometry factor. At the moment of frac-
ture equation 2.10 becomes:
10
Theory
K Ic = Yσ f c c , (2.11)
where KIc is the critical stress intensity, also called fracture toughness, σf is the applied stress
at fracture and cc is the critical crack length. The different crack geometries differ only in the
geometry factor, as e.g. the geometry factor of a double-ended straight crack with a length of 2c
in an infinite specimen is equal to Y = π1/2 (= 1.77), for an edge crack with length c to
Y = 1.12π1/2 (= 1.99) and for a semi-circular penny shaped surface crack with radius c to
Y = 2.24π-1/2 (= 1.26).
2.3 Fracture mechanics: Energy approach
2.3.1 Griffith energy balance

Griffith extended the analysis of Inglis of a loaded plate with a crack with an energy based ap-
proach [4] using an infinitely sharp crack. Only two energy terms are dealing with the extension
of the crack under constant displacement conditions: mechanical energy (UM) due to the loading
(i.e. strain energy) and fracture energy (UF) due to the increase of surface. The mechanical en-
ergy decreases in this case with crack growth assuming constant thickness of the plate:
d
U <0 (2.12)
dc M
and the fracture energy increases:
d
U > 0. (2.13)
dc F
The equilibrium for the crack system is given by:
d d
U = ( U + UF ) = 0 . (2.14)
dc dc M
Using the stress distribution as given by Inglis for a double-ended crack with a length of 2c in
an infinite plate with a constant thickness as shown in figure 2.1, but with an infinitely sharp
crack (ρ → 0), Griffith derived an expression for the stored strain energy for a plate of unit
width:
2 2
πσ A c
UM = ---------------
-, (2.15)
E′
11
Chapter 2
where E′ is E under plane stress ("thin" plate) or E / (1 + ν2) under plane strain ("thick" plate)
conditions, E is the Young’s modulus and ν is the Poisson’s ratio. Furthermore, the fracture en-
ergy of unit width is set to:
U F = 2cR , (2.16)
where R is the specific fracture energy, which is assumed to be a constant. In his original anal-
ysis, Griffith equalled the specific fracture energy to the specific surface energy 2γ.
The total energy given by adding equations 2.15 and 2.16 and in combination with the Griffith
condition in equation 2.14 and a critical crack size cc leads to an expression for the critical stress
σc:
RE′
σc = --------- . (2.17)
πc c
As long as σA < σc, crack growth needs more energy than stored in the system and, therefore,
the crack will not extent. On the other hand, as σA > σc, more energy is stored in the system than
necessary required for crack extension resulting in crack growth. Moreover, since the first and
second derivative of the total energy to the crack length are negative the crack will grow in an
unstable manner.
2.3.2 Mechanical energy release rate

Applying a force F on an elastic body with an edge crack as shown in figure 2.3 results in a dis-
placement u. Furthermore, assuming traction free walls, a workless constraint at the crack tip
preventing crack extension and a linear elastic response to the applied load described by
Hooke’s Law
u = CF , (2.18)
-1
where C is the compliance factor (= S , S is the stiffness), provides an expression for the me-
chanical energy:
u
2 2
u Fu F C
UM = ∫ F ( x ) dx = ------- = ------- = ---------- .
2C 2 2
(2.19)
0
If the constraint preventing the extension of the crack is released, the compliance of the body
will increase (dC > 0) with the crack extension from c to c + dc. This follows from the crack
extension requirements du > 0 and dF < 0 and the differential of equation 2.18:
12
Theory
u c dc
Figure 2.3: Elastic body with crack as used in the mechanical energy release rate treatise.
du = CdF + FdC . (2.20)

The increase in compliance leads to a decrease in mechanical energy. It can be shown that for
both constant displacement and constant force conditions the change in mechanical energy is
given by:
2
dUM = – F
dC .
------------- (2.21)
2
The mechanical energy release rate G is then defined as:
dU M
G = – ----------- , (2.22)
dA
where A is the area of newly formed surfaces. Furthermore, the mechanical release rate for a
straight crack per unit width is given by:
dU M
G = – ----------- . (2.23)
dc
It can be proven (e.g. [2]) that under constant displacement conditions the mechanical energy
release rate is a function of the stress intensity implying that the several contributions of differ-
ent loading are additive:
13
Chapter 2
dU M
G = – ----------- = G I ( K I ) + GII ( K II ) + G III ( K III )
dc u
. (2.24)
2 2 2
K K ( 1 + ν )K III
= -----I- + ------II- + -------------------------
-
E′ E′ E
2.3.3 Intrinsic work of fracture

The increase in crack length (dc > 0) results in an increase in fracture energy:
dUF = Rdc , (2.25)
which introduces the intrinsic work of fracture R per unit width opposing crack extension as:
dU
R = ---------F- . (2.26)
dc
Griffith set in his analysis this work rate equal to twice the surface energy γ in a vacuum
(Ro = 2γ). However, it is known that the work rate is, among others, also dependent on the load-
ing rate, temperature and the crack length. The latter results in the so-called R-curve behaviour.
Nevertheless, the work rate remains proportional to the surface energy.
2.3.4 Failure criterion

The balance between the mechanical and fracture energies can be written in a differential form
as:
dU = dUM + d U F = – Gdc + Rdc = ( R – G )dc . (2.27)
The (R - G) term defines the crack extension force. At Griffith’s equilibrium, G = GIc, this leads
for mode I to:
2
K
G Ic = ------Ic- = R . (2.28)
E′
If G > R, the crack extends and if G < R, the crack "retracts". For instable crack extension also
the criteria dU / dc < 0 and d2U / dc2 < 0 must be fulfilled.
The applied load/stress is only introduced in this Griffith’s energy balance via the mechanical
stress rate implying a critical load/stress when a crack starts to propagate leading to (possible)
failure. At this critical applied stress, the stress intensity factor is defined as the fracture tough-
ness KIc. Theoretically, the fracture toughness is a material constant under plane strain condi-
tions. But practically, the fracture toughness is not constant even under plane strain conditions
due to its relation with the intrinsic work of fracture R as seen from equations 2.24 and 2.28.
14
Theory
The intrinsic work of fracture is dependent on the surface energy, which can be lowered by ad-
sorbing molecules on the surface. Therefore, it is required to quantify the influence of adsorp-
tion on the intrinsic work of fracture.
2.4 Adsorption
2.4.1 Adsorption isotherm

Gaseous molecules X adsorb non-dissociatively on the surface on unoccupied sites Γ* with a
certain rate k1 and, simultaneously, desorb again from the surface with a rate k2. On a surface
with a maximum of ΓM active surface sites, ΓX sites are occupied and Γ* = ΓM−ΓX unoccupied.
In a dynamic equilibrium, the following relation holds:
k1 pX Γ* = k 1 pX ( ΓM – Γ X ) = k 2 Γ X , (2.29)
where pX is defined as the ratio between the actual partial pressure and the equilibrium partial
pressure at the operating temperature. In the case of water vapour, this equals the relative hu-
midity. Using the relative surface coverage θ defined as ΓX / ΓΜ, equation 2.29 can be rewritten
as:
bpX
θ = ------------------
-, (2.30)
1 + bp X
where b is equal to k1 / k2.
Equation 2.30 shows the relation between the surface coverage and the applied relative partial
pressure of the adsorbing molecules, which is known as the Langmuir adsorption isotherm [5-
6]. Furthermore, the constant b is also known as the Langmuir adsorption coefficient. The Lang-
muir adsorption isotherm for several values of b is shown in figure 2.4.
Strictly speaking, the Langmuir adsorption isotherm only describes monolayer adsorption, but
multilayer adsorption can be described by an adaption of Langmuir’s analysis by Brunauer, Em-
mett and Teller known as the BET-equation [7]. Restricting to n layers, the BET-equation be-
comes [8]:
n n+1
1 – ( n + 1 )p X + np X
θ = cp X -------------------------------------------------------------------------------
n+1
, (2.31)
( 1 – p X ) ( 1 + ( c – 1 )p X – cp X )
where c is approximately given by:
15
Chapter 2
1 .0
c
0 .8
0 .6
θ [-]
b
0 .4
0 .2 a
0 .0
0 .0 0 .2 0 .4 0 .6 0 .8 1 .0
pX [- ]
Figure 2.4: Langmuir adsorption isotherms with different Langmuir adsorption coefficient b:
a) 0.25, b) 1 and c) 20.
Q1 – Qv
c ≈ exp  ------------------- , (2.32)
 RT 
where Q1 and Qv are the heats of condensation of the first layer and the liquid absorbing species,
respectively, R is the gas constant and T is the temperature.
The restricted BET-equation and the Langmuir adsorption isotherm describe the adsorption
well in the presence of opposing walls as in e.g. capillaries and cracks, since these walls phys-
ically limit the number of adsorbed layers. However, in the absence of such limitations, the re-
stricted BET-equation and the Langmuir adsorption isotherm only describe the adsorption
incorrectly in the high relative pressure range.
2.4.2 Adsorption and fracture energy

The intrinsic work of fracture is proportional to the surface energy in the analysis of Griffith.
The surface energy will decrease with ∆γads in the presence of adsorbing molecules X and thus
also the intrinsic work of fracture:
dU ads
R X = R o – 2 ------------- = R o – 2∆γads , (2.33)
dA
where dUads is the adsorption energy. The change in surface energy can be calculated using the
Gibbs-equation:
16
Theory
d ∆γ = k B TΓ ( a X ) , (2.34)
d ln a X ads
where aX is the chemical activity of the adsorbing molecules, Γ is the excess concentration of
the adsorbing molecules on the surface, kB is Boltzmann’s constant and T is the temperature.
The change in surface energy can be written from equation 2.34 as:
pX
θ
∆γads = k B TΓ M ∫ ------ dp X , (2.35)
pX
0
where ΓM is the maximum excess concentration, if the adsorption isotherm is known and also
continuously increasing, since the partial pressure pX is related to the chemical activity. Apply-
ing the Langmuir adsorption isotherm to equation 2.35 provides a relation between the intrinsic
fracture work energy and the partial pressure given by:
R X = R o – 2k B TΓ M ln ( 1 + bp X ) . (2.36)
2.4.3 Adsorption and fracture toughness

Two ways to decrease the required applied stress for fracture σf are revealed by rewriting equa-
tion 2.11 to:
K Ic
σ f = ------------ . (2.37)
Y cc
The applied stress can thus be decreased by both a decrease in fracture toughness and an in-
crease in crack length.
The fracture toughness without any influence of reacting or adsorbing species is called the inert
fracture toughness Ko and can be measured in vacuum. The inert fracture toughness of a body
with an initial crack length co is given for a mode I loading by:
K o = Yσ o c o , (2.38)
where σo is the applied stress at fracture.
When molecules adsorb on the newly formed fracture surfaces, the surface energy is lowered,
which decreases also the intrinsic work of fracture as shown in equation 2.33. This reduces the
inert fracture toughness to the adsorption controlled fracture toughness Kads, which is for a body
in mode I loading with an initial crack length co given by:
17
Chapter 2
K ads = Yσ ads c o , (2.39)
where σads is the applied stress at fracture.
The relation between the inert and adsorption controlled fracture toughness can be given by us-
ing the Griffith equilibrium as in equation 2.28 and the relation between the intrinsic work of
fracture with and without adsorbing species:
K ads = K o 1 – φ ln ( 1 + bpX ) , (2.40)
with the constant φ given by:
2k B Γ M T
φ = --------------------
-. (2.41)
Ro
The second manner for decreasing the fracture toughness is crack extension from its initial
length co to cc due to the presence of gaseous molecules leading to the process of subcritical
crack growth (SCG), which will be treated in the following sections. The lowering of fracture
toughness due to subcritical crack growth and adsorption can be formulated as:
K ads = Yσ SCG c c , (2.42)
where σSCG is the applied stress at fracture and σSCG < σads.
2.5 Subcritical crack growth
2.5.1 General
The gaseous molecules in the environment do not necessarily have to be involved in adsorption
processes only. Some types of molecules interact also with the bonds in the crack and, especial-
ly, with the stretched bonds in the vicinity of the crack tip. The reacting molecules facilitate
crack growth below the fracture toughness due to a lowering of the activation barrier for bond
breaking. Michalske and Freiman [11] have proposed a chemical model for these reactions in
silica. This process is called subcritical crack growth (SCG).
Subcritical crack growth is occurring in a large number of ceramic materials (e.g. [2]) and is
therefore a long studied phenomenon. For instance, Wiederhorn [12] has shown that the crack
growth rate during subcritical crack growth is controlled by the rate of reaction of the active in-
gredient in the environment with the chemical bonds at the crack tip. Furthermore, Freiman et
al. [13] and Wiederhorn et al. [14] have shown that subcritical crack growth is not only due to
water molecules, but also due to other reactive molecules as e.g. ethanol.
18
Theory
Region I II III
vt
vlim
ln v
vth
KI,th KI,lim KIc

ln KI
Figure 2.5: Typical double logarithmic plot of crack growth rate vs. stress intensity.
2.5.2 Constitutive model

In many materials, a crack grows below the critical applied stress when subjected to an environ-
ment with reactive (gaseous) molecules. Under these circumstances, the rate of crack growth v
(= dc / dt) as a function of the stress intensity shows typically several stages as shown in figure
2.5. Firstly, below the so-called threshold stress intensity KI,th the crack growth is absent [9].
Subsequently, the crack starts to grow slowly above this treshhold value and enters Region I. It
starts to grow more rapidly with increasing crack length and thus stress intensity, where the de-
pendence of ln v on ln KI is approximately linear. However next, at higher stress intensities, the
bulk diffusion of the gaseous molecules to the crack tip is limited and not sufficient any more
to increase the growth rate. The crack growth rate vlim after the limiting stress intensity KI,lim
remains constant and indicates Region II. Finally, Region III is entered as the crack growth rate
rapidly increases to the terminal velocity vt before reaching the fracture toughness.
2.5.3 Empirical power law

Subcritical crack growth, also denoted as stress corrosion or slow crack growth, is an important
parameter in life-time prediction. Subcritical crack growth in Region I is the only necessary part
to take into account for the prediction of time-to-failure due to the fact that the crack will remain
the most of the time-to-failure in this region. Furthermore, the crack growth rate vlim in Region
19
Chapter 2
II is too high to have any practical influence on the time-to-failure and, moreover, Regions II
and III are not always present in all materials.
A linear dependence between ln v and ln KI exists in Region I for most materials. Therefore, the
crack growth rate is empirically approximated by a power law expression [10]:
KI n
v = v o  ------ , (2.43)
Ko
where vo is a pre-exponential factor and n is the SCG-parameter equalling the slope in the
ln v - ln KI curve. It is assumed that the pre-exponential and SCG-parameters are not influenced
by the environment. The activity a of the reactive molecules can be introduced into the pre-ex-
ponential factor to account for its effects as:
η
vo = v η a , (2.44)
which can be, assuming an ideal gas, written as:
η
vo = v η pX , (2.45)
where pX is the partial pressure of the reactive molecules.
2.5.4 Combined kinetic and adsorption model

Reactive gaseous molecules can thus interact in two ways in the process zone at the crack tip.
Firstly, by forming a transition state complex with a stretched bond at the crack tip as is shown
in figure 2.6. This transition state complex decreases the activation barrier for the bond breaking
reaction resulting in an enhanced crack growth. Secondly, by decreasing the surface energy via
adsorption as also shown in figure 2.6. This gives a lower resistance to fracture resulting also in
an enhanced crack growth.
The crack growth can be seen as a molecular reaction between gaseous molecules with a certain
partial pressure pX and the bonds of a solid allowing for the approximation of the crack growth
rate by the rate of the rate determining reaction step. Classical theory of rate processes provides
an expression for the crack growth rate:
η kB T ∆U ∆U
v = pX l o --------- exp  – ----------F- – exp  – ----------B- , (2.46)
h kB T kB T
20
Theory
a) b)
Figure 2.6: Schematic atomistic representation of two possible bond breaking processes: a)
transition state complex formation and b) adsorption.
21
Chapter 2
where lo is the characteristic crack growth step length, η is the (pseudo-)reaction order of pX,
kB is Boltzmann’s constant, T is the temperature, h is Planck’s constant and ∆UF and ∆UB are
the activation energy barriers for the forward and backward reaction, respectively [2, 15]. How-
ever, the activation energies change by the presence of an applied stress resulting in an intro-
duction of a function of the crack extension force (RX - G) according to Griffith’s analysis:
η kB T ∆U F – α ( G – RX ) ∆U B + α ( G – RX )
v = pX l o --------- exp  – ------------------------------------------
- – exp  – -------------------------------------------
 
- ,
 (2.47)
h kB T kBT
where α is the activation area. The mechanical release rate introduces the applied stress and thus
the applied mechanical energy and the intrinsic work of fracture the surface energy effects.
The crack extension force can be rewritten using equations 2.24, 2.36 and 2.40 to:
K o  K2 
G – RX = ------  -----I- – 1 + Φ ln ( 1 + bp X ) . (2.48)
E′  K 2

o
Inserting this expression in equation 2.47, where the backward reaction is usually neglected,
gives:
α ( G – RX )
v = v o p X exp  --------------------------
η
kBT
2 , (2.49)
η   K  βΦ
= v o p X exp  – β  1 – -----I-  ( 1 + bp X )
2
  K o 
with
kB T ∆U
v o = l o --------- exp  – ----------F- (2.50)
h  k T
B
and
αR
β = ---------o- . (2.51)
kBT
When the inert fracture toughness is much larger than the applied stress intensity factors and β
a
has a large value, equation 2.49 can be simplified using exp ( – ax ) ≈ ( 1 – x ) to:
nΦ
------- K n
η 2  I
v = v o p X ( 1 + bp X ) ------
 K o , (2.52)
22
Theory
where the subcritical growth factor n is given by
2αR
n = 2β = ------------o- . (2.53)
kBT
A further rewriting of equation 2.52 produces the familiar empirical power law formula using
equation 2.40 as:
KI n
v = v p  ---------- . (2.54)
K ads
The contribution of the reaction kinetic vkin and adsorption vads factors in the pre-exponential
factor vp are separable as:
n
v p = v kin v ads 1 – Φ ln ( 1 + bp X ) , (2.55)
where
η
v kin = v o p X (2.56)
and
nΦ
-------
2
v ads = ( 1 + bpX ) . (2.57)
2.6 Experimental mechanical tests
2.6.1 Fracture toughness: SENB

A method of determining the fracture toughness of materials is by fracturing a test specimen
with an artificially made large notch. The key element of these methods is that the notch will be
the location of fracture and it simulates a natural crack, but with a known size. Several methods
with several specimen geometries are developed. One of most widely used methods is putting
a single edge notched beam (SENB) specimen with a straight notch in a four-point bending set-
up as shown in figure 2.7. Subsequently, a constant stress rate is applied to determine the frac-
ture stress σf, which decreases with decreasing stress rates if the material is susceptible to sub-
critical crack growth. Generally, the original crack length co is used to calculate the (apparent)
fracture toughness Kapp omitting explicitly the occurrence of subcritical crack growth.
The apparent fracture toughness measured with SENB specimen is given by:
23
Chapter 2
a) F b)
w
h
li
co
lo
Figure 2.7: a) Four-point bending set-up with a SENB specimen. b) Cross-section of a SENB
specimen with the notch.
3Ff ( l o – l i )
K app = Y S σ f c o = Y S --------------------------
2
- co , (2.58)
2wh
where lo and li are the outer and inner span of the four-point bending set-up, respectively, w and
h are the width and the height of the specimen, respectively, as shown in figure 2.7, σf and Ff
are the applied stress and force at fracture, respectively. Furthermore, the geometry factor YS is
given by the Gross-Srawley equation [16-17]:
2 3 4
Y S = 1.99 – 2.47α + 12.97α – 23.17α + 24.8α , (2.59)
where α = co / h, and which is accurate within 0.2 % for the valid range of 0 ≤ α ≤ 0.6.
The geometry factor YS shows a minimum around α = 0.15 and, moreover, changes only slight-
ly close to the minimum. It can be considered as a constant and, consequently, the notches in
the SENB specimen are made around this minimum. Furthermore, since the crack lengths will
not exceed the validity range of the Gross-Srawley equation, this equation is used.
2.6.2 Effect SCG in SENB test

The omission of subcritical crack growth in SENB experiments by taking the initial notch size
co leads to an underestimation of the fracture toughness of materials which are susceptible to
subcritical crack growth. When the subcritical crack growth is taken into account during SENB
measurements, it must be assumed that the geometry factor YS taken at the original notch length
remains constant during the experiment when the notch extends from co to cc, which is only true
around the minimum.
24
Theory
Substituting equation 2.58 into the derived empirical power law expression 2.54 for crack
growth in the presence of reactive gaseous molecules gives:
n· n
dc K app n vp YS σs n n ⁄ 2
v = ----- = v p  ---------- = -------------------
-t c , (2.60)
dt K ads n
K ads
· ·
where the applied stress is entered as a function of time: σ = σ s ⋅ t and σ s = dσ / dt (stressing
rate).
Separation of variables in equation 2.60 gives:
cc n · n tf
1 vp YS σs n
∫ ---------
n⁄2 n
K ads
- ∫ t dt ,
- dc = ------------------- (2.61)
c
co 0
The right-hand side can be expressed as:
n · n tf n n+1
v p YS σs n p YS σf
1 - v----------
-------------------- ∫ t dt = ----------- - --------------
· , (2.62)
n
K ads n + 1 Kn σs
0 ads
using
n+1
· n n+1 σf
σs tf = --------------
· . (2.63)
σs
The left-hand side can be expressed as:
cc
1 2 1 n – 2  --------
1 - n – 2
∫ ---------
- dc = ----------------  --------- –
n⁄2
c (n – 2)  c   c
o c
co , (2.64)
2 Y S σ f n – 2  Y S σ f n – 2
= ----------------  ----------- – -----------
( n – 2 ) K app   K ads 
using equations 2.42 and 2.58 for the adsorption/subcritical crack growth controlled fracture
toughness and the apparent fracture toughness, respectively.
Combining equations 2.62 and 2.64 into equation 2.61 gives an expression for the ratio of the
apparent fracture toughness and the adsorption/subcritical crack growth controlled fracture
toughness:
25
Chapter 2
a) F b)
w
h
lo
Figure 2.8: a) Three-point bending set-up with a strength specimen. b) Cross-section of a

chamfered strength specimen.
1
2 3 ------------
 p YS σf 
2–n
K app n – 2 - v----------
---------- =  1 + ------------------- - -------
K ads  2 ( n + 1 ) K 2 σ· s 
ads
. (2.65)
1 -
-----------
3
 n – 2 v p K app-  n
2 –
=  1 + -------------------- ----- ------------- 
 2 ( n + 1 ) c o K 2 K· 
ads
2.6.3 Strength: Three-point bending

In practice, the large notches, as used in SENB specimens, do not occur in applied materials.
Therefore, it is necessary to determine the applied stress when the fracture starts on natural de-
fects. This applied stress is called strength σf (or S), but it depends on the measuring method:
e.g. tensile strength, compressive strength, shear strength or bending strength. It is important to
realise the differences between these kinds of strengths, since a high compressive strength does
not automatically imply a good bending strength (e.g. concrete). However, as far as only bend-
ing strength is treated, this will be shortened to strength in the remainder of this thesis.
The (bending) strength of a material can be determined using a three-point bending set-up as
shown in figure 2.8. The strength of a material is given by:
3 Ff lo
σ f = --- ---------2 , (2.66)
2 wh
where Ff is the applied force at fracture, w is the width and h is the height of the specimen. The
specimens have to be chamfered in order to avoid edge fracture from abnormal defects intro-
duced by cutting and grinding during the specimen preparation.
26
Theory
2.6.4 Fracture toughness - strength ratio

An expression for the influence of subcritical crack growth in strength specimens is given by a
combination of equations 2.61 and 2.62:
1
c ------------
 · c
n+1
σi n 1
σ f =  ( n + 1 ) ----------n- K ads ∫ ---------- dc , (2.67)
n⁄2
 v p iY c 
co
·
where Yi is the geometry factor of the initial defect and σ i is the applied stressing rate. Using
the assumption that the adsorption/subcritical crack growth controlled strength is larger than the
apparent strength, equation 2.67 becomes:
1
------------
 2 ( n + 1 ) σ· i n 1 n – 2 n + 1
σ f =  -------------------- ----------n- K ads  --------  , (2.68)
 ( n – 2 ) vpYi ci 
where ci is the initial defect size in the strength specimen.
An expression for the apparent fracture toughness can be obtained by a similar derivation using
the assumption that the adsorption/subcritical crack growth controlled fracture toughness is
larger than the apparent fracture toughness:
1
------------
 2 ( n + 1 ) σ· s n 3
n+1
K app =  -------------------- ----- Y S K ads c o  . (2.69)
 ( n – 2 ) vp 
The fracture toughness-strength (Kapp-σf) ratio can be calculated from equations 2.68 and 2.69:
1
· 3 ------------
K app  σs YS c o  n + 1
---------- = Y i c i  -----------------------
- . (2.70)
σf  σ· i Y i c i 3 
If the Kapp-σf ratio remains constant for all combinations of partial pressures and stressing rates,
it can be concluded that the susceptibility to the effects of the gaseous molecules is a material
property and does neither depend on the type of test nor on the used geometry. This allows for
the conclusion that SENB experiments can be used to study subcritical crack growth behaviour
since the effects of the gaseous molecules in the crack is a material property.
27
Chapter 2
2.7 Computer simulations
2.7.1 General
Computer simulations are a widely used tool in engineering sciences to predict the behaviour of
materials and structures. In the field of mechanical engineering finite element methods are used
to model, among others, mechanical behaviour of structures. Predictions can be made from
these calculations where stress concentrations occur indicating possible failure locations.
Finite element methods approach the reality on a macroscale. However, fracture mechanics are
also determined by intrinsic material properties on a microscale. For instance, the fracture
toughness is given by:
K Ic = ER , (2.71)
where E is the Young’s modulus and R is the specific fracture energy. Computer simulations
can be used to calculate e.g. the elastic constants, lattice vibrations and the surface energy (γ),
which appears in the expression of the specific fracture energy as:
·
R = 2f(T, ε, …)γ . (2.72)
Generally, the calculation of these and other intrinsic material properties follows the same pro-
cedure. Atoms are set up in a starting configuration using the symmetry of the crystal lattices
and using periodic boundary conditions. Subsequently, potentials describing the atomic inter-
actions are used to move the atoms to an equilibrium configuration where the overall energy is
minimized.
2.7.2 Bulk and surface properties

When the equilibrium configuration is reached, several properties can be determined. Firstly,
the elastic constants (Cij) can be calculated by taking the second derivative of the Helmholtz en-
ergy F under isothermal conditions, which under adiabatic conditions equals the energy U, with
respect to the applied strain (using the pseudo-vector notation):
2 2
C ij = ∂ F =
∂U
. (2.73)
∂ ε i ∂ε j ∂ ε i ∂ε j
T, ε' S, ε'
In the case of a spinel structure, the elastic constants C11, C12 and C44 can be calculated by dis-
torting the lattice parameters of the equilibrium unit cell by a small amount δ but keeping the
same volume. These distortions of the lattice parameters for the tetrahedral and shear distortions
are given by the following matrices, respectively:
28
Theory
1+δ 0 0
0 1+δ 0 , and (2.74)
–2
0 0 (1 + δ)
1 δ 0
δ 1 0 . (2.75)
2 –1
0 0 (1 – δ )
A second order polynomial fit of the energy-distortion curve is made from which the elastic con-
stants can be obtained via:
2
 ∂ U
 2 = 6 ( C 11 – C 12 ) – 36 ( C 11 – C 12 )δ , and (2.76)
 ∂ δ  tetra
2
 ∂ U
 2 = 4C 44 . (2.77)
 ∂ δ  shear
Secondly, the frequencies of the lattice vibrations are derived from the dynamical matrix, which
is on its turn constructed from the atomic force constants. The atomic force constants φij(k,l) are
defined as the second order term in the expansion of the potential energy φ in small displace-
ments ui of the kth atom due to a displacement uj of the lth atom:
2
∂ φ
φij ( k, l ) = -----------------------------
-. (2.78)
∂u i ( k )∂u j ( l )
Assuming a cell with N atoms and harmonic approximation, the elements of the (3N-3)×(3N-3)
dynamical matrix D are defined as:
φij ( k, l )
D ij = -----------------
-, (2.79)
mk m l
where mk and ml are the masses of the kth and lth atom, respectively. The phonon eigenfrequen-
cies squared (ω2) are obtained as the solutions of the secular equation:
2
D-ω I = 0 , (2.80)
where I is the (3N-3)×(3N-3) unit matrix. The vibrational part of several thermophysical prop-
erties can be calculated using these phonon frequencies.
29
Chapter 2
a)
b)
Bulk region
Near-surface region
Figure 2.10: Schematic representation of the approach of Tasker. a) Structure of crystal cell
for calculation of equilibrium configuration. b) Structure of the crystal cell with a near-surface
and bulk region for calculation of surface structure and energy.
Finally, the surface energy can be obtained by generating a surface in the equilibrium configu-
ration by "cleaving" the crystal and minimizing the energy of the new configuration using the
same potentials as for the bulk energy calculations. The approach of Tasker [18] can be fol-
lowed, where the crystal is constructed by two regions (see figure 2.10): a bulk region where the
atoms are fixed at the equilibrium configuration positions and a near-surface region where the
atoms are allowed to move to minimize the overall energy. The bulk region is required for the
fixation of the atoms in the lower layers of the near-surface region providing a smooth transition
to the bulk configuration and for the application of periodic boundaries required for the calcu-
lations. The surface energy can be calculated by dividing the difference in energy between the
bulk and surface calculations by the surface area.
2.7.3 Potentials
The accuracy of the computer simulations is crucially dependent on the model used of the atom-
ic interactions. Although quantum mechanics provides the complete formalism, the implemen-
tation of this formalism is rather tedious. The number of particles to be considered increases
rapidly with increasing nuclei. This results in (unacceptable) time consuming calculations, re-
stricting these quantum mechanical calculations only to systems with a relative small number
of atoms. Therefore, several techniques have been developed to circumvent these problems.
Techniques as pair potentials (PP, used in chapter 7) and Density Functional Theory (DFT, used
in chapter 8) are widely applied.
30
Theory
2.7.3.1 Pair potentials (PP)1

The interaction between the nuclei is composed of, among others, electrostatic forces and Van
der Waals forces. The electrostatic forces contain both charge and polarization interactions. No-
tably, the polarization contribution of the oxygen atoms has to be taken into consideration dur-
ing calculations. This is being achieved by assuming a spring system between the core and the
(electron) shell of the oxygen atom with a certain spring constant (shell model). Furthermore,
the Van der Waals forces are included using the Buckingham potential, since the description of
the repulsive part of the Van der Waals forces (exchange forces) using an exponential term is
more suited than the r-12-term in the standard Lennard-Jones 12-6 potential. The potential (V)
is then given by:
1
V = --- ∑ V ij , (2.81)
2
ij
with
qi qj r ij  C ij
- + Aij exp  – -----
V ij = V electro + V rep + VVdW = -------- - – ------ , (2.82)
r ij  ρ  6
ij r ij
where qi and qj are the charges of ions i and j respectively, rij is the distance between the ions
and Aij, ρij and Cij are adjustable parameters to describe the potential.
Applying the Ewald summation [19] to equation 2.81 and moving the positions of the nuclei,
the total energy (U) is minimized obtaining the equilibrium configuration:
d
d rj ∑ i
U = 0. (2.83)
In order to diminish the amount of calculations a cut-off distance is frequently used beyond
which the energy contribution is neglected.
2.7.3.2 Density Functional Theory

The electronic structure of solids can be quantum mechanically calculated the conventional way
by solving approximately the classical Schrödinger equation ( H |Ψ〉 = E |Ψ〉 ) via the variation
principle. However, the size of the system has to be limited for computational reasons. Alterna-
tively, the Density Functional Theory approach can be used to calculate the electronic structure
of the solid. In the DFT-approach it is stated the complete information about the structure is
1. This chapter contains only a brief summary of the pair potential and density functional theory tech-
niques. The reader is referred to specialized literature for an extended treatise on the underlying theo-
ries and implementations.
31
Chapter 2
stored in the charge density ρ(r) implying that all properties, in particular potential and energy,
are a function of the charge density (first Hohenberg-Kohn theorem). Furthermore, only the true
ground-state density ρο(r) provides the true energy (second Hohenberg-Kohn theorem). Since
the energy is a functional of the charge density, the Hamiltonian (H) and its components must
also be:
H [ ρ ( r ) ] = Hkin [ ρ ( r ) ] + H ne [ ρ ( r ) ] + Hee [ ρ ( r ) ] + Hxc [ ρ ( r ) ] , (2.84)
where Hkin[ρ(r)], Hne[ρ(r)], Hee[ρ(r)] and Hxc[ρ(r)] are the kinetic, nucleus-electron interac-
tion, coulombic electron-electron interaction and the exchange-correlation Hamiltonians, re-
spectively. The first three terms can be expressed in the analytical functionals of the charge
density, but not the exchange-correlation term. This problem can be circumvented by e.g. ap-
plying the Local Density Approximation (LDA), where a homogeneous electron gas system is
assumed. This system is the only system where the exchange and correlation terms are known
and can be expressed as a functional of the charge density.
The energy optimization in a DFT-calculation with respect to the charge density depends on the
representation of the charge density. Kohn and Sham [21] introduced an approach where the
density is generated from a Slater determinant with one-electron wavefunctions called "Kohn-
Sham" orbitals θi(r). The charge density is in this approach defined as:
ρ( r ) = ∑ |θi ( r )〉 〈θi ( r )| . (2.85)
The energies of the orbitals can be calculated using the Kohn-Sham equations:
F KS [ ρ ( r ), i ] |θ i ( r )〉 = ε i [ ρ ( r ) ] |θ i ( r )〉 , (2.86)
where the Kohn-Sham operator (FKS) is related to the Hamiltonian via:
H[ ρ( r ) ] = ∑ FKS [ ρ ( r ), i ] . (2.87)
By solving the Kohn-Sham equations the Kohn-Sham orbitals θi(r) are obtained, which yield
on their turn the charge density as shown in equation 2.85. Since the operators in the Kohn-
Sham equations are defined in terms of charge density, a self-consistent iterative process has to
be applied to obtain the lowest energy U. Subsequently, the structure is optimized to obtain the
equilibrium configuration.
32
Theory
2.8 References
[1] M.A.H. Donners, Fracture of MnZn ferrites, Ph.D. Thesis, Eindhoven University of
Technology, Eindhoven, The Netherlands (1998)
[2] B.R. Lawn, Fracture of Brittle solids, 2nd Ed., Cambridge University Press, Cambridge,
UK, (1993)
[3] C.E. Inglis, Stresses in a plate due to the presence of cracks and sharp corners, Trans.
Inst. Naval Archit., 55 (1913), 219-241
[4] A.A. Griffith, The phenomena of rupture and flow in solids, Phil. Trans. Roy. Soc.
Lond., A221 (1920), 163-198
[5] I. Langmuir, Constitution and fundamental properties of solids and liquids. I. Solids, J.
Am. Chem. Soc., 38 (1916), 2221-2295
[6] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and platinum, J.
Am. Chem. Soc., 40 (1918), 1361-1402
[7] S. Brunauer, P.H. Emmett, E. Teller, Adsorption of gases in multimolecular layers, J.
Am. Chem. Soc., 60 (1938), 309-319
[8] S. Brunauer, The adsorption of gases and vapors, Vol. 1, Princeton University Press,
Princeton, USA, (1945)
[9] D.K. Shetty, A.R. Rosenfield, W.H. Duckworth and G.K. Bansal, The static fatigue limit
in the thermal activation approach to subcritical crack growth, J. Am. Ceram. Soc., 62
(1979), 536-537
[10] R.J. Charles, Static fatigue of glass II, J. Appl. Phys., 28 (1958), 1554-1560
[11] T.A. Michalske and S.W. Freiman, A molecular interpretation of stress corrosion in sil-
ica, Nature, 295 (1982), 511-512
[12] S.M. Wiederhorn, Influence of water vapor on crack propagation in soda-lime glass, J.
Am. Ceram. Soc., 50 (1967), 407-414
[13] S.W. Freiman, G.S. White and E.R. Fuller, Environmentally enhanched crack growth in
soda-lime glass, J. Am. Ceram. Soc., 68 (1985), 108-112
[14] S.M. Wiederhorn, S.W. Freiman, E.R. Fuller and C.J. Simmons, Effects of water and
other dielectrics on crack growth, J. Mat. Sci., 17 (1982), 3460-3478
[15] A.S. Krausz and K. Krausz, Fracture kinetics of crack growth, 1st Ed., Kluwer Academic
Publishers, Dordrecht, The Netherlands, (1988)
[16] B. Gross and J.E. Srawley, Stress-intensity factors for single-edge-notch specimen in
bending or combined bending and tension by boundary collocation of a stress function,
Technical Note D-2603, NASA, USA, (1965)
[17] W.F. Brown and J.E. Srawley, Plane strain crack toughness testing of high strength
metallic materials, ASTM Spec. Tech. Publ., 410 (1967), 13-14
[18] P.W. Tasker, The surface energies, surface tensions and surface structure of the alkali
halide crystals, Phil. Mag. A., 39 (1979), 119-136
[19] P. Ewald, Die Berechnung optischer und elektrostatischer Gitterpotentials, Ann. Phys.,
64 (1921), 253-287
33
Chapter 2
[20] P. Hohenberg and W. Kohn, Inhomogeneous electron gas, Phys. Rev., 136 (1964), B864-
B871
[21] W. Kohn and L.J. Sham, Self-consistent equations including exchange and correlation
effects, Phys. Rev., 140 (1965), A1133-A1138
34
-3-
Water vapour influence on the fracture of

commercially applied oxide ceramics
3.1 Introduction
The selection of materials for a certain application depends generally on a number of criteria.
One of the most important criteria is the expected mechanical lifetime of the component when
subjected to the practical conditions (temperature, chemical environment, etc.). One of the proc-
esses which reduces the lifetime is subcritical crack growth (SCG). Subcritical crack growth can
occur when gaseous molecules from the environment enter the crack and lower the strength and/
or fracture toughness of the material. However, how the molecules from the environment inter-
act exactly with the material is still under debate.
Two mechanisms have been proposed. Firstly, a chemical attack of the gaseous molecules on
the stretched bonds at the crack tip and, secondly, adsorption of gaseous molecules on the newly
formed surfaces reducing the surface energy, which opposes fracture. It is shown for hexafer-
rites [1] and MnZn ferrites [2] that the latter mechanism cannot be disregarded. The question is
addressed whether this is a general feature of oxide ceramics. Therefore, the focus was directed
to other oxide ceramics, since the complex composition and surface chemistry of MnZn ferrites
and hexaferrites can play a role too.
In this chapter the results of fracture experiments at different loading rates on seven different
materials are discussed. The experiments were performed on commercially applied materials
35
Chapter 3
Table 3.1: Examples of applications of the materials investigated

Material Applications
Alumina Bearings, artificial teeth, electronic insulating substrates
Translucent alumina lamp bulbs, windows
PZT Transducers, actuators, oscillators
Mg-PSZ Armour, ionic conductors, structural parts
(see table 3.1): two types of polycrystalline alumina (Wesgo995 and Wesgo997), translucent
alumina with and without erbium additives (DGA and DGA-Er), lead zirconate titanate (PZT),
magnesium-partially stabilize zirconia (Mg-PSZ) and a traditional ceramic as applied in floor
tiles. The experiments were conducted at different relative humidities in a mixture of dry nitro-
gen gas and (humidified) air to measure the fracture toughness of all materials using a single
edge notched beam (SENB) technique and the strength of Wesgo995 with a three-point bending
technique.
3.2 Experimental
3.2.1 Materials and specimens

The materials were commercially obtained as blocks and cut and ground into the required di-
mensions of the specimens as given in table 3.2. For the fracture toughness the notch of the
SENB specimens was cut up to ~15 % of the specimen’s height using a 100 µm diamond saw
blade resulting in a notch width of ~125-150 µm.
Table 3.2: Set-up and specimen dimensions

Material Inner span Outer span Specimen SEM specimen
(w×h×l) (w×h×l)
[mm] [mm] [mm] [mm]
Wesgo995 15 30 3×3.75×40 2×3×50
Wesgo997 15 30 3.5×4.5×50 2×3×50
DGA 15 40 ~4.6×50a 2×3×50
DGA-Er 15 40 ~4.6×50a 2×3×50
PZT 15 40 3×4×50 3×4×50
Mg-PSZ 15 40 3×4×50 1.5×3×50
Floor tiles 15 80 ~7×~20.2×120 3×4×40
a. The DGA and DGA-Er specimen were solid round bars. The dimensions are given as
diameter × length [mm]. The bars were slightly flattened off to prevent rolling. The notch
was perpendicular to the flattened plane.
36
Commercially applied oxide ceramics
The specimens of Wesgo995, Wesgo997 (both from Western Gold & Platinum Company,
USA), Mg-PSZ (2.5 % magnesium and 0.5 % hafnium additives [3] from ICI, UK) and PZT
(PbZr0.54Ti0.46O3 doped with 1 % Nb2O5, poled, from Morgan Electro Ceramics, The Nether-
lands) were rectangular bars. The latter specimens have a composition near the morphotropic
phase boundary and have an upper and bottom side covered with a 0.4 µm thick layer of a
NiCrNi electrode, which is assumed not to have influence on the fracture toughness. The DGA
and DGA-Er specimens (Philips Lighting, The Netherlands) were solid round bars. The speci-
men cut from floor tiles (Trega International, The Netherlands) were ground up to the desired
height with the glaze left intact and the notch was made opposite the glaze.
3.2.2 Fracture toughness and strength

A four point bending set-up was used to measure the fracture toughness of all the materials. The
inner (li) and outer span (lo) of this set-up were adjusted to the dimensions of the specimens in-
vestigated and are given in table 3.2. Using this set-up, the apparent fracture toughness KIc of
all the materials measured with rectangular bars is calculated by:
3F ( l o – l i )
K Ic = Y S σ f c o = Y S ------------------------
2
- co , (3.1)
2wh
where σf is the stress at fracture, co is the initial notch length, F is the force at fracture, w and h
are the width and height of the specimen, respectively, and YS is the geometry factor given by
the Gross-Srawley equation [4,5]:
2 3 4
Y S = 1.99 – 2.47α + 12.97α – 23.17α + 24.8α , (3.2)
where α = co / h.
The apparent fracture toughness for the round solid bars of translucent alumina is given by:
8F ( l o – l i )
K Ic = Yσ f c o = Y ------------------------
3
- co , (3.3)
πd
where d is the diameter and Y is the geometry factor given by [6]:
2 3 4
Y = 0.7438 – 1.6478α + 5.9538α – 3.7273α + 3.1061α , (3.4)
where a = co / d. In order to prevent rolling in the set-up, the round bars were slightly double
sided flattened off, but the original radius was used in the calculation of the relative notch
length, since the change in moment of inertia by flattening was negligible.
37
Chapter 3
Furthermore, the fracture strength of Wesgo995 was measured using a three point bending set-
up with a span of 30 mm on chamfered specimens with the same dimensions as the fracture
toughness specimen.
3.2.3 Measurement
The experiments were performed at room temperature on an universal Erichsen testing machine
with a calibrated Test GmbH 500 N load cell except for PZT which was measured using a cal-
ibrated Erichsen 50 N load cell. Before each experiment the specimen was preloaded at
0.2 mm min-1 up to 5 or 20 N depending on the material. During the experiment, the crosshead
velocity was constant and preset on the testing machine at 0.2, 2.0 and 20 mm min-1, which cor-
responds to the experimentally determined average stressing rates of the materials investigated
as shown in table 3.3. Furthermore, an additional experiment was performed with a lower stress-
ing rate on special testing machine1 mounted with a calibrated Test GmbH 500 N load cell. On
this testing machine, the fracture toughness of translucent alumina without erbium additives
was measured with a stressing rate of 0.076 MPa s-1.
The experiments at different humidities were performed inside a perspex chamber mounted in
the testing machine with a gas and hygrometer inlet. The relative humidity (RH) inside the
chamber was calculated as the ratio of the partial pressure at the actual dew point inside, which
was measured by a Panametrics system III hygrometer, and the equilibrium partial pressure at
room temperature. The relative humidity between 2 and 80% was controlled by the inlet of dry
nitrogen gas in case of humidity lowering or by the inlet of nitrogen gas led through water in
case of humidity increase.
Table 3.3: Average stressing rates at different crosshead velocities

Material 0.2 mm min-1 2.0 mm min-1 20 mm min-1
[MPa s-1] [MPa s-1] [MPa s-1]
Wesgo995 1.37 18.6 141
Wesgo997 0.97 12.8 105
DGA 1.79 23.5 175
DGA-Er 1.79 22.7 188
Mg-PSZ 1.70 21.6 197
PZT 0.56 8.3 78
1. Testing machine constructed in the Central Workshop of the Eindhoven University of Technology;
stressing rate range: ~0.025 - ~2.5 MPa s-1.
38
The experiments at 0% humidity were performed inside a Scanning Electron Microscope

(SEM) on a special four point bending testing machine (Deben UK Ltd., UK). For these exper-
iments special specimens, for which the dimensions are given in Table 1, are required since the
maximum load of this machine is 160 N. The floor tile samples were disposed of the glaze and
the DGA and DGA-Er specimens were sawn to rectangular bars. All the notches were 15% of
the specimen height.
After fracture the fracture surfaces were investigated using a SEM in order to determine the
fracture mode. The fracture surfaces were gold-coated by sputtering in order to prevent charging
effects.
3.3 Results and discussion
3.3.1 Fractography
Since the stressing rate and the relative humidity may have an influence on the fracture mode
and in this way an indirect effect on the fracture toughness, the fracture surfaces were examined
by SEM. Images of several typical fracture surfaces are shown in figure 3.1.
The fracture surfaces of DGA and DGA-Er show both a mixed trans- and intergranular fracture
mode. Investigation of the fracture surfaces of DGA-Er using energy dispersive X-ray tech-
nique did not reveal the presence of erbium. This is probably due to the low amount of erbium
additives (approximately 50 ppm [7]), which is supposed to be segregated to the grain bounda-
ries. The surfaces of both other types of alumina do show both also a mixed inter- and trans-
granular fracture mode with a tendency towards transgranular. Both Wesgo995 and Wegso997
have a fracture mode ratio which is independent of the relative humidity.
The fracture surfaces of floor tiles show predominately a transgranular fracture mode. The same
is also observed for Mg-PSZ, which fracture mode does not alter with increasing relative hu-
midity. However, Leach and Lambov have found for magnesium partially stabilized zirconia an
intergranular fracture behaviour below 600 °C [8]. The hafnium additives in the zirconia inves-
tigated might explain this difference. The fracture surface of PZT does show predominantly an
intergranular fracture mode, which is in agreement with the results of Kim et al. [9]. The frac-
ture mode did also not appear to be dependent on the relative humidity.
From these observations it is concluded that the fracture mode is essentially independent of the
stressing rate and the relative humidity.
39
Chapter 3
a) b)
c) d)
e) f)
Figure 3.1: SEM images of typical fracture surfaces of a) Wegso995, b) Wesgo997, c) DGA, d)
PZT, e) Mg-PSZ and f) floor tiles.
40

The fracture toughness of the materials investigated at different relative humidities and different
crosshead velocities are shown in figures 3.2-3.5. The fracture toughness of all materials de-
creases with increasing relative humidity. Furthermore, it is observed that the fracture toughness
measured at 0.2 mm min-1 is always lower than the fracture toughness measured at 2.0 and
20 mm min-1. The fracture toughness of the latter two crosshead velocities is almost the same,
indicating that fracture at these loading rates is rapidly catastrophic so that subcritical crack
growth hardly occurs at these loading rates.
Taking the results of MnZn ferrites [2] into account, two types of behaviour can be distin-
guished. The first type, designated as Type I, is characterised by a very sharp decrease in frac-
ture toughness between the relative humidities of 0 and 2 %. Subsequently, the fracture
toughness decreases slowly or not at all with increasing relative humidity above 2 %. This be-
haviour is observed for all the aluminas, PZT, the floor tile ceramics and zirconia. The relative
constant behaviour of the fracture toughness of Type I materials with respect to the humidity
above 2 % implies that the contribution of adsorption remains constant. This suggests that either
the surface is already fully covered at 2 % or that the extra water adsorption, whether chemical
or physical, does not have an effect.
Adsorption experiments on the (0001) surface of a single crystal α-alumina, where the surface
was heat-treated, by Liu et al. [10] showed that below 4 % humidity hydroxylation of the sur-
face does not take place, even at longer exposure times. The small amount of hydroxyl groups
detected on the surface was due to adsorption on defect sites. Also Elam et al., [11] performed
adsorption experiments on the (0001) surface of single crystal α-alumina, where the surface was
chemically etched, at different exposure times and vapour pressures. Their results indicated that
at 2 % humidity ~48 % of the surface will be covered by hydroxyl groups in approximately 55 s.
This is approximately the same time between the application of the load an the catastrophic fail-
ure in the conducted fracture experiments when subcritical crack growth occurs. The coverage
increased to ~74% of a monolayer at 80 % humidity. This indicates that the largest part of the
coverage is already reached in the first 2 % humidity.
The amount of defect sites can explain the discrepancy between the results of Liu and Elam due
to different surface preparation procedures. Since fracture surfaces are in general not perfect,
41
Chapter 3
a) 2 .0
Fracture tou ghn es s [M P a m ]

1 .8
1/2
1 .6
1 .4
1 .2
1 .0
0 20 40 60 80 1 00
R elativ e h um id ity [ % ]
5 .5
b)
5 .0
1/2
4 .5
4 .0
3 .5
3 .0
0 20 40 60 80 1 00
Figure 3.2: The fracture toughness of two type of alumina: a) Wesgo995 and b) Wesgo997 vs.
the relative humidity at different loading rates (0.2 (), 2.0 (z) and 20 mm min-1 (5)). The
fracture toughness at a relative humidity of 0 % is measured inside a SEM.
42
a) 5 .5
5 .0
1/2
4 .5
4 .0
3 .5
3 .0
2 .5
0 20 40 60 80 1 00
5 .5
b)
5 .0
1/2
4 .5
4 .0
3 .5
3 .0
2 .5
0 20 40 60 80 1 00
Figure 3.3: The fracture toughness of a) translucent alumina (DGA) and b) translucent alu-
mina with erbium additives (DGA-Er) vs. the relative humidity at different loading rates (0.2
(), 2.0 (z) and 20 mm min-1 (5)). The fracture toughness at a relative humidity of 0 % is
measured inside a SEM.
43
Chapter 3
a)
1/2
Fracture tou ghn es s [M P a m ] 1 .2
1 .1
1 .0
0 .9
0 .8
0 20 40 60 80 1 00
13 .0
b)
12 .5
Fracture tou gh ness [MP a m ]
1/2
12 .0
11 .5
11 .0
10 .5
10 .0
9 .5
9 .0
0 20 40 60 80 1 00
R elativ e h um id ity [% ]
Figure 3.4: The fracture toughness of a) PZT and b) magnesium partially stabilised zirconia
(Mg-PSZ) vs. the relative humidity at different loading rates (0.2 (), 2.0 (z) and 20 mm min-1
(5)). The fracture toughness at a relative humidity of 0 % is measured inside a SEM.
44
2 .0
1 .8
Fracture tou gh n es s [M P a m ]
1/2
1 .6
1 .4
1 .2
1 .0
0 20 40 60 80 1 00
Figure 3.5: The fracture toughness of floor tile ceramics vs. the relative humidity at different
loading rates (0.2 (), 2.0 (z) and 20 mm min-1 (S)). The fracture toughness at a relative
humidity of 0 % is measured inside a SEM.
this could imply that for the aluminas, which had both a trans- and intergranular fracture mode,
below 2 % already the surface is fully covered, with at least one monolayer.
A series of experiments with translucent alumina without erbium additives at a lower stressing
rate at different humidities shows also Type I behaviour as shown in figure 3.6. However, an
extra experiment was performed at a low relative humidity of 0.15 % resulting in a higher frac-
ture toughness value. This supports the idea that certainly in the first 2 % adsorption plays a role.
The second type of behaviour, designated as Type II, is characterised by a continuous decrease
on the fracture toughness over the whole range of humidity. The sharp decrease below 10 % hu-
midity is absent and from 20 % relative humidity onwards the toughness still decreases showing
that the influence of adsorption is still present after 2 %. This behaviour is observed for MnZn
ferrites [2]. The exact origin of the difference between Type I and Type II behaviour is still un-
known.
3.3.3 Relation between fracture strength and fracture toughness for Wesgo995
The fracture strength of Wesgo995 measured at different loading rates is given in figure 3.7. It
is steadily decreasing with increasing relative humidity. However, the strength at a loading rate
45
Chapter 3
5 .5
5 .0
1/2
4 .5
4 .0
3 .5
3 .0
2 .5
0 20 40 60 80 1 00
Figure 3.6: The fracture toughness of translucent alumina without erbium additives (DGA) vs.
the relative humidity with a stressing rate of 0.076 () and 1.76 MPa s-1 (z, 0.2 mm min-1).
3 25
3 00
F ractu re s treng th [ MP a]
2 75
2 50
2 25
2 00
1 75
0 20 40 60 80 1 00
Re lat iv e h um id ity [% ]
Figure 3.7: The fracture strength of Wesgo995 measured at different humidities at different
loading rates (0.2 (), 2.0 (z) and 20 mm min-1 (5)).
46
of 0.2 mm min-1 attains a kind of plateau at 40 % relative humidity indicating that the adsorp-
tion processes are not contributing any more to the decrease. A similar behaviour is found by
Cho et al. [12].
The apparent fracture toughness vs. strength (Kapp - σf) ratio is given approximately by the for-
mula as derived by Donners et al. [2]:
1
------------
K app  σ· Y c 3 n + 1
S S
c i  ------------------------
o
---------- = Y i , (3.5)
σf  · 3
 σi Yi c i 
· ·
where n is the subcritical crack growth factor, σ S and σ i are the stressing rates of the SENB
and strength specimen, respectively, YS and Yi are the geometry factors of the notch in the SENB
specimen and the initial defect in the strength specimen, respectively, and co and ci are the initial
length of the notch and the initial defect, respectively.
If the Kapp - σf ratio remains constant, it can be concluded that the influence of humidity is a
material property and not dependent on the used experimental set-up or specimen geometry.
This Kapp - σf ratio for Wesgo995 is indeed constant at a value of 1.46×10-2 ± 0.05×10-2 m1/2,
as seen in figure 3.8.
A value for the subcritical crack growth factor of n = 26 and an initial defect size of ci = 62 µm
are obtained after fitting equation 3.5 to the data using a notch length of the SENB specimen of
562.5 µm, YS = 1.85 and a stressing rate of 1.37 and 2.74 MPa s-1 for SENB and strength ex-
periments, respectively. Furthermore, it is assumed that the initial defect in the strength speci-
men is a semi-circular flaw (Yi = 1.26).
The value for the subcritical crack growth factor is typical for alumina, while the initial defect
size in not unreasonable. Unfortunately, fractography could not reveal the various fracture ori-
gins.
3.4 Conclusions
In order to investigate the effect of adsorption of water on the fracture process, the fracture
toughness of seven different ceramic materials was investigated at different humidities and
loading rates. It can be concluded that adsorption of water can play an important role in the frac-
ture process of oxide ceramics next to the kinetic effect. However, the role of adsorption is de-
pendent on the material.
47
Chapter 3
0 .0 20
0 .0 18
K app- σ f ratio [m ]
1/2
0 .0 16
0 .0 14
0 .0 12
0 .0 10
0 20 40 60 80 1 00
Figure 3.8: Fracture toughness - strength ratio vs. relative humidity for Wesgo995 alumina.
The dashed line is the average.
Two types of behaviour can be distinguished. For Type I materials, a sharp decrease in fracture
toughness from the 0 to 2 % humidity is observed and an insignificant decrease for humidities
above 2-10 %, indicating that adsorption only has an influence in the first 2-10 % humidity. The
investigated aluminas, PZT, floor tile ceramics and zirconia show this behaviour.
On the other hand, Type II materials show over the whole range of humidities a steady decrease
of the fracture toughness, indicating that adsorption still plays a significant role above 20%.
MnZn ferrites show this behaviour.
This investigation shows that it is important to determine whether the material is a Type I or a
Type II material. The reported fracture toughness values can be used for Type I materials, since
they are almost independent of humidity. However, the reported fracture toughness values for
Type II materials are significantly depending on the relative humidity and the proper value for
the condition of use should be taken.
3.5 Acknowledgements
Philips Lighting, Morgan Electro Ceramics and Trega International are acknowledged for pro-
viding the materials. Hans Onstenk (Central Workshop TU/e) is acknowledged for the specimen
preparation.
48
3.6 References
[1] G. de With, Anisotropy in mechanical properties of sintered Sr-hexaferrite, Silicates
Industrielles, 295 (1984), 185-189
[3] P.T.H. van den Berg, Zirconia ceramics and mechanical surface interaction, Ph.D. The-
sis, Eindhoven University of Technology, Eindhoven, The Netherlands (1992)
[4] B. Gross and J.E. Srawley, Stress-intensity factors for single-edge-notch specimen in
bending or combined bending and tension by boundary collocation of a stress function,
Technical Note D-2603, NASA, USA, (1965)
[5] W.F. Brown and J.E. Srawley, Plane strain crack toughness testing of high strength
metallic materials, ASTM Spec. Tech. Publ., 410 (1967), 12-14
[6] E. Si. Stress intensity factors for edge cracks in round bars, Eng. Frac. Mech., 37 (1990),
805-812
[7] Private communication with Dr. Th. Kappen, Philips Lighting
[8] C. Leach and N. Lambov, Temperature dependence of crack propagation in magnesia
partially stabilized zirconia (Mg-PSZ), Mater. Sci. Monogr., 66C (1991), 1519-1525
[9] S.-B. Kim, D.-Y. Kim, J.-J. Kim and S.-H. Cho, Effect of grain size and poling on the
fracture mode of lead zirconate titanate ceramics, J. Am. Ceram. Soc., 73 (1990), 161-
163
[10] P. Liu, T. Kendelewicz, G.E. Brown, E.J. Nelson and S.A. Chambers, Reaction of water
vapor with α-Al2O3(0001) and α-Fe2O3(0001) surfaces: sychnotron X-ray photoemis-
sion studies and thermodynamic calculations, Surf. Sci., 417 (1998), 53-65
[11] J.W. Elam, C.E. Nelson, M.A. Cameron, M.A. Tolbert and S.M. George, Adsorption of
H2O on a single-crystal α-Al2O3(0001) surface, J. Phys. Chem. B, 102 (1998), 7008-
7015
[12] S.-J. Cho, K.-J. Yoon, J.-J. Kim and K.-H. Kim, Influence of humidity on the flexural
strength of alumina, J. Eur. Ceram. Soc., 20 (2000), 761-764
49
Chapter 3
50
-4-
Subcritical crack growth in calcium

hydroxyapatite
4.1 Introduction
The rigid skeletal system enables the body of humans and other vertebrates to maintain its
shape, to protect vital organs, to serve as a centre of metabolic activity and to transmit forces of
muscular contraction between parts of the body during movement. The bones and teeth are com-
posite materials built up from oriented small needle-like mineral crystals (~4×4×50 nm3) locat-
ed in a collagen fibre matrix. The mineral crystals are found with X-ray diffraction to be an
analogue of the geological mineral apatite (Ca10(PO4)6(OH/F)2) [1], but the elemental compo-
sition of these crystals varies (e.g. F- for OH- or CO32- for PO43-). The amount and size of hy-
droxyapatite crystals determine the physical properties of bone and teeth. For example, the
enamel, the toplayer of teeth, can withstand high compressive stresses during eating due to a
high volume of large hydroxyapatite crystals, while the underlying dentin has less and smaller
hydroxyapatite crystals, providing a better shock absorbance (see table 4.1). However, the phys-
ical properties can change with changing mineral content due to e.g. the unrepairable degener-
ation of hydroxyapatite in enamel due to acids formed by mouth bacteria from sugars in food
and (notably soft) drinks, which causes serious caries leading to cavities.
The similarity in elemental composition and structure of hydroxyapatite with the minerals in
bone makes hydroxyapatite ceramics a very favourable material for implants. Dense and porous
hydroxyapatite ceramics show a very good biocompatibility (no rejection by living tissue) and
51
Chapter 4
bioactivity (source of tissue generation), where the latter even allows the regeneration of new
natural bone material inside the pores and channels and can later dissolve inside the body. Hy-
droxyapatite can also be used as a coating on metallic implants (e.g. titanium alloy) to prevent
rejection by the surrounding tissue. However, bulk hydroxyapatite ceramics show a very poor
mechanical behaviour. A low fracture toughness, a pronounced sensitivity towards subcritical
crack growth and a small resistance to impact restricts the use of hydroxyapatite for clinical use
to coatings, composites and pastes.
Subcritical crack growth in dense hydroxyapatite has been studied by different authors under
different conditions. Thomas et al. [5] found a subcritical crack growth parameter n = 80 (recal-
culation of the provided data gives n = 92 [6]), implying a high resistance to fatigue in air. On
the other hand, De With et al. [6,7] found n = 26 and n = 12 for dense hydroxyapatite in air and
water, respectively, using dynamic fatigue testing indicating substantial subcritical crack
growth. The reported results by Raynaud et al. [8] of n = 22 and n = 14 in air and water, respec-
tively, are in agreement with the latter authors. De With et al. [6] also found a subcritical crack
growth parameter of n = 11 using double torsion specimens in air.
It is thus evident that the mechanical properties like fracture toughness and strength depend on
the environment. However, it is unclear whether the amount of water present (i.e. relative hu-
midity) has an influence on these properties. It this chapter, the influence of humidity on the
fracture toughness of dense hydroxyapatite ceramics is investigated. The fracture toughness was
determined at different loading rates and humidities in a mixture of dry nitrogen gas and (hu-
midified) air using a single edge notched beam (SENB) technique.
Table 4.1: Typical physical properties of bone and teetha

Tissue Mineral Crystal size Elastic Tensile Compressive
content modulus strength strength
[wt %] width thickness [GPa] [MPa] [MPa]
[nm] [nm]
Enamel 96 68 26 84 10 384
Dentin 70 30 3 12 37 305
Femurb 69 4 50 18 121 167
a. Data combined from [2,3,4], exact data are dependent on sex, age and testing condition (dry/
wet)
b. Longitudinal direction
52
Calcium hydroxyapatite
4.2 Experimental
4.2.1 Synthesis
Hydroxyapatite powder from Merck A.G. (Darmstadt, Germany) was sieved to remove agglom-
erates. Next, the powder was prepressed at 5 MPa to a block in a stainless steel die with an area
of 6×6 cm2 using a 10 % oleic acid in petroleum ether mixture as a lubricant resulting in a block
with a relative density of ρ = 25 % (theoretical density of hydroxyapatite is 3.156 g cm-3). Sub-
sequently, the prepressed block was cold isostatically pressed in a rubber bag at 100 MPa,
reaching a green density of ρ = 45 %. Finally, the green bodies were sintered at temperatures
between 1150 °C and 1350 °C for 6 h with a heating and cooling rate of 3 and 1 °C min-1, re-
spectively, in moist air, which was created by leading air through distilled water.
The resulting hydroxyapatite blocks after firing were subjected to X-ray diffraction (XRD) on
a Rigaku Geigerflex using CuKα1 radiation in order to detect the presence of several calcium-
phosphate phases, which can form during sintering. The microstructure was investigated using
a scanning electron microscope (SEM, Jeol JSM 840a) on samples which were polished with
diamond paste to 0.5 µm, etched for 1 min in 1 % citric acid and gold coated to prevent charg-
ing. Furthermore, the density was determined using the Archimedes’ method.
4.2.3 Fracture
The fracture toughness of hydroxyapatite was determined on SENB specimens using a four
point set-up with an inner (li) and outer (lo) span of 15 and 30 mm, respectively. The specimens
were cut and ground from the blocks into rectangular bars of 3×4×36 mm3 (w×h×l). The notch
of the specimens was cut to ~15 % of the height with a 100 µm diamond saw blade resulting in
a notch width of ~150 µm.
The experiments were performed at room temperature on an universal testing machine (Erich-
sen GmbH, Germany) with a calibrated 500 N load cell (Test GmbH, Germany). Prior to each
experiment, the specimen was preloaded up to 5 N with a crosshead velocity of 0.2 mm min-1.
During the experiment, the crosshead velocity was constant and preset to 0.2, 2.0 and
20 mm min-1.
chamber was calculated as the ratio of the partial pressure at the actual dew point inside, which
was measured using a Panametrics system III hygrometer, and the equilibrium partial pressure
53
Chapter 4
Intensity [-]
10
10 20
20 30
30 40
40 50
50 60
2θ [°]
Figure 4.1: XRD spectrum of hydroxyapatite sintered at 1300 °C.
at room temperature. The relative humidity between 2 and 80 % was controlled by the inlet of
dry nitrogen gas in case of humidity decrease or by the inlet of nitrogen gas led through water
in case of humidity increase. The experiments at 0 % humidity to obtain the inert fracture tough-
ness were performed inside a SEM (pH2O < 7×10-4 Pa) on a special four point bending testing
machine (Deben UK Ltd., Debenham, UK) with an inner and outer span of 5 and 20 mm, re-
spectively.
4.3.1 Synthesis and characterisation

XRD measurements on the blocks sintered at different temperatures are shown in figure 4.1 and
show only the presence of hydroxyapatite (JCPDS-file 09-0432) indicating for all temperatures
the prevention of formation of other stable calcium phosphate phases like tricalcium phosphate
(TCP, Ca3(PO4)2, JCPDS-file 32-0176), tetracalcium phosphate (TTCP, Ca4P2O9, JCPDS-file
11-0232) and calcium oxide (CaO, JCPDS-file 28-0775) during sintering.
The density of the blocks sintered at different temperatures is shown in figure 4.2. A relative
density of ρ = 98 % is reached at 1275 °C and hardly increases with further increasing sintering
temperature. The maximum relative density is in agreement with reported data in literature [6-
10].
54
1 00
95
R elative den sity [% ]
90
85
80
75
11 00 12 00 13 00 14 00
Sin ter in g tem p eratur e [°C ]
Figure 4.2: Relative density of hydroxyapatite sintered at different temperatures.
The microstructure of polished and etched surfaces of the hydroxyapatite ceramics was inves-
itigated. The porosity decreases with increasing sintering temperature as shown in figure 4.3.
Simultaneously, the average grain size, estimated visually from the SEM images, increases
from 1, 1, 2 to 3 µm for a sintering temperature of 1200, 1250, 1300 and 1350 °C, respectively.
4.3.2 Fractography
Since the relative humidity might have an influence on the fracture mode and in this way an in-
direct effect on the fracture toughness, the fracture surfaces were examined by SEM, as shown
in figure 4.4. The fracture is predominately transgranular as reported by De With et al. [6] and
Suchanek et al. [11]. It was observed that the fracture mode is independent of relative humidity.

The fracture toughness of hydroxyapatite, sintered at 1300 °C (ρ = 98 %), at different humidi-
ties and crosshead velocities of 0.2, 2.0 and 20 mm min-1 is shown in figure 4.5. The inert frac-
ture toughness was measured to be 1.42 MPa m1/2 independent of the used crosshead velocities
of 0.05 and 0.20 mm min-1 confirming that the inert fracture toughness does not depend on
stressing rate as also shown for MnZn ferrites [12]. The fracture toughness values at ambient
conditions (room temperature and RH = ~40 %) are ~1 and 1.27 MPa m1/2 for the lowest and
55
Chapter 4
b)
d)
a)
c)
Figure 4.3: The microstructure of hydroxyapatite sintered at a) 1200, b) 1250, c) 1300 and d)
1350 °C.
56
Figure 4.4: Fracture surfaces of hydroxyapatite ceramics sintered at 1300 °C.
1 .6
Fracture tough ness [MP a m ]
1/2
1 .4
1 .2
1 .0
0 .8
0 20 40 60 80 1 00
R elative hum id ity [ % ]
Figure 4.5: Fracture toughness of hydroxyapatite sintered at 1300 °C vs. relative humidity
with a loading rate of 0.2 (), 2.0 (z) and 20 mm min-1 (S). The fracture toughness at 0 %
humidity is measured inside a SEM.
57
Chapter 4
the two highest crosshead velocities. The fracture toughness at the lowest humidity is compara-
ble with other values obtained by several authors [6,13], although caution should be taken for
the wide variety of reported data in literature due to the high sensitivity of properties of hy-
droxyapatite to preparation and sintering [14], see table 4.2.
The fracture toughness is continuously decreasing with increasing humidity. The smooth de-
crease of fracture toughness for hydroxyapatite indicates that at all humidities the contribution
of adsorption is present. This is in contrast to e.g. alumina, where a sharp decrease of the fracture
toughness between 0 and 10 % relative humidity and a constant toughness onwards is observed
[16]. The sharp decrease indicates that the adsorption of water contributes significantly to the
decrease in fracture toughness at lower humidities, but the constant toughness onwards indi-
cates that at higher humidities the adsorption has only a negligible contribution despite the in-
creasing water availability. Materials showing the latter behaviour in fracture toughness (e.g.
alumina) are designated as Type I materials and showing the first behaviour as Type II. Fracture
toughness data reported in literature of Type II materials should be treated with extra caution,
since they do depend on the humidity present during measurement. Hydroxyapatite is the sec-
ond known Type II material next to MnZn ferrites.
Table 4.2: Fracture toughness data for polycrystalline hydroxyapatite ceramics

Ref. KIc Methoda ρ Grain Sinter- Remarks
size ingb
[MPa m1/2] [%] [µm]
[6] 1.0 SN >95 ~4.0 C Sintering in moist air
[7] 1.33 SN 98 1.0 C Sintering in moist air
0.93 SN 94 2.9 C Sintering in moist air
[9] 0.70 CN 99.0 ~0.5 C Grain size measured
with 5 % Ag particles
[13] 1.0 VI 97.8 0.2 HIP
0.65 VI 98.9 0.4 HIP
[15] 0.70 SN 99.9 0.64 C+HIP
0.86 SN 99.9 1.07 C
This 0.99 SN 98 2 C
work
a. SN = straight notch, CN = cevron notch, VI = Vickers indent
b. C = conventional sintering in air, HIP = hot isostatic pressing under argon
58
4.3.4 Analysis
The relation between the measured (apparent) fracture toughness (K) and the adsorption con-
trolled fracture toughness (Kads) for Type II materials is given by [12]:
1
------------
 3
n – 2 vp K  2 – n
K = K ads  1 + -------------------- ----- ----------------
- , (4.1)
 2 ( n + 1 ) c o K 2 K· 
ads
where n is the subcritical crack growth factor, vp is the pre-exponential factor in the subcritical
crack growth power law equation v = vp(K / Ko)n with Ko as the inert fracture toughness, co is
the initial notch length and K· = dK ⁄ dt . Using standard Matlab [17] fitting routines the param-
eters n, vp,RH and Kads,RH (RH = 2, 10, 20, 60, 80 %) are determined assuming that the subcrit-
ical crack growth factor n is constant for all humidities. The results of the fit procedure are
shown in table 4.3.
The fit resulted in a value of 9.4 for subcritical crack growth factor n, which is low compared to
data in literature (n ~26). However, the subcritical crack growth parameter in these studies is
calculated without taking the contribution of adsorption into account. Moreover, the higher n-
values are measured using strength specimens which have microflaws as the origin of fracture.
On the other hand, a value of n = 11 has been reported using double torsion technique [6] with
a macroflaw resembling the flaw in the SENB specimen used in this work.
The adsorption controlled fracture toughness data (Kads) are shown in figure 4.6. The relation
between the inert fracture toughness and the adsorption controlled fracture toughness is given
by
K ads = K o 1 – φ ln ( 1 + bpX ) , (4.2)
Table 4.3: Data from fit with n = 9.4

RH Kads vp
1/2
[%] [MPa m ] [10 m s-1]
-4
2 1.44 0.1296
10 1.34 0.7140
20 1.29 3.1217
60 1.18 1.4375
80 1.20 5.6215
59
Chapter 4
1 .6
1 .5
1 .4
K a ds [M Pa m ]
1/2
1 .3
1 .2
1 .1
1 .0
0 20 40 60 80 1 00
R elative hu m id ity [% ]
Figure 4.6: The fitted values of the adsorption controlled fracture toughness of hydroxyapatite
vs. the relative humidity.
where φ is a constant, b is the Langmuir adsorption coefficient and pX is the relative humidity.
Fitting the adsorption controlled fracture toughness data to this equation results in values of
1.48 MPa m1/2, 0.82 and 23.6 for the inert fracture toughness, φ and b, respectively. The fitted
value of 1.48 MPa m1/2 for the inert fracture toughness is in good agreement with the experi-
mental determined value of 1.42 MPa m1/2 in the SEM. The constant φ represents the ratio of
energy released by adsorption to the surface energy required for generating two surfaces during
fracture under inert conditions. The fitted value of 0.82 is comparable to the high φ-value of 0.94
of MnZn ferrites [12], whereas a low φ-value would indicate an insensitivity of the fracture
toughness towards adsorption. The high Langmuir constant b of 23.6 indicates a rapid increase
of coverage at low humidities. This implies that the monolayer coverage is rapidly reached as
indicated by experimental adsorption studies of water on natural bone and synthetic hydroxya-
patite [18]. These results confirm, firstly, the usefulness of the combined analysis and, secondly,
the sensitivity of hydroxyapatite for subcritical crack growth.
4.4 Conclusions
Dense hydroxyapatite ceramics have been made by sintering cold isostatic pressed blocks from
powder at several temperatures in moist air. The fracture toughness of hydroxyapatite sintered
at 1300 °C is measured using the SENB technique at different loading rates and relative humid-
60
ities. Hydroxyapatite fractures predominantly transgranular. Furthermore, it is observed that the

fracture toughness decreases with increasing humidity. The smooth decrease makes hydroxya-
patite a Type II material like MnZn ferrites indicating that care should be taken with the usage
of reported data in literature, since the fracture toughness depends heavily on the humidity. The
subcritical crack growth parameter n is determined to be 9.4 using fitting with the combined ki-
netic-adsorption model showing that hydroxyapatite is a very sensitive material towards sub-
critical crack growth. Furthermore, the inert fracture toughness obtained from fitting of
1.48 MPa m1/2 is in good agreement with the measured inert fracture toughness of
1.42 MPa m1/2.
A.J.M. van Dijk (Eindhoven University of Technology) is acknowledged for his major contri-
bution to this chapter performed within the framework of the graduation work for his Masters
thesis [19].
4.6 References
[1] W.F. de Jong, La substance minérale dans les os, Rec. Trav. Chim. Pays-Bas, 45 (1926),
445-448
[2] K.E. Healy, Dentin and Enamel, in: "Handbook of biomaterial properties",1st Ed., Eds: J.
Black and G. Hastings, Chapman & Hall, London, UK, (1998)
[3] J. Currey, Cortical bone, in: "Handbook of biomaterial properties",1st Ed., Eds: J. Black
and G. Hastings, Chapman & Hall, London, UK, (1998)
[4] J.B. Park and R.S. Lakes, Biomaterials: An introduction, 2nd Ed., Plenum Press, New
York, USA (1992)
[5] M.B. Thomas, R.H. Doremus, M. Jahro and R.L. Salsbury, Dense hydroxylapatite:
fatigue and fracture strength after various treatment from diametral tests, J. Mater. Sci.,
15 (1980), 891-894
[6] G. de With, H.J.A. van Dijk, N. Hattu and K. Prijs, Preparation, microstructure and
mechanical properties of dense polycrystalline hydroxy apatite, J. Mater. Sci., 16 (1981),
1592-1598
[7] G. de With, H.J.A. van Dijk and N. Hattu, Mechanical behaviour of biocompatible
hydroxyapatite ceramics, Proc. Brit. Ceram. Soc., 31 (1981), 181-189
[8] S. Raynaud, E. Champion, D. Bernache-Assolant and D. Tetard, Dynamic fatigue and
degradation in solution of hydroxyapatite ceramics, J. Mater. Sci.: Mater. in Med., 9
(1998), 221-227
[9] X. Zhang, G.H.M. Gubbels, R.A. Terpstra and R. Metselaar, Toughening of calcium
hydroxyapatite with silver particles, J. Mater. Sci., 32 (1997), 235-243
61
Chapter 4
[10] S. Raynaud, E. Champion and D. Bernache-Assollant, Calcium phosphate apatites with

variable Ca/P atomic ratio II. Calcination and sintering, Biomaterials, 23 (2002), 1073-
1080
[11] W. Suchanek, M. Masamoto, M. Kakihana and M. Yoshimura, Hydroxyapatite/
hydroxyapatite-whisker composites without sintering additives: mechanical properties
and microstructural evolution, J. Am. Ceram. Soc., 80 (1997), 2805-2815
[13] S. Raynaud, E. Champion, J.P. Lafon and D. Bernache-Assollant, Calcium phosphate
apatites with variable Ca/P atomic ration III. Mechanical properties and degradation in
solution of hot pressed ceramics, Biomaterials, 23 (2002), 1081-1089
[14] Z.Z. Zyman, I.G. Ivanov and V.I. Glushko, Possibilities for strengthening hydroxyapatite
ceramics, J. Biomed. Mater. Res., 46 (1999), 73-79
[15] T. Nonami and F. Wakai, Evaluation of crack propagation in hydroxyapatite by double-
torsion method in air, water and toluene, J. Ceram. Soc. Jpn., 103 (1995), 648-652
[16] N.J. van der Laag, A.J.M van Dijk, L.J.M.G. Dortmans and G. de With, The role of water
adsorption on the fracture of ceramic oxides, J. Eur. Ceram. Soc., (submitted)
[17] Matlab v.5.3, The Mathworks Inc. Nathick, MA, USA
[18] M.E. Dry and R.A. Beebe, Adsorption studies on bone mineral and synthetic hydroxyap-
atite, J. Phys. Chem., 64 (1960), 1300-1304
[19] A.J.M. van Dijk, The influence of loading rate and environment on brittle fracture of
ceramics, M.Sc. Thesis, Eindhoven University of Technology, Eindhoven, The Nether-
lands, (2001)
62
-5-
Fracture of magnesium aluminate spinel

(MgAl2O4)
5.1 Introduction
Magnesium aluminate spinel (MgAl2O4) is an interesting ceramic material. It has an excellent
combination of desired properties for e.g. refractory applications like a high melting tempera-
ture, high strength at elevated temperatures, good thermal shock resistance, low thermal expan-
sion and a high inertness to chemical attack. Magnesium aluminate is in combination with its
excellent optical properties suitable for making strong windows or lenses for e.g. armoured ve-
hicles and cruise missiles. Furthermore, magnesium aluminate shows an unusual inertness to
high-fluence neutron irradiation concerning mechanical properties. This allows the material to
be used in (low) nuclear applications as a buffer material [1].
Figure 5.1 shows the phase diagram of magnesium aluminate indicating that spinel formation
is possible with a large range in stoichiometry. The synthesis of magnesium aluminate powder
is relative easily achieved by mixing magnesia and alumina and firing at elevated temperatures.
Magnesium aluminate ceramics can be obtained from these powders using conventional ceram-
ic processing like cold or hot pressing and conventional sintering.
One of the important questions raised during the selection process of (ceramic) materials con-
cerns the life time expectancy of the material under thermomechanical loading. An important
phenomena in this field is subcritical crack growth due to the presence of water. Subcritical
63
Chapter 5
2827 °C
Liquid
2600
2200 2105 °C
2054 °C
Temperature [°C]
1800 Spinel
1400
1000
0 20 40 60 80 100
MgO Al2O3
Mol.% Al2O3
Figure 5.1: Phase diagram of MgO-Al2O3 [2].
crack growth in magnesium aluminate is also very intriguing due to the fact that of its constitu-
ents magnesia does not show substantial subcritical crack growth behaviour, but alumina does.
Unfortunately, only one paper by Rice et al. [3] deals with subcritical crack growth in magne-
sium aluminate. They performed tests in liquid nitrogen (- 196 °C), where the influence of water
is not present and found a 20-30 % higher value for the strength of polycrystalline magnesium
aluminate than at ambient temperature and humidity (22 °C and ~30 %). Since the temperature
dependence of the Young’s modulus can only explain a 3 % higher value, the remainder should
be attributed to the absence of water.
In this chapter, the influence of humidity on the mechanical properties of two types of magne-
sium aluminate ceramics is investigated. Also, the influence of humidity on the fracture of sin-
gle crystals along low index planes is determined. Furthermore, the fracture path of magnesium
aluminate has been investigated using Electron Backscattering Diffraction (EBSD), in order to
see whether texture and crystallite orientation are important parameters. Finally, hydrated sur-
face investigations have been performed using Low Energy Ion Scattering (LEIS) and Diffuse
Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) in order to obtain an insight in
the adsorption of water on fracture surfaces.
64
Magnesium aluminate
5.2 Experimental
5.2.1 Material preparation and characterisation

The mechanical properties of two types of polycrystalline magnesium aluminate ceramics are
investigated. Type A is a commercially obtained ceramic from Custom Technical Ceramics
(Arvada, CO, USA) in the form of 5 x 50 x 50 mm3 blocks. Type B are ceramic discs
(∅ 60 mm x 10 mm) made by conventional sintering (1600 °C, 4 h) in air of prepressed
(40 MPa) and subsequently cold isostatically pressed (250 MPa) submicrometer magnesium
aluminate powder from Baikowski (Annecy, France). Furthermore, samples cut from a Ver-
neuil-grown single crystal were used for the single crystal experiments and a hot-pressed coarse
grained sample for EBSD experiments.
The density of the ceramics is determined by the Archimedes’ method using distilled water. The
Young’s, shear and bulk modulus and Poisson’s ratio are determined using ultrasonic measure-
ments (Panametrics, 25DL) on plane-parallel polished samples. The average grain size was vis-
ually estimated by typically measuring some twenty grains on polished (down to 0.25 µm) and
chemically etched (85 % phosphoric acid,~175 °C, 10 min) samples, which were gold sput-
tered, using a Scanning Electron Microscope (SEM, Jeol 840).
5.2.2 Mechanical testing

Single edge notched beam (SENB) specimens were used to measure the fracture toughness. The
rectangular polycrystalline specimen were cut and ground into the dimensions shown in table
5.1 from the blocks or discs. The specimens from the single crystals were cut and ground after
establishing the correct orientation using the Laue backscattering method within ~3 °. The
length of the specimens was at least 5 mm longer than the outer span. The notch of the SENB
specimens was cut to ~15 % of the specimen height using a 100 µm diamond blade saw result-
ing in a notch width of ~120 µm. The notch of the single crystal specimen were sharpened with
a razor blade up to ~50 µm using a 2-6 µm diamond suspension.
The fracture toughness experiments were performed at room temperature on an universal Erich-
sen testing machine with a calibrated Test GmbH 500 N load cell for the polycrystalline samples
and a calibrated Erichsen 50 N load cell for the single crystals. The experiments used a four-
point bending set-up with an inner (li) and outer (lo) span depending on the length of the speci-
men as given in table 5.1. The experiments were carried out with a constant crosshead velocity
of 0.2 mm min-1 for the single crystal specimens and 0.2, 2.0 and 20 mm min-1 for the polycrys-
65
Chapter 5
Table 5.1: Set-up and specimen dimensions

Sample Inner span Outer span Specimen SEM Specimen
(w x h) (w x h)
[mm] [mm] [mm] [mm]
Type A 5 20 3x4 3x4
15 30
Type B 5 15 3x4 2x4
100 5 15 2x3
111 5 15 2x3
talline specimens. The experimentally observed stressing rates for the polycrystalline speci-
mens are shown in table 5.2. Prior to each experiment, the specimens were preloaded upto 20 N
for the polycrystalline material and 5 N for the single crystals using a crosshead velocity of 0.2
mm min-1.
chamber was calculated as the ratio of the partial pressure (pH2O) at the actual dew point inside,
which was measured by a Panametrics MM35 hygrometer, and the equilibrium partial pressure
at room temperature. The relative humidity between 2 and 80 % was controlled by the inlet of
dry nitrogen gas in the case of a humidity decrease or by the inlet of nitrogen gas led through
water in the case of a humidity increase.
The fracture toughness experiments for the polycrystalline magnesium aluminate at RH = 0 %

were performed inside the vacuum chamber of a scanning electron microscope (pH2O <
7×10-4 Pa) on a special four-point bending set-up (Deben UK Ltd., Debenham, UK). The inner
and outer span were 15 and 36 mm for type A and 5 and 20 mm for type B, respectively. The
crosshead velocity was preset to 0.05 mm min-1.
Table 5.2: Average stressing rates of polycrystalline magnesium aluminate ceramic

Loading rate Type A Type B
[mm s-1] [MPa s-1] [MPa s-1]
0.2 1.13 0.92
2 14.3 13.6
20 93 104
66
Magnesium aluminate
5.2.3 Surface investigation preparation

The microtexture of a coarse grained hot-pressed magnesium aluminate sample with cracks was
studied using EBSD (see also the appendix to this chapter). The measurements were performed
on an electron probe microanalyser (EPMA, Superprobe Jeol JXA 8600 SX) with a standard
EBSD set-up from TexSEM Laboratories (Draper, UT, USA). The magnesium aluminate sam-
ple was embedded in a conducting polymer matrix and polished down to 3 µm with diamond
discs and diamond suspension. Since diamond polishing introduces mechanical damage (resid-
ual stresses) preventing the generation of indexible EBSD-patterns, this damage is eliminated
by polishing for 8 hours using a colloidal silica suspension. Subsequently, cracks were generat-
ed by indenting using Vickers indents.
The electrically non-conductivity of magnesium aluminate requires precautionary measures to

prevent surface charging effects, without influencing the EBSD-patterns. Therefore, colloidal
graphite was deposited inside the cracks and indents and the complete sample was coated with
a ~20 nm thick carbon layer. Additional carbon bridges were required in some cases.
The hydroxyl groups resulting from the dissociative adsorption of water on the surface of mag-
nesium aluminate were investigated using DRIFTS and LEIS. The magnesium aluminate pow-
der for the DRIFTS experiment was heated to 900 °C for 6 h in air to remove the bulk water
collected during storage. Subsequently, the powder put in an in-situ chamber of a SpectraTech
Collector DRIFT cell in a Nicolet Protége 460 spectrometer with a MCT detector. The pow-
der was outgassed at 550 °C for 1 h in flowing helium gas (10 ml min-1) prior to measuring the
spectrum at room temperature.
The fracture surfaces of single crystals are investigated using LEIS, which provides information
about the topmost atomic layer. The LEIS instrument “Calipso” at Calipso BV [5], which is de-
scribed in [6], is used since this set-up is more sensitive than normal LEIS instruments. Surfac-
es, (100) and (111) orientated, were created by fracturing single crystals with a relative small
and high amount of water inside a glove box (pH2O < 0.7 Pa, RH = ~0.02 %) and in air, respec-
tively. The samples fractured inside the glove box were transported to the LEIS apparatus in a
special device completely isolated from the air. The (100) oriented sample that was broken in
the glove-box was taken out of the apparatus and exposed to the air for 45 minutes, which was
the same time that the (100) oriented sample broken in air was left in air prior to measuring. A
relatively high energy 4He+ ion beam (5 and 4 keV for the (100) and (111) oriented samples)
67
Chapter 5
was used for the LEIS measurements in order to get a good distinction between the magnesium
and aluminium signals. Some oxygen sputtering was applied prior to the measurements to re-
move possible contaminations on the surface. This process is supposed to have no influence on
the surface itself.
5.3 Results and discussion of bulk properties
The density of the investigated magnesium aluminate ceramics has been determined using the
Archimedes’ method with water as the displaced fluid. Type A magnesium aluminate has a den-
sity of 87 % of the theoretical density and Type B 98 %, see table 5.3. The SEM images of the
surfaces of the two polycrystalline ceramics are shown in figure 5.2. Type A magnesium alumi-
nate shows a large number of pores, which are located at the grain boundaries, triple points and
inside the grains indicating that enhancement in the sintering procedure is possible. On the other
hand, Type B shows only small pores at the triple points. The SEM images allow for an estima-
tion of the average grain size, which is 10 and 2 µm for Type A and Type B, respectively.
5.3.2 Mechanical characterisation

The elastic properties of the two polycrystalline ceramics are shown in table 5.3. The low values
for Type A can be contributed to the large fraction of pores in the material. The values for Type
B are in agreement with the results from Baudín et al. [7] for a polycrystalline magnesium alu-
minate with similar microstructural properties.
The fracture toughness at ambient conditions (room temperature, ~40 % humidity) is measured
using the SENB method with a crosshead speed of 0.2 mm min-1 for comparison with published
data in literature. The toughness is 2.10 and 2.99 MPa m1/2 for Type A and B, respectively. The
fracture toughness of polycrystalline stoichiometric magnesium aluminate has been reported by
several authors [7-10] and is shown in table 5.4. The range of toughness data is between 1.8 and
Table 5.3: Density and elastic properties of magnesium aluminate ceramics

Spinel Type A Type B
-1
ρ [g cm ] 3.183 3.562
E [GPa] 196 259
ν [-] 0.27 0.32
G [GPa] 76.9 98.4
K [GPa] 143 238
68
Magnesium aluminate
a) b)
c) d)
Figure 5.2: SEM images of polished and chemically etched surfaces of Type A (a & b) and
Type B (c & d) magnesium aluminate ceramic.
Table 5.4: Fracture toughness data for polycrystalline magnesium aluminate

Reference Crosshead Methoda Grain size ρ KIc
speed
[mm min-1] [µm] [%] [MPa m1/2]
[7] 0.5 SN 1.5 98 3.0
[9] 0.1 SN 35 100 1.46
CN 35 100 1.79
KI 35 100 1.81
b
[10] 0.005 CN 150 2.2
c
[8] 2.5 KI 5 1.94
c
12 1.98
c
25 1.83
c
38 1.97
This work 0.2 SN 10 87 2.08
2 98 2.99
a. SN = straight notch, CN = chevron notch, KI = Knoop microflaw induced fracture
b. Minimization of impurities and porosity if emphasized
c. Theoretical dense
69
Chapter 5
2.2 MPa m1/2 and is just a little higher than the fracture toughness of single crystals along the
three low-index crystallographic planes: 1.18, 1.54 and 1.90 MPa m1/2 for the (100), (110) and
(111) planes [11]. The small difference in toughness between the single crystals and polycrys-
talline samples can be explained by the fracture mode which is mixed intergranular/transgran-
ular [8,10] or 100 % transgranular [3] implying that the fracture of a single grain can act as a
starter for the overall fracture.
The value for Type A is in the range as reported in the literature. However, a 50 % higher tough-
ness value of ~3 MPa m1/2 is found for Type B, as did Baudín et al. [7]. The grain size is the
main difference between these studies and the others. A grain size effect is absent for magnesi-
um aluminate ceramics with grains larger than 5 µm according to Stewart and Bradt [8]. How-
ever, the high toughness ceramics have grain sizes of 1.5-2 µm. Bhaduri and Bhaduri [12] found
a value of 3.45 MPa m1/2 for a magnesia-rich magnesium aluminate with a grain size of 0.1-
0.15 µm. The smaller grains provide an explanation for the high toughness values as they can
not act as a starter for fracture on their own. The flaw starting in one grain should pass a grain
boundary via e.g. subcritical crack growth and fracture a second grain in order to start the over-
all fracture. The grain boundary acts in this case as an extra toughening mechanism. Rice and
Wu [3] have suggested this possibility of a flaw growing into a second grain, but rejected this
possibility for the resulting high values of ~3.4 MPa m1/2 which they considered as unrealistic.
The fracture toughness of the magnesium aluminates as a function of relative humidity and at
different crosshead velocities is shown in figure 5.3. It is observed that the fracture toughness
of magnesium aluminate is decreasing substantially with increasing humidity for all crosshead
velocities, indicating subcritical crack growth. This decrease was also observed by Rice and Wu
[3] in bending strength experiments, but they could not detect a decrease in fracture toughness
due to problems with flaw size identification. The decrease in toughness for Type B magnesium
aluminate is continuous with increasing humidity indicating that adsorption of water molecules
in the wake field of the crack does play an important role in the fracture process next to the
chemical reaction at the crack tip. This continuous decreasing behaviour of the toughness is sim-
ilar to MnZn ferrites [13] and calcium hydroxyapatite [14] making magnesium aluminate the
third known material to have a Type II behaviour.
70
Magnesium aluminate
a) 3 .0
2 .8
1/2
2 .6
2 .4
2 .2
2 .0
1 .8
0 20 40 60 80 1 00
R elative h um idity [% ]
b) 4 .2
4 .0
1/2
3 .8
3 .6
3 .4
3 .2
3 .0
2 .8
2 .6
0 20 40 60 80 1 00
R elative h um idity [% ]
Figure 5.3: Fracture toughness of magnesium aluminate ceramics a) Type A and b) Type B as
a function of relative humidity and at crosshead velocities of 0.2 (), 2.0 (z) and 20 mm min-1
(5). The lines provide a guide for the eye.
71
Chapter 5
However, while dense magnesium aluminate shows a Type II behaviour, porous magnesium
aluminate as Type A does not. The decrease in fracture toughness with increasing humidity is
characterised by a sharp drop between 0 % and 2-10 % relative humidity and a slowly decreas-
ing toughness onwards. This is typical for a Type I behaviour as e.g. alumina or lead zirconate
titanate shows [14]. This indicates that adsorption can play a role in the decrease of fracture
toughness, but microstructural aspects as e.g. pores interact as well.
The exact interaction of pores on adsorption remains unrevealed. The interaction is only partly
explained by the reduction of fractured surface area. Another explanation for this interaction
might be that the crack tip moves too fast while travelling trough the pores impeding the catch-
ing up of the (energy) contribution of the adsorption to the process zone. Furthermore, the ad-
sorption energy from the adsorption on the surface of the pores is less than on the fractured
surface as the surface is already relaxed.
The subcritical crack growth of spinel has been studied using single crystal specimens. Special-
ly prepared specimen were fractured with a crosshead speed of 0.2 mm min-1 along the (100)
and (111) plane at a relative humidity of 2 and 40 %. The results of three specimens at each com-
bination of humidity and orientation are shown in table 5.5. A decrease of 17 and 18 % due to
subcritical crack growth is observed for the (100) and (111) orientations, respectively, which is
somewhat smaller than the decrease of 26 % obtained by Rice and Wu [3] for the (100) orien-
tation using strength measurements. This can probably be explained by the fact that in this work
the low humidity measurements were performed at 2 % humidity and by Rice in liquid nitrogen.
A single experiment was performed for comparison with the data of Stewart and Bradt [11] at
a relative humidity of ~30 % and a crosshead velocity of 2.5 mm min-1 with a (111) oriented
Table 5.5: Fracture toughness and fracture surface energy of single crystal spinel
Relative KIc [MPa m1/2] γf [J m-2]
humidity
[%] (100) (111) (100) (111)
2 1.30 1.97 4.33 5.21
(±0.07) (±0.12)
40 1.07 1.63 2.93 3.56
(±0.09) (±0.12)
72
Magnesium aluminate
specimen. The resulting fracture toughness of 1.86 MPa m1/2 is in good agreement with the val-
ue of 1.90 MPa m1/2 of these authors.
The fracture surface energy (γf) can be calculated by:
2 2
K Ic ( 1 – ν )
γ f = --------------------------
-, (5.1)
2E
where E and ν are the orientation dependent Young’s modulus and Poisson’s ratio, respectively,
which can be calculated using the single crystal elastic parameters [15]. The decrease in fracture
surface energy is ~46 %, as shown in table 5.5.
Fang et al. [16] have performed computer simulations of the reduction of surface energy of dif-
ferent fracture planes in spinel with increasing coverage of hydroxyl groups. They concluded
using the experiments of Rice and Wu in combination with their theoretical results that the frac-
ture planes will only be partially hydrated. The present work confirms this idea.
5.4 Results and discussion of surface properties
5.4.1 EBSD
The EBSD image of a coarse grained hot-pressed magnesium aluminate ceramic with a com-
bined crack originating from two different Vickers indents is shown in figure 5.4 together with
a SEM image of the same region. The EBSD image is composed of three separate EBSD scans,
which are separately edited for the confidence level, image quality and crystal growth function.
The small differences between the same grain measured in two EBSD scans are due to the used
interplanar angle tolerance of 5 °, sample movement during the two scans and the used growth
function, which deviates near the edges of the scans. The pole figures of the image, shown in
figure 5.5, indicate the absence of texture.
The Euler angles of the grains, describing the orientation of the grain with respect to the speci-
men axes, along the left and right side of the wide crack in figure 5.4 are shown in table 5.6. It
is shown from the image and the Euler angles, that the fracture is both trans- and intergranular.
The pole figures of the orientations of the grains along the crack, shown in figure 5.6, indicate
that a preferenced orientation for the crack path is absent.
73
Chapter 5
a) b)
20 µm 10 µm
c)
111
100 110
Figure 5.4: a) ESBD image of a magnesium aluminate ceramic with a crack showing the ori-
entation of the grains, b) SEM image of the same region, c) transgranular fractured grains in
a).
74
Magnesium aluminate
Table 5.6: Orientation of the grains from top to bottom along the crack in figure 5.4 in
Euler anglesa
Left side Trans Right side
granular
ϕ1 [°] Φ [°] ϕ2 [°] ϕ1 [°] Φ [°] ϕ2 [°]
208.4 18.7 242.1 143.5 71.0 339.2
107.8 49.8 1.4 154.8 70.6 321.0
159.7 37.4 264.0 109.6 39.3 304.9
162.4 30.3 290.5 87.8 13.0 19.3
122.2 35.3 321.1 103.2 52.3 20.6
283.7 13.3 188.7 225.0 26.1 271.1
169.1 41.4 322.1 127.1 78.3 306.7
102.8 39.9 15.2 209.6 19.3 264.3
221.4 34.0 267.3 67.8 62.1 12.1
95.0 28.7 23.1 105.9 23.9 338.7
106.1 29.0 12.2 101.4 48.5 305.0
111.5 55.1 9.9 20.2 16.6 90.5
111.2 56.6 10.2 205.8 26.1 275.9
28.0 18.6 93.4 77.9 29.6 343.0
7.2 17.0 42.6 177.4 49.2 242.9
176.8 50.2 242.4 74.1 56.0 36.3
122.3 32.5 13.5 125.9 35.6 319.5
73.8 55.7 36.8 111.8 31.9 328.9
72.7 38.0 346.1 203.1 46.3 248.1
65.8 50.9 43.3 9.5 19.3 43.2
269.5 11.5 140.0 131.2 64.6 301.2
197.0 43.0 304.8 160.1 29.2 293.9
87.7 50.4 331.3 139.8 38.4 273.0
138.5 38.3 282.6 88.4 48.9 330.3
62.5 62.6 16.3 137.5 50.2 351.5
142.7 79.8 315.7
a. The arrows indicate the grains which have been broken transgranular. These are shown in figure
5.4c.
75
Chapter 5
(100) (111)
y/TD y/TD
x/RD x/RD
Figure 5.5: (100) and (111) pole figures of all the grains in figure 5.4a.
(100) (111)
y/TD y/TD
x/RD x/RD
Figure 5.6: (100) and (111) pole figures of grains along the crack in figure 5.4a.
5.4.2 LEIS
Since a preferred fracture plane is absent, the focus is laid on the fracture along the low-index
planes. Therefore, the composition of the outmost atomic layer of the fracture surfaces of single
crystals is investigated with LEIS. The LEIS spectra of the fracture surfaces of the (100) and
(111) planes broken at pH2O < 0.7 Pa and in air are shown in figure 5.7. The composition can
be estimated from the peak areas after subtraction of the background and is shown in table 5.7
with the peak area of the oxygen peak set to 100. However, the peak areas are very dependent
on the applied background making it easy to obtain different Al/Mg ratios between ~1.0-1.5.
Therefore, it must be concluded that the composition more or less remains the same regardless
of applied water vapour pressure.
76
Magnesium aluminate
a) 50
O Mg Al
40 III
LEIS y ield [coun ts /nC ]
I
30
20
II
10
0
14 00 16 00 18 00 20 00 220 0 24 00 26 00 28 00 30 00
En erg y [eV ]
b) 1 00
O Mg Al
80
LEIS yield [cou nts/nC ]
60 I
40
20
II
0
12 00 14 00 16 00 18 00 20 00 22 00 24 00
Energy [eV ]
Figure 5.7: LEIS spectra of oxygen treated fracture surfaces of single crystals with a) (100)
direction (5 keV) and b) (111) direction (4 keV). I = fractured at pH2O < 0.7 Pa, II = fractured
in air and III = fractured at pH2O < 0.7 Pa and subsequently exposed to air for 45 minutes.
77
Chapter 5
Table 5.7: Relative composition of fracture surfaces of single crystal spinel

Sample O Mg Al Al/Mg
(100), < 0.7 Pa 100 118 149 1.26
(100), exposed to air 100 135 152 1.13
(100), air 100 117 125 1.07
(111), < 0.7 Pa 100 89 126 1.41
(111), air 100 103 100 0.97
It is noted that both magnesium and aluminium cations are present on the surface. This is re-
markable, since under normal conditions magnesium cations in the tetrahedral interstices are
not visible with LEIS [18]. On the other hand, computer simulations of (100) fracture surfaces
indicate that a magnesium cation (in the tetrahedral interstice) terminated surface is the most
stable [16]. This difference between simulation and experiment can be explained by the absence
of the inversion process in the simulations. In this process, a magnesium cation in the tetrahedral
interstice and an aluminium cation in the octahedral interstice swap their interstices in the lat-
tice. In a single crystal up to 30 % of the magnesium cations can be in octahedral interstices
[17], which can explain the presence of both cations. However, this cannot explain completely
the Al/Mg ratio indicating that some magnesium in tetrahedral interstices must be visible on
fracture surfaces for LEIS.
5.4.3 DRIFTS
The stretching region of the hydroxyl groups on the surface of magnesium aluminate powder in
the DRIFTS spectrum is shown in figure 5.8. The spectrum is similar to the reported spectra in
literature [19-21], although it is more resolved due to outgassing under a helium flow in contrast
to air used by the latter authors. Nevertheless, bulk water is still present on the sample, which is
indicated by the broad peak at ~3300 cm-1 from the hydrogen bridges and the sharp small peak
at ~3695 cm-1 of the hydroxyl-stretching of bulk water. The presence of bulk water can be ex-
plained by the outgassing temperature of 550 °C, since at that temperature only ~90 % of the
bulk water is removed in 1 h [19].
The peak at ~3680 cm-1 is due to bridging hydroxyl groups on trivalent aluminium cations1. The
sharp small peak at ~3790 cm-1 can be contributed to hydroxyl groups on an aluminium cation
in a tetrahedral interstice proving the presence of inversion at the surface as indicated by the
1. The absorption region of the surface hydroxyl groups are taken from Busca et al. [21].
78
Magnesium aluminate
0.40
0.35
Absorbance [Kubelka-Munk]
0.30
0.25
0.20
0.15
0.10
0.05
0.00
4000 3800 3600 3400 3200 3000 2800
-1
W avenumbers [cm ]
Figure 5.8: DRIFTS spectrum of the hydroxyl-stretching region on magnesium aluminate.
LEIS experiments. The broad peak with shoulders between ~3700 and ~3780 cm-1 cannot be
unambiguously assigned to aluminium cations in the tetrahedral interstice (~3800 - 3760 cm-1)/
octahedral interstice (~3750 - 3720 cm-1), to the magnesium cations in the octahedral or tetra-
hedral interstices (~3750 - 3700 cm-1) or to a combination of these possibilities.
5.5 Conclusions
The fracture toughness of dense and porous magnesium aluminate ceramics has been investi-
gated at ambient conditions. It is observed that the fracture toughness of dense magnesium alu-
minate is ~3.0 MPa m1/2, which is ~50 % higher than reported data in literature. This is due to
the grain size, which is in this work 1.5-2 µm and in the literature more than 5 µm. The fracture
toughness of porous magnesium aluminate is in the range of the reported data in literature.
Furthermore, the role of water on the fracture of magnesium aluminate spinel is investigated.
The fracture toughness of polycrystalline magnesium aluminate, measured using the SENB
technique, decreases with increasing humidity, showing the typical Type II behaviour indicat-
ing that adsorption plays an important role in the fracture process. The only other materials
known to have this behaviour are hydroxyapatite and MnZn ferrite. However, porous magnesi-
um aluminate shows a typical Type I behaviour indicating that microstructural aspects as e.g.
pores have an influence too. The latter exact mechanism is still unknown.
79
Chapter 5
The subcritical crack growth along low-index planes of single crystal spinel is investigated us-
ing a SENB set-up. Comparing the decrease in fracture surface energy of ~46 % between 2 and
40 % relative humidity to the surface energy values obtained from computer simulations indi-
cates that during fracture the surface is only partially hydrated.
The texture of the grains along a crack in magnesium aluminate is investigated using EBSD.
The investigation of a non-conductive material with this technique is not straightforward (see
appendix) and special precautions must be taken to use EBSD. EBSD revealed that the fracture
is both trans- and intergranular. The grains along the crack do not show texture, which would
have indicated a preference in fracture mode.
Although computer simulations predicted a magnesium terminated (100) surface, both magne-
sium and aluminium cations are found in the outermost layer of the fracture surface using LEIS.
This difference can be partially attributed to the presence of inversion, which is absent in the
simulations. DRIFTS measurements of hydroxyl groups on powders confirm the presence of in-
version by the detection of hydroxyl groups on aluminium cations in a tetrahedral interstice.
However, it is shown that the hydroxyl groups are at least present on the aluminium cations, but
the presence on magnesium cations cannot be excluded.
5.6 Appendix: Fracture and EBSD

An electron backscattered diffraction pattern (Kikuchi pattern) is created by focusing an elec-
tron beam on the surface of a specimen inclined with respect to the incoming beam. While strik-
ing the sample, some electrons in a small volume are scattered on the atomic planes. These
backscattered electrons collide with a phosphoric screen forming Kikuchi patterns, see figure
5.9. The reflection bands in these patterns correlate directly to the crystallographic planes in the
diffracting volume. The images of these patterns are recorded and processed by a computer pro-
gram obtaining the indexation of the reflection bands in the pattern and quality parameters like
confidence index (how well could the pattern be indexed?) and image quality. Overall micro-
textural information can be obtained by scanning the surface of the specimen point by point.
It is possible to study the fracture surfaces with the EBSD technique to get more information
about the role of texture in the fracture process. However, there are some difficulties attached
to such an investigation. Only a fraction of the grain facets are oriented adequately for obtaining
80
Magnesium aluminate
EPMA-chamber
Phosphoric screen
e-
Camera Computer
specimen
70 °
Generation Detection Processing

Figure 5.9: Schematic representation of an EBSD set-up.
the Kikuchi diffraction patterns. This requires to reorient the specimen multiple times to get a
good statistical result [22].
An easier approach is to determine the orientation of the grains along the crack normal to the
crack surface and to compare these with the orientation of the other grains. Sharp cracks in con-
ductive materials, like e.g. a titanium alloy [23], can be investigated easily in this way. Howev-
er, for non conductive materials charging at the edges of the crack is throwing a spanner. This
can be avoided by generating a relative wide crack, which is filled with a conductive material
like e.g. colloidal graphite.
B.G. Anderson (Eindhoven University of Technology) is acknowledged for the DRIFTS meas-
urements and N. Lousberg (Eindhoven University of Technology) for the EBSD experiments.
A. Knoester, A. Gildenpfenning, M. Viitanen and H.H. Brongersma (Calipso, Eindhoven Uni-
versity of Technology) are acknowledged for the LEIS experiments and discussions. Further-
more, H. Gorter (Institute of Applied Physics, TNO-TPD) is acknowledged for providing the
Type B magnesium aluminate ceramics and A.J.M. van Dijk (Eindhoven University of Tech-
nology) [24] for the Type A magnesium aluminate ceramic fracture experiments.
81
Chapter 5
5.8 References
[1] T. Yano, Effects of neutron irradiation on the mechanical properties of magnesium alu-
minate spinel single crystals and polycrystals, J. Am. Ceram. Soc., 82 (1999), 3355-3364
[2] B. Hallstedt, Thermodynamic assessment of the system MgO-Al2O3, J. Am. Ceram. Soc.
75 (1992), 1497-1507
[3] R.W. Rice and C.CM. Wu, Slow crack growth in MgAl2O4 single- and polycrystals, J.
Mater. Sci. Lett., 14 (1995), 723-727
[4] Custom Technical Ceramics Inc., Arvada, CO, USA
[5] Calipso BV, Eindhoven, The Netherlands, see also www.calipso.nl
[6] H.H. Brongersma, A. Gildenpfennig, A.W. Denier van der Gon, R.D. van de Grampel,
W.P.A. Jansen, A. Knoester, J. Laven and M.M. Viitanen, Insight in the outside: New
applications of low-energy ion scattering, Nucl. Instr. and Meth. in Phys. Rev. B, 190
(2002), 11-18
[7] C. Baudín, R. Martínez and P. Pena, High temperature mechanical behaviour of stoichio-
metric magnesium spinel, J. Am. Ceram. Soc., 78 (1995), 1857-1862
[8] R.L. Stewart and R.C. Bradt, Fracture of polycrystalline MgAl2O4, J. Am. Ceram. Soc.,
63 (1980), 619-623
[9] A. Ghosh, K.W. White, M.G. Jenkins, A.S. Kobayashi and R.C. Bradt, Fracture resist-
ance of a transparent magnesium aluminate spinel, J. Am. Ceram. Soc., 74 (1991), 1624-
1630
[10] K.W. White and G. P. Kelkar, Fracture mechanisms of a course-grained, transparent
MgAl2O4 at elevated temperatures, J. Am. Ceram. Soc., 75 (1992), 3440-3444
[11] R.L. Stewart and R.C. Bradt, Fracture of single crystal MgAl2O4, J. Mater. Sci., 15
(1980), 67-72
[12] S. Bhaduri and S.B. Bhaduri, Microstructural and mechanical properties of nanocrystal-
line spinel and related properties, Ceram. Intern., 28 (2002), 153-158
[14] N.J. van der Laag, A.J.M. van Dijk, L.J.M.G. Dortmans and G. de With, The role of
water adsorption on the fracture of ceramic oxides, J. Eur. Ceram. Soc., (submitted)
[15] J.F. Nye, Physical properties of crystals, 2nd Ed., Clarendon Press, Oxford, UK (1990)
[16] C.M. Fang, G. de With and S.C. Parker, Computer simulation of dissociative adsorption
of water on the surfaces of spinel MgAl2O4, Phys. Rev. B, (accepted)
[17] K.E. Sickafus, J.M. Wills and N.W. Grimes, Structure of spinel, J. Am. Ceram. Soc., 82
(1999), 3279-3292
[18] J.-P. Jacobs, A. Maltha, J.G.H. Reintjes, J. Drimal, V. Ponec and H.H. Brongersma, The
surface of catalytically active spinels, J. Catal., 147 (1994), 294-300
[19] C. Morterra, G. Ghiotti, F. Boccuzzi and S. Coluccia, An infrared spectroscopic investi-
gation of the surface properties of magnesium aluminate spinel, J. Catal., 51 (1978),
299-313
82
Magnesium aluminate
[20] P.F. Rossi, G. Busca, V. Lorenzelli, M. Waqif, O. Saur and J.-C. Lavalley, Surface basic-
ity of mixed oxides: magnesium and zinc aluminates, Langmuir, 7 (1991), 2677-2681
[21] G. Busca, V. Lorenzelli, G. Ramis and R.J. Willey, Surface sites on spinel-type and
corundum-type metal oxide powders, Langmuir, 9 (1993), 1492-1499
[22] D.P. Field, Recent advances in the application of orientation imaging, Ultramicroscopy,
67 (1997), 1-9
[23] S.I. Wright and D.P. Field, Recent studies of local texture and its influence on failure,
Mater. Sci. Eng., A257 (1998), 165-170
[24] A.J.M. van Dijk, The influence of loading rate and environment on brittle fracture of
ceramics, M.Sc. Thesis, Eindhoven University of Technology, Eindhoven, The Nether-
lands, (2001)
83
Chapter 5
84
-6-
Structural, mechanical, thermophysical and

dielectric properties of zinc aluminate
(ZnAl2O4)
6.1 Introduction
Zinc aluminate (ZnAl2O4) is a member of the spinel family, whose natural occurrence is the
mineral gahnite. It was discovered near Falun (Sweden) in 1807 and was originally called au-
tomolite, but later renamed after its discoverer the Swedish chemist J.G. Gahn (1745-1818) [1].
The gahnite crystals occur in an octahedral, dodecahedral or cubic shape and have a blackish,
greenish appearance. In general, the crystals have magnesium, iron and - in rare cases- manga-
nese impurities. Gahnite is mainly found in granitic pegmatites, but also in contact altered lime-
stone and metasomatic replacement veins and ores. The major localities of gahnite are the
replacement ores in Franklin, NJ, USA and Falun and in the metasomatic deposit in Western
Australia [2].
At present, zinc aluminate is used as a catalyst for the dehydration of saturated alcohols to ole-
fins [3], methanol and higher alcohol synthesis [4,5], preparation of polymethylbenzenes [6],
synthesis of styrenes from acetophenons [7] and double bond isomerisation of alkenes [8]. Fur-
thermore, zinc aluminate can also be used as a catalyst support, since it has a high thermal sta-
bility, low acidity and a hydrophobic behaviour. Moreover, it has a strong metal-support
interaction preventing e.g. platinum and platinum/tin to sinter [9]. Finally, zinc aluminate can
85
Chapter 6
be used as a second phase in glaze layers of white ceramic tiles to improve wear resistance and
mechanical properties and to preserve whiteness [10].
Zinc aluminate is normally synthesised via a solid-state reaction of zinc and aluminium oxides
above 800 °C [11,12] or via coprecipitation [9,14], hydrothermal [13] and sol-gel methods with
several organic precursors [12,14-16]. It could be used as a ceramic material like e.g. magnesi-
um aluminate (MgAl2O4) and manganese-zinc ferrites ((Mn,Zn)Fe2O4). However, in literature
only a few papers have been published about the sintering of zinc aluminate [11,17-19], imply-
ing many unknown bulk properties like e.g. Young’s modulus. In this chapter, it is attempted to
manufacture dense zinc aluminate ceramics and to determine some of its bulk properties. Fur-
thermore, since cation inversion in spinels can influence the properties, the effect of the prepa-
ration method of the zinc aluminate powders on this inversion is investigated.
6.2 Crystallographic aspects of zinc aluminate

The crystal structure of spinel stricto sensu (MgAl2O4) has been determined independently by
Bragg [20] and Nishikawa [21] in 1915. It has the space group Fd3m (Oh7; number 227 in the
International Tables [22]) and has a cubic structure made of eight molecular units (AB2O4).
There are three main groups of compounds with the spinel structure and the chemical formula
AB2O4: II-III spinels, IV-II spinels and defect-spinels. In the first group the A cation is divalent
and the B cations trivalent. Magnesium aluminate and zinc aluminate are examples of this
group. In the second group the A cation is tetravalent en the B cations divalent. Ülvospinel
(Fe2TiO4) is a well-known member of this group. Spinels from the third group have vacancies
on locations where cations should be. A well-known example is γ-alumina.
One unit cell of a compound with the spinel structure is built up from 32 oxygen atoms arranged
in a fcc-lattice, giving 64 tetrahedral and 32 octahedral interstices. In a II-III spinel the divalent
A cations occupy 8 tetrahedral interstices and the trivalent B cations occupy 16 octahedral in-
terstices. This distribution of the cations is designated as normal. However, this is thermody-
namically not the most stable situation, since the configurational entropy counteracts the site
preference energy. Therefore, A and B cations interchange interstices via diffusion, eventually
leading to the situation where all the A cations are in octahedral interstices. The latter extreme
situation is designated as inverted.
All distributions between the two extremes are possible and the degree of inversion is given by
the inversion parameter x, which is defined as the fraction of A cations in octahedral sites. The
86
Zinc aluminate (bulk)
inversion parameter x can be obtained via careful single crystal X-ray diffraction or via nuclear
magnetic resonance with magic angle spinning (MAS-NMR). In the latter case, x can be ob-
tained for aluminates from the peak areas by:
2
x = ---------------------------------------
-, (6.1)
VI IV
1 + ( Al ⁄ Al )
where AlVI is the peak area of aluminium cations in an octahedral surrounding (~0-10 ppm) and
AlIV of the aluminium cations in a tetrahedral surrounding (~60-70 ppm).
The inversion in zinc aluminate is known, by X-ray diffraction [26-28], to be small in contrast
to e.g. magnesium aluminate [29]. Moreover, in computer simulations the inversion of zinc and
aluminium atoms is also found to be energetically unfavourable [30,31]. Furthermore, NMR
studies to the cation inversion in zinc aluminate, which is prepared via the solid state synthesis
route, confirm the virtual absence of inversion [32]. However, to some extent, inversion has
been found in zinc aluminate synthesized using a sol-gel method with alkoxides depending on
the temperature [16].
6.3 Instrumentation
The structural properties of zinc aluminate powders were investigated by powder X-ray diffrac-
tion (XRD) on a Rigaku Geigerflex using CuKα1 radiation. Furthermore, one-dimensional solid
state 27Al MAS-NMR spectra were measured with a ~6 mg sample for quantitative comparison
on a Bruker DMX500 spectrometer operating at an 27Al NMR frequency of 130.32 MHz using
a spinning speed of 30 kHz. Rotor-synchronised echoes were recorded using the two-pulse se-
quence p1-τ-p2-τ-FID (Hahn spin-echo pulse [23,24]) with a dwell time (τ) of 1 µs and opti-
mised pulse lengths p1 and p2 of 1.2 and 2.4 µs, respectively. A delay time of 10 s was applied
between each of the 128 scans. The dielectric properties were determined on a HP 4284A LCR
meter and the elastic properties with a Panametrics model 25DL, using the pulse-echo method
[25]. The thermophysical properties were determined on a Compotherm XP/20X (diffusivity)
and Differential Scanning Calorimeter (DSC) of Perkin Elmer model Pyris 1 (heat capacity).
87
Chapter 6
6.4 Preparation
6.4.1 Powder synthesis

Zinc aluminate was made via three different routes: solid state synthesis, coprecipitation and a
sol-gel method. In the solid state synthesis route equimolar amounts of zinc oxide (Merck,
>99%) and γ-alumina (Degussa) with a total weight of 90 g were put into a plastic container.
Distilled water was added and the mixture was mixed overnight. After evaporating most of the
water, the mixture was dried at 110 °C for 2 h and, subsequently, the large agglomerates were
were pulverized in an agate mortar. The mixture was divided in three batches, each put in an
alumina crucible covered with an alumina lid in order to prevent contamination of the furnace
with zinc. In separate experiments the batches were heated in air to 1000 ºC for 8 h, 800 ºC for
8 h and 12 h, respectively, with a heating rate of 10 ºC min-1. The batches were dried (without
the lid) for 1 hour at 110 ºC prior to the heating.
In the coprecipitation method, described in [14], an equimolar amount of zinc nitrate and alu-
minium nitrate (both from Merck, >99 %) was dissolved in a citric acid solution of pH = 2 under
stirring. A solution of 16 wt% ammonia nitrate (Merck, >99 %) was slowly added until the so-
lution was neutral and a chelate was formed. The chelate was dried in air for 20 h and subse-
quently dried in a furnace at 50 ºC (68 h) and 110 ºC (20 h). The resulting powder was divided
into three batches.
As in the solid state route, the batches were heated in air to 1000 ºC for 8 h, 800 ºC for 8 h and
12 h, respectively, with a heating rate of 10 ºC min-1. Although the batches were put into an alu-
mina crucible, this time the lid was removed in order to let the nitrogenous fumes evaporate.
The batches were dried at 110 ºC (1 h) and 300 °C (6 h) prior to calcining in order to remove
the nitrates.
Zinc aluminate was synthesized using a sol-gel method based on the method described by Mon-
rós et al. [33]. Aluminium and zinc chloride (Merck, >99 %) were dissolved in 100 ml water,
resulting in an aluminium and zinc cation concentration of 0.6 M and 0.3 M, respectively. Fur-
thermore, 10 g of gelatin (Merck, >99 %) is dissolved in 100 ml of water under stirring and
heating to obtain a homogeneous solution. The warm gelatin solution was added to the cation
solution under heating and stirring, until a homogeneous mixture was obtained, subsequently
followed by cooling in a refrigerator (4 °C) for 30 min. The resulting gel was aged for 96 h at
room temperature and dried at 80 °C for 40 h.
88
In order to burn out the gelatin, the dried gel was put in an alumina vessel and heated up to
400 °C at a rate of 3 °C min-1, and kept at that temperature for 7 h in a gas flow of 80 % N2/
20 % O2. After cooling down at a rate of 3 °C min-1, the powder was ground and subsequently
reheated at 3 °C min-1 to 800 °C. The zinc aluminate powder was kept at that temperature for
12 h in 80 % N2/20 % O2 gas mixture and, subsequently, cooled to room temperature at
3 °C min-1.
In additional experiment this powder was reheated to 1000 °C at 10 °C min-1 and kept at that
temperature for 8 h.
6.4.2 Compaction and sintering

Zinc aluminate powder prepared via the solid state route at 1000 °C for 8 h was ball-milled for
24 h with a small amount of isopropanol. Subsequently, the powder was sieved in a copper sieve
with a mesh of 50 µm. Finally to improve sintering, a small amount of distilled water was added
to the powder, before it was stored in a closed plastic container at 70 °C for 24 h.
The powder was put in a steel die with a diameter of 12 or 15 mm, which was lubricated with a
90% petroleum ether-10% oleic acid mixture, followed by uniaxially pressing to 70 MPa or
150 MPa. The resulting tablets were put with some extra zinc aluminate powder in an alumina
crucible closed with an alumina lid. The tablets were heated to different temperatures between
1200 and 1600 °C at 3 °C min-1 and kept at those temperatures for 8 h.
6.5.1 Structural properties

6.5.1.1 XRD
XRD measurements showed that zinc aluminate powder (JCPDS file 05-0669) has been formed
(see figure 6.1). However, in all samples zinc oxide (JCPDS file 36-1451) was present, except
those calcined at 1000 °C and prepared via the sol-gel method. This is in agreement with the
results from Keller et al. [12], who found that at 1000 °C ~95 % zinc aluminate would be made.
The presence of alumina (JCPDS file 47-1292) could not be detected in any sample, since the
peak positions of alumina coincide with those of zinc aluminate.
6.5.1.2 Composition
The zinc-aluminium ratio of the single phase zinc aluminate prepared via the solid state route,
coprecipitation and the sol-gel method at 1000 °C is determined using atomic absorption spec-
89
Chapter 6
c
I
II
20 30 40 50 60 70
2θ [°]
Figure 6.1: XRD spectra of zinc aluminate powders prepared via a) the sol-gel method
(800 °C, 12 h), b) coprecipitation (800 °C, 12 h) and c) solid state route (1000 °C, 8 h). Fur-
thermore, the JCPDS files of I) gahnite (05-0669) and II) zincite (36-1451) are shown.
troscopy (AAS). The composition is Zn0.95Al2O4, Zn0.83Al2O4 and Zn0.48Al2O4 (accuracy:

± 5%) for the solid state, coprecipitation and the sol-gel prepared zinc aluminate, respectively.
The zinc-aluminium ratio of the zinc aluminate ceramics determined by energy dispersive X-
ray (EDX) on polished surfaces is 0.99:2, consistent with the zinc deficient character of the
starting powders.
The formation of zinc deficient zinc aluminate is due to the volatile nature of zinc oxide (zinc
oxide, pZn = 9×10-4 Pa at 1000 °C [34]; aluminium oxide, pAl = 4×10-13 Pa [35]; magnesium
oxide, pMg = 4×10-8 Pa [35]). The large surface area and presence of a flow in the furnace, in-
creases the deficiency for the zinc aluminate prepared via the sol-gel method as compared to the
material prepared via the solid state route.
6.5.1.3 MAS-NMR
The NMR spectra of the zinc aluminate powders prepared via the solid state and coprecipitation
are shown in figures 6.2 and 6.3 respectively. The presence of a peak at ~60 ppm indicates that
there is some inversion present in all the powders. However, the size of the peak indicates that
the amount of inversion is very small. Kashii et al. [32] found the same results, but they kept
zinc aluminate at 900 °C for 40 h in contrast to 800 °C for 8 h used in this investigation. Fur-
90
c)
b)
a)
120 100 80 60 40 20 0 -20 -40

ppm
Figure 6.2: 27Al MAS NMR spectra of zinc aluminate prepared following the solid state synthe-
sis route at a) 1000 °C for 8 h, b) 800 °C for 8 h and c) 800 °C for 12 h.
c)
b)
a)
120 100 80 60 40 20 0 -20 -40

ppm
Figure 6.3: 27Al MAS NMR spectra of zinc aluminate prepared following the coprecipitation
route at a) 1000 °C for 8 h, b) 800 °C for 8 h and c) 800 °C for 12 h.
91
Chapter 6
b)
a)
120 100 80 60 40 20 0 -20 -40

ppm
Figure 6.4: 27Al MAS NMR spectra of zinc aluminate prepared by a) sol-gel synthesis and b)
solid state synthesis for comparison.
thermore, it is clear that there in no difference between the two preparation methods and that the
temperature or the calcining time does not have a significant influence.
The NMR spectra of the zinc aluminate powder prepared by the sol-gel method are shown in
figure 6.4 together with a spectrum of zinc aluminate prepared via the solid state synthesis route
for comparison. In contrast to the other methods, the sol-gel method prepared zinc aluminate
has a large degree of inversion. The normal degree of inversion, as obtained by the other meth-
ods, could not be reached after an additional reheating for 8 h at 1000 °C. This is in contrast with
the results of Mathur et al. [16], who found a large degree of inversion at 600 °C, but a small
one at 1000 °C.
The presence of a large inversion in the sol-gel prepared zinc aluminate could be attributed to
the presence of aluminium cations with a four or five oxygen atom surroundings at the surface,
since zinc aluminate prepared via the sol-gel route has a large surface area [36]. However, the
NMR experiments were performed in a quantitative manner, revealing that all aluminium cati-
ons are detected and that no magnetic shielding occurred. This implies that the inversion is oc-
curring in the bulk and is not an artefact of surface aluminium cations, since they are only a
minor fraction of all the aluminium cations.
92
The NMR spectra have been measured on zinc deficient zinc aluminate, which implies an ex-
cess of aluminium cations forming aluminium oxide. The absence of second phase in XRD
spectra suggests that a solid solution of the spinel phase of aluminium oxide (γ-alumina) and
zinc aluminate has been formed.
However, in γ-alumina 25 % of the aluminium cations are located at tetrahedral interstices [37]
and contribute to the peak at 60 ppm. In order to determine the inversion parameter of pure zinc
aluminate from these spectra, a correction to equation 6.1 for this γ-alumina contribution must
be made. The inversion parameter for zinc deficient zinc alumina (Zn1-yAl2O4) is given by:
2 1
- – --- y .
x = --------------------------------------- (6.2)
1 + ( Al ⁄ Al ) 2
VI IV
The first term on the right hand side of equation 6.2, for all powders prepared via the solid state
route and coprecipitation, equals 0.04 ±0.01 and for the sol-gel method 0.23 ±0.02. Application
of the correction for the zinc aluminate prepared via the solid state route (y = 0.05) and sol-gel
method (y = 0.52) gives an inversion parameter of 0.015 and -0.01, respectively. However, a
systematic error is present in estimating the inversion parameter from MAS-NMR spectra due
to the location of some intensity of in the spinning side bands and to baseline correction. The
results obtained are within the error range concluding that MAS-NMR is not the proper method
to determine the inversion parameter for zinc aluminate.
6.5.2 Mechanical properties

The density of the sintered zinc aluminate tablets has been measured by the Archimedes’ meth-
od with water as the displaceable fluid for densities higher than 90 % and below 90 % by the
measuring the dimensions and weight of the tablet. The density as a function of the sintering
temperature is shown in figure 6.5. The density increases with sintering temperature and re-
mains constant at 93 % from 1300 °C onwards.
Sidorov found that single phase zinc aluminate powder calcined at 1250 °C did not sinter with-
out additives like TiO2 up to 1650 °C [17]. However, Hong et al. found that single phase powder
calcined at 1300 °C did sinter, but reached at 1400 °C a maximum density of 80 % [11]. In this
work, the zinc aluminate powder was calcined at 1000 °C, indicating that some zinc oxide and
aluminium oxide is still present. These latter compounds react during sintering and can contrib-
ute to an extra densification. However, since the combined densities of zinc oxide
93
Chapter 6
1 00
95
90
85
Relative density [% ]
80
75
70
65
60
55
50
12 00 13 00 14 00 15 00 16 00
Sin ter tem peratu re [ °C ]
Figure 6.5: Density as a function of sintering temperature of zinc aluminate uniaxially pre-
pressed at 70 MPa.
(5.679 g cm-3) and aluminium oxide (3.990 g cm-3) is smaller that the density of zinc aluminate
(4.611 g cm-3), this reaction will leave pores and therefore a 100% density cannot be reached.
The Young’s modulus has been measured using a pulse-echo method. The Young’s modulus as
a function of density is shown in figure 6.6. The absence of experimental data above the density
of 95 % makes it impossible to predict an accurate value for the zero porosity Young’s modulus.
However, an estimation can be made by linear extrapolation, yielding 242 GPa.

6.5.3.1 Heat capacity
The heat capacity of zinc aluminate powder has been measured using differential scanning ca-
lorimetry between 15 °C and 100 °C on zinc aluminate powder reheated up to 1400 °C for 8 h
and is shown in figure 6.7.
94
2 40
Yo ung's modu lu s [ GP a]
2 30
2 20
2 10
2 00
1 30
1 20
1 10
70 75 90 92 94 96
Rela tiv e de n sity [%]
Figure 6.6: Young’s modulus of zinc aluminate as a function of density.
150
140
C p [J mol K ]
130
-1
-1
120
110
100
280 300 320 340 360 380 400
Temperature [K]
Figure 6.7: Heat capacity at constant pressure of zinc aluminate. The step character of the
graph originates from the data acquisition during measuring.
95
Chapter 6
6.5.3.2 Thermal diffusivity

The thermal diffusivity (a) of sintered zinc aluminate ceramics has been determined using the
flash method on a tablet (1600 °C, 70 MPa) with a thickness of 1.37 mm and a density of 91 %
using the flash method [38]. The results are given in table 6.1.
Thermal conduction in ceramics predominantly takes place via lattice vibrations (i.e. phonon
conductivity). It is being determined by lattice characteristics (intrinsic properties) and defects
as impurities, grain boundaries and pores (extrinsic properties).
At sufficiently high temperature, T > ΘDr ⁄ b , where ΘD r is the reduced Debye temperature
(ΘD) and b is a constant (≈2), the inverse of the thermal diffusivity is given by:
1 bA A
--- =  -------- T +  B – --- = A′T + B′ , (6.3)
a  ΘD r  2
where A is related to the phonon-phonon scattering processes (intrinsic lattice diffusivity), B is

related to the phonon-scattering processes due to impurities, grain boundaries, etc., and ΘD r is
the reduced Debye temperature defined as ΘD ⁄ 3 n , where n is the number of atoms per primi-
tive unit cell (n = 14 for zinc aluminate) [39].
In figure 6.8 the graph of the inverse thermal diffusivity vs. absolute temperature is shown for
a zinc aluminate with a 91 % density. The slope A′ is 580.6 ± 18.1 s m-2 K-1 and B′ is
38.1 ± 7.36×103 s m-2 (R = 0.9981).
For the determination of the maximum thermal diffusivity (B = 0) [39], the intercept at the in-
verse thermal diffusivity axis (= A/2) or the intercept at the temperature axis (= ΘDr /2b) should
be known in combination with the slope A′(= bA/ ΘDr ). The estimated maximum thermal diffu-
Table 6.1: Thermal diffusivity of zinc aluminate

Temperature a Error
[K] [10 m2 s-1]
-4
[%]
296.15 0.04766 5
338.15 0.04220 5
378.15 0.03893 3
423.15 0.03550 3
469.15 0.03259 3
503.15 0.02992 3
96
3 60
3 40
3 20
3 00
a [ 10 s m ]
-2
2 80
3
2 60
-1
2 40
2 20
2 00
2 50 3 00 3 50 4 00 4 50 5 00 5 50
Tem p eratu re [K ]
Figure 6.8: Inverse thermal diffusivity vs. absolute temperature for zinc aluminate ceramics.
sivity at 300 K is 0.08318×10-4 m2 s-1, using ΘD = 896 K as calculated from the phonon spec-
trum [40] using n = 14 and b = 2.
6.5.3.3 Thermal conductivity

The thermal conductivity (κ) can be obtained by:
κ = aρC p , (6.4)
where ρ is the density [mol m-3], which is for zinc aluminate 25141.8 mol m-3, and Cp is the
heat capacity at constant pressure [J mol-1 K-1]. The thermal conductivity between 20 °C and
100 °C is shown in 6.9. The maximum achievable thermal conductivity at 300 K is about
26 W m1 K-1 as compared with the measured value of 14.7 W m-1 K-1. This large difference
can be explained by the large porosity, but such a difference is not uncommon: e.g. ~28 and
~23 W m-1 K-1 for the maximum achievable and measured thermal conductivity, respectively,
of fully dense MgSiN2 ceramics containing impurities [39].
6.5.4 Dielectric properties

Two 0.5 mm thick parallel plate capacitors have been prepared from a tablet (1400 °C,
150 MPa) with a relative density of 90 %. On these capacitors, round silver electrode areas of
12.566 mm2 have been evaporated. Since the capacitors are not made of a fully dense polycrys-
97
Chapter 6
16
Thermal conductivity [W m K ]
-1
-1
15
14
13
12
280 300 320 340 360 380 400
Temperature [K]
Figure 6.9: Thermal conductivity of zinc aluminate.
talline material, the real part of the measured dielectric constants (k′meas) is related to the real
part of the single crystal dielectric constant (k′) by:
3–ρ
k' =  ------------ k' meas , (6.5)
2ρ
where ρ is the relative density [41].
The results are shown in table 6.2. An accuracy of 10 % is reached.
The polarizability (α) is the ability of ions or atoms to deform under an externally applied elec-
tric field and consists of space-charge, dipole, ionic and electronic components. The dielectric
Table 6.2: Dielectric constants of zinc aluminate

Frequency k′meas k′
[MHz] [-] [-]
k′0 0.1 10.4 11.94
k′ 1 9.23 10.60
tan δ 0.01815
k′∞ 10 9.46 10.86
98
polarizability (αD) is, on a microscopic level, related to the experimentally determined dielec-
tric constant by the Clausius-Mosotti equation:
1 ( k′ – 1 )
α D = --- V m ------------------ , (6.6)
b ( k′ + 2 )
where b is defined as 4π/3, Vm the molar volume in Å3 and k′ is the real part of the complex
dielectric constant, which is measured between 1 kHz and 10 MHz [42-44]. The dielectric po-
larizability is in this range only composed of the ionic and electronic components, where the
electronic component itself is related to the refractive index n by the Lorenz-Lorentz equation
[45,46]:
2
1 ( n – 1 )-
α e = --- V m ------------------ . (6.7)
b 2
(n + 2)
The dipole and space-charge components are not contributing to the polarizability at these fre-
quencies. These mechanisms have a large relaxation time as compared to the frequencies used.
The dielectric polarizability of zinc aluminate calculated from k′ = 10.60 is 12.06 Å3

(Vm = 66.08 Å3). The electronic polarizability, calculated from refractive index n = 1.7725 [47]
is 6.57 Å3, giving 5.49 Å3 for the ionic polarizability.
The concept of additivity of polarizabilities is the assumption that the polarizability of a com-
plex compound is the sum of the polarizabilities of the simpler compounds. It has been applied
to both electronic and dielectric polarizabilities (see e.g. [48]). The additivity rule for oxide
compounds with the spinel structure is then given by:
α ( AB 2 O 4 ) = α ( AO ) + α ( B 2 O3 ) (6.8)
The results for the application of the oxide additivity rule to magnesium aluminate and zinc alu-
minate is given in table 6.3. The difference between the measured value and the predicted value
of the dielectric polarizability is 2.5 %. This is slightly larger than the typical values of 0.5-
1.0 % found for other aluminates, beryllates, borates, gallates, silicates and phosphates (refer-
ences in [50]), but the large experimental error should be taken into account. However, there are
several explanations for the higher estimates of the dielectric polarizability in spinels. Firstly,
the discrepancy can originate from the inaccuracy in measuring or the presence of impurities
with a high dielectric constant, like e.g. water molecules. Secondly, in analogy to magnesium
aluminate by Shannon and Rossman [50], there exists an imbalance between the "rattling" alu-
99
Chapter 6
Table 6.3: Comparison between measured and calculated dielectric polarizabilities

Compound k′ Vm αD(exp) αD(calc) ∆ Ref.
[-] [Å3] [Å3] [Å3] [%]
MgO 9.83 18.67 3.33 - - [49]
ZnO 9.30 23.55 4.13 - - [49]
Al2O3 10.12 42.45 7.63 - - [49]
MgAl2O4 8.18 65.93 11.10 10.96 +1.3 [48]
ZnAl2O4 10.60 66.08 12.06 11.76 +2.5 This work
minium cations in the octahedral interstices with a valence somewhat less than 3.0 (= 2.93 [51])
and "compressed" zinc cations in the tetrahedral interstices with a valence somewhat higher
than 2.0 (= 2.11 [51]). Finally, for completeness, Grimes [52] indicates that at low frequencies,
due to inversion of the cations, the anti-ferroelectric array of dipole moments is unbalanced in
combination with a crystallographic reorientation from Fd3m to F43m, which affects the overall
polarizability.
6.6 Conclusions
The structural, mechanical, thermophysical and dielectric properties of zinc aluminate ceramics
have been investigated. Zinc aluminate powders have been prepared at different temperatures,
with different sintering times and via different preparation routes (solid state, coprecipitation
and sol-gel). It has been revealed that zinc deficient zinc aluminate has been made, which is due
to the volatile nature of zinc oxide during calcining. Furthermore, it is established that MAS-
NMR is not the proper method for determining the inversion parameter in zinc aluminate.
Zinc aluminate ceramics have been made by sintering uniaxially prepressed tablets at tempera-
tures above 1200 °C. The maximum density of 93 % is reached at 1300 °C and remains constant
for higher sintering temperatures. The dielectric constant of zinc aluminate ceramic is 10.60 and
its polarizability is 12.06 Å3. The prediction of this value from the polarizabilities of zinc and
aluminium oxides using the oxide additivity rule gave a larger than typical difference of 2.5 %.
The thermal conductivity of zinc aluminate is determined from the measured heat capacity
(124 J mol-1 K-1) and thermal diffusivity (0.04711×10-4 m2 s-1), giving a value of
14.7 W m-1 K-1. The maximum achievable thermal conductivity for pore and impurity free zinc
aluminate ceramics can be estimated at 26 W m-1 K-1.
100
M.M.R.M Hendrix (Eindhoven University of Technology, The Netherlands) is acknowledged
for the XRD measurements, S. Tappe (RWTH Aachen University of Technology, Germany) for
the dielectric measurements, E.M. van Oers and P.C.M.M. Magusin (Eindhoven University of
Technology, The Netherlands) for the NMR experiments, B. Norder (Delft University of Tech-
nology) for the heat capacity measurements. Furthermore, M.D. Snel (Eindhoven University of
Technology) is acknowledged for the synthesis of the sol-gel zinc aluminate [53].
6.8 References
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103
Chapter 6
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104
-7-
Computational investigation of bulk and

surface properties of zinc aluminate
(ZnAl2O4)
7.1 Introduction
Zinc aluminate (ZnAl2O4, also known as gahnite or zinc spinel) is a member of the spinel family
and is being used as a catalyst and as an addition to glaze layers for floor tile and dental appli-
cations. It has the same crystallographic structure as the natural occurring mineral spinel
(MgAl2O4) having the space group Fd3m. It has a cubic structure made out of eight molecular
units (ZnAl2O4), where the 32 oxygen atoms form a fcc-lattice with 8 zinc cations located in the
tetrahedral holes and 16 aluminium cations located in the octahedral holes.
Zinc aluminate is from computational point of view a very interesting compound. The spinel
family is a model material for the ternary oxides, which have been investigated much less than
the binary oxides like MgO and Al2O3. However, the natural occurring process of inversion,
where some bivalent and trivalent cations swap positions, affects the physical properties, but is
generally not taken into account during computational investigations. The inversion process is
almost absent in zinc aluminate due to the very large positive octahedral site preference energy
of zinc cations (~+32 kJ for zinc and e.g. ~+4 kJ for magnesium) [1]. The absence of inversion
makes it possible to compare computational results directly with experimental data.
105
Chapter 7
Several properties of zinc aluminate have been studied using different computational methods:
cation distribution [2-4], structure [4,5], vibrational spectra [4], electronic structure [6], me-
chanical properties [5,7] and phonon spectra [7]. In this chapter, the surface properties of low-
index planes of zinc aluminate are studied using computational methods. Furthermore, the prop-
erties of hydrated surfaces are experimentally investigated with Diffuse Reflectance Infrared
Fourier Transform Spectroscopy (DRIFTS) and compared to previously reported surface inves-
tigations.
7.2 Experimental
Zinc aluminate powder was made via a solid state synthesis route. Equimolar amounts of zinc
oxide (from Merck) and γ-alumina (Degussa) were mixed overnight in some distilled water in
a plastic container. After evaporation of the water, the mixture was dried at 110 °C for 2 h and,
subsequently, pulverised in an agate mortar. The mixture was put in an alumina crucible with
an alumina lid and calcined in air at 1000 °C for 8 h with a heating rate of 10 °C min-1. The re-
sulting powder was determined to be single phase zinc aluminate using powder X-ray measure-
ments (Rigaku Geigerflux using CuKα1 radiation) and had, as determined by atomic adsorption
spectroscopy (AAS), a zinc deficient composition: Zn0.95Al2O4. This zinc deficiency should be
taken into account when comparing between experimental and computational results. The zinc
aluminate powder for DRIFTS measurements was put in an in-situ chamber of a SpectraTech
Collector DRIFT cell in a Nicolet Protége 460 spectrometer with a MCT detector. The pow-
der was outgassed at 450 °C for 2 h in flowing helium gas (10 ml min-1) prior to measuring the
spectrum.
7.3 Computational methods
7.3.1 Potentials
The surfaces of zinc aluminate for all possibilities along the low-index directions are investigat-
ed using the computer code Metadise [8], which is designed for simulation of dislocations, sur-
faces and interfaces. Within Metadise, the zinc aluminate crystal is considered as a cell which
is periodic in two dimensions and with the surface in the remaining third direction. The cell is
divided in two regions according to the approach of Tasker [9]: a near-surface region with a
thickness of two unit cells containing the atoms near the surface and the bulk region with a
thickness of ten unit cells containing the remainder of the atoms. The atoms in the near-surface
region are allowed to relax via free-energy minimisation, while the atoms in the bulk region are
fixed to the equilibrium positions.
106
Zinc aluminate (surface)
Table 7.1: Potential parameters

Ions Charges Core-shell
interaction
Core Shell [eV Å-2]
Zn +2.0
Al +3.0
O +1.0 -3.0 78.30
Ion Pair Buckingham potential
A [eV] ρ [eV] C [eV Å6]
Al-O 1725.02 0.2897 0.0
Zn-O 529.70 0.3581 0.0
O-O 22764.3 0.1490 27.88
Full valence charges and a Buckingham short-range potential were used as the electrostatic and
short-range interactions, respectively, to model the forces between the ions i and j:
qi qj r C
- + A ij exp  – -----ij- – -----ij- ,
V ij = -------- (7.1)
r  ρ ij  6
r
where qi and qj are the charges of ions i and j respectively, rij is the distance between the ions
and Aij, ρij and Cij are adjustable parameters to describe the potential. The oxygen polarizability
was included via the shell model using the potential parameters derived by Lewis and Catlow
[10]. The cut-off distance of the static-interaction between the ions employed in calculations is
13 Å. The parameters used in the simulations are shown in table 7.1.
7.3.2 Surface energy

The surface energy (γ) is defined as the difference of the energy of the atoms in the near surface
region when they are encapsulated in the bulk (Ebulk) and when they are relaxed after cleavage
of the cell (Esurf):
( Esurf – E bulk )
γ = --------------------------------
-, (7.2)
2A
where A is the area of the surface unit cell. It is required for these calculations that the unit cell
does not have a dipole perpendicular to the surface.
107
Chapter 7
Table 7.2: Experimental and calculated properties of zinc aluminate

Property Experimental This work Fang [7]a Pandey [5]b Sampath [6]c
Structural properties
a [Å] 8.086 [11] 8.167 7.998 8.21 7.91
u [-] 0.390 [11] 0.390 0.389 0.386 0.389
Elastic and mechanical properties
C11 [GPa] 354.6 316 341.8
C12 [GPa] 202.3 169 246.8
C44 [GPa] 155.5 148 150.4
Ed [GPa] 242 [13] 303 286 255
Kd [GPa] 202 [12] 253 218 278e
Gd [GPa] 117 112 94.9
νd [-] 0.29 0.28 0.34
Dielectric properties
εo [-] 11.94 [13] 8.55 11.16
ε∞ [-] 2.37 5.11
a. using first principle molecular dynamics
b. using pair-potentials with oxygen polarizability
c. using tight-binding muffin-thin orbital method
d. Calculated from elastic constants using the Voigt-Reuss-Hill average assuming an isotropic
polycrystalline material.
e. Pandey et al. determined a value of 273 GPa by minimizing the energy vs. volume.
7.4.1 Structural and bulk properties

The lattice parameter a is 8.167 Å in the equilibrium state after relaxation and the anion param-
eter u is 0.390. These data are within ~1 % of the experimental determined data of 8.086 Å and
0.390 [11]. The elastic coefficients C11, C12 and C44 are 354.6, 202.3 and 155.5 GPa respective-
ly, but, unfortunately, experimental data of single crystals is not available to verify these data.
However, the Young’s, bulk and shear modulus and the Poisson’s ratio can be calculated from
the elastic constants using the Voigt-Reuss-Hill averages assuming an isotropic polycrystalline
material. The bulk modulus is 253 GPa and the Young’s modulus is 303 GPa, which differ from
the experimental data of 202 GPa [12] and 242 GPa (estimated) [13], respectively. This large
difference is quite common for calculations using pair potentials. A better agreement with ex-
perimental data is obtained by using ab-initio methods [7]. An overview of calculated data com-
pared with experimental data is shown in table 7.2.
108
(100) (110) (111)
↑ ↑ ↑
OO OO OOO

 Al  (a)  Al  (a) O
OO OO (c)
 Al  (a)
 Zn  (b)
OO (c) O (c)

 Al  Zn  O  Al  O (b) OOO
OO
 Zn 
 Zn 
 Al  (b)
OO OO
 Al 
OO  Zn 
Figure 7.1: Schematic overview of the stacking in zinc aluminate spinel.
7.4.2 Surfaces (simulation)

The stacking of the atoms layers along the three low index directions in zinc aluminate is shown
in figure 7.1. Just three different possible cleavage planes producing two non-polar surfaces are
present along each direction and indicated by (a), (b) and (c)1. During cleavage of the a- and b-
layers two equal surfaces are created, but cleavage of the c-layer gives two different, but com-
plementary, surfaces (c1 and c2). The cleavage surface energy (γcleav) of these layers is shown
in table 7.3 together with the surface energy after relaxation (γrelax). The average of surface en-
ergy of the c1- and c2-layers should be taken for comparison with the surface energies of the
other layers.
The lowest surface energy after relaxation of all possibilities is obtained by cleaving (100)b:
1.88 J m-2. The created surface is characterised by the presence of two zinc cations on top of the
surface, which are somewhat nestled inside the oxygen layer (see figure 7.2a). Furthermore, this
b-plane is also the preferred plane for fracture/cleavage, since it has also the lowest cleavage
surface energy. The energy gain due to relaxation for this configuration is small, since the atoms
do not move in the lateral directions but only in the normal direction. This results in more con-
1. The x-plane along the (uvw) direction is denoted as (uvw)x.
109
Chapter 7
a)
b)
c)
Figure 7.2: Surfaces of a) (100)b, b) (110)a and c) (111)b. Red is oxygen, blue is zinc and green
is aluminium.
110
Table 7.3: Surface energy of zinc aluminate after cleaving and relaxation
Plane (100) (110) (111)
γcleav γrelax γcleav γrelax γcleav γrelax
-2 -2 -2 -2 -2
[J m ] [J m ] [J m ] [J m ] [J m ] [J m-2]
a 13.03 3.80 9.91 2.44 19.63 3.65
b 3.57 1.88 6.70 2.66 7.35 3.06
c1 5.21 2.08 5.58 2.91 9.48 3.10
c2 5.21 2.71 5.58 2.55 11.47 3.24
tracted upper layers as indicated by the decrease of the zinc-oxygen distance from its bulk value
of 1.97 Å to 1.75 Å in the outmost layer.
The large cleavage surface energy and large energy gain by relaxation of the (100)a can be ex-
plained by the presence of the four aluminium cations on top in the unrelaxed configuration. The
large charge density of aluminium (σ = 3.67×1020 C m-2) is not compensated by the absence of
surrounding oxygen anions making this configuration energetically very unfavourable. A large
relaxation is made by submerging the aluminium cations in the oxygen layer making this oxy-
gen layer the outmost layer. Furthermore, the zinc cations from the subsurface layers are
brought up to just below the surface or are exposed on the surface itself, which can be explained
by the relative low charge density of zinc cations (σ = 0.82×1020 C m-2) as compared to alumin-
ium cations.
The relaxed surface energies of the planes along the (110) direction are quite similar. The (110)a
(see figure 7.2b) has the lowest value, but the relaxed configuration shows again the presence
of zinc cations on the surface despite the presence of aluminium cations in the outer layer. The
only surface without zinc cations present on the surface is the (110)c1-layer, which is due to the
absence of zinc cations in the subsurface layer resulting in the highest surface energy for this
direction.
The relaxed surface energies of planes along the (111) direction resulting from the cleavage
along the (111)b (see figure 7.2c) and (111)c are the lowest and quite similar. Both layers have
zinc cations in their subsurface layer which emerge on the surface as stabilisers. Surfaces
formed by cleaving of the a-plane do not have these zinc cations in the subsurface layer and
therefore have a higher surface energy.
111
Chapter 7
Figure 7.3: Small crystals of natural gahnite with {100}, {221} and {111} facets. The width of
the image is 0.5 mm. Reprinted with permission [16].
The surface energies of cleaved surfaces of magnesium aluminate have been reported in litera-
ture [7,14,15]. The (100)b plane has also the lowest surface energy: 2.27 J m-2. This value is
larger than the value for zinc aluminate since the charge density of magnesium cations
(σ = 1.46×1020 C m-2) is larger than of zinc cations disallowing the same reduction as in zinc
aluminate. This explains also the generally observed trend of higher surface energies of magne-
sium aluminate for the same surfaces. However, the (111)b direction has in magnesium alumi-
nate a much higher surface energy than the c-planes in contrast to zinc aluminate. This is due to
the different rearrangement of the aluminium cations on the surface of magnesium and zinc alu-
minate. The surface energy of the planes along the (110) direction is similar as is observed in
zinc aluminate.
7.4.3 Surfaces (experimental)

The morphology of zinc aluminate based on the surface energy calculations is expected to be
{100} > {110} > {111}. However, large natural gahnite crystals occur primarily in an octahe-
dral shape showing the opposite morphology: {111} >> {110} >> {100} [16]. At first glance
this appears to be contradictive, but it should be taken into account that if the surface energy
determines the morphology, kinetic mechanisms during growth must be absent. The situation
where the growth is solely determined by thermodynamics is only valid for small single crystals.
Small crystals of natural gahnite with large {100} and {111} facets and (probably) small {221}
facets are shown in figure 7.3 indicating the transition from thermodynamical determined
112
A bsorbance [K ulbelka-M unk] 0.20
0.15
0.10
0.05
0.00
40 00 38 00 36 00 34 00 32 00 30 00 28 00
-1
W av enu mb er [cm ]
Figure 7.4: DRIFTS spectrum of the hydroxyl-stretching region on zinc aluminate immediately
after outgassing.
growth to kinetically determined growth1. Another possibility for the change in morphology is
adsorption of water on the surface changing the surface energy. Computer simulations of disso-
ciative adsorption of water on magnesium aluminate provides an indication for this morphology
change [17].
The hydroxyl groups on the surface of zinc aluminate powder are investigated using DRIFTS,
which is shown in figure 7.4. The spectrum, measured immediately after outgassing at 450 °C,
shows a single peak at ~3660 cm-1 of the Zn-OH vibration, whereas the peak of the Al-OH vi-
brations (~3730-3790 cm-1) is absent [18]. The spectrum is similar to earlier reported data by
Rossi et al. [19]. However, Rossi et al. had some zinc oxide contamination present in their pow-
der in contrast to the powder used indicating that this small contamination does not play a role.
A spectrum measured at room temperature immediately after cooling down showed only a sin-
gle broad peak in the hydroxyl-stretching region indicating a rapid adsorption of water on zinc
aluminate. Furthermore, it is remarkable that hydroxyl groups are solely located on top of zinc
cations and not on aluminium cations as is on e.g. magnesium aluminate [20] indicating that
zinc cations must be present at the surface.
1. It should be noted that natural crystals are almost never 100% pure compounds.
113
Chapter 7
Jacobs et al. [21] have studied the surface composition of zinc manganese aluminate
(Zn1-xMnxAl2O4; 0 < x < 1) powders synthesised by coprecipitation and a two step-calcining
process (900 °C; 1150 °C) using Low Energy Ion Scattering (LEIS), which is sensitive only to
the outmost atomic layer. They did not detect any zinc on the surfaces, which is not due to a low
sensitivity of the apparatus for zinc, since zinc in zinc oxide could easily be detected. Valenzue-
la et al. [22] confirmed this absence on their (doped) zinc aluminate powder synthesised at
800 °C via coprecipitation. They concluded from the absence of zinc cations using additional
results from MnAl2O4 and CoAl2O4 that tetrahedral sites generally do not appear on the surfac-
es of spinel oxide powders and that the surfaces consist out of octahedral interstices.
X-ray Photoelectron Spectroscopy (XPS) by Maltha et al. on the same zinc manganese alumi-
nate powders as measured by Jacobs et al. shows a reduction of ~25 % in zinc content in the
outmost ~5 atomic layers (~15 Å), which is the penetration depth of the photoelectrons for zinc
[23]. Elemental analysis of the bulk composition, which was in good agreement with the desired
composition, showed that the reduction of concentration of zinc is a near-surface phenomenon,
which was also shown by Inabe and Matsui using EPMA analysis of MnZn ferrite ceramics after
heating [24]. The reduction indicates a depletion of zinc during calcining. This is not uncommon
for reactions with zinc oxide present since zinc oxide at high temperatures has a high partial
pressure (pZn = 9×10-4 Pa at 1000 °C [25]) as compared to e.g. aluminium oxide
(pAl = 4×10-13 Pa [26]) or magnesium oxide (pMg = 4×10-8 Pa [26]) and will vaporize [27].
Since in the outmost 15 Å of zinc aluminate 12 zinc cations per unit area are located, approxi-
mately 3 must have been evaporated, which can explain the absence of zinc cations on the sur-
face. However, the absence of zinc cations due to depletion on its own does not provide
conclusive proof for the absence of tetrahedral sites on the surface.
Jacobs et al. [21] used for their interpretation a model of the spinel surfaces based on the model
from Knözinger and Ratnasamy [28]. The latter model is based on the ideal surfaces of γ-alu-
mina, which has a defect spinel structure. However, the model used shows some imperfections.
The surface structures are made by extending the bulk structure to the surface. This implies the
absence of relaxation leading to possible reconstruction. Furthermore, it does not take a differ-
ence between bi- and trivalent cations on the relaxation into account, which results in a different
surface geometry.
The two surfaces without tetrahedral sites according to Knözinger and Ratnasamy/Jacobs et al.
correspond with the cleavage of the (111)a and (110)a planes in notation used in this work. A
114
careful examination of these surfaces after relaxation, as calculated in this chapter, shows that
on both planes a hill and valley structure is present. The hills consist out of aluminium and ox-
ygen atoms with on the (110)a plane also zinc in the "interior" of the hill. On the other hand, the
valleys consist out of zinc and oxygen atoms, which is a subsurface layer that emerges on the
surface. Actually, many reconstructed surfaces show zinc cations from the subsurface layer
emerging on the surface.
The conclusion that the surfaces of zinc aluminate do not contain tetrahedral interstices is not
unequivocally founded. The primary indication was the conclusion that zinc was not detected
on the surface of zinc aluminate using LEIS. However, there are several questions to be made.
Firstly, XPS measurements indicate that ~25 % of the zinc cations in the outmost 15 Å is vola-
tilised during the heating stage in the synthesis process, most likely being those are the cations
at the surface. Secondly, DRIFTS measurements show that hydroxyl groups are exclusively lo-
cated on zinc cations. The oxygen of these hydroxyl groups can screen the underlying zinc cat-
ions from detection.
LEIS studies on surfaces made by fracturing single crystals of ZnAl2O4 in the absence of water
vapour or in vacuum should indicate whether zinc is indeed absent on the {110} and {111} sur-
faces. An absence of zinc would confirm the conclusion that tetrahedral sites are not present on
the surface. A presence of zinc would indicate that absence of zinc in the powders is due to evap-
oration of zinc oxide during synthesis or to screening of zinc by oxygen. Forced adsorption of
water by immersion of the sample in water and subsequently drying and measuring, would be
able to distinguish between the evaporation and the screening options.
7.5 Conclusions
Computer simulations of the low-index planes of zinc aluminate showed that the (100)b plane
has the lowest surface energy after relaxation: 1.88 J m-2, and will be the preferred plane for
fracture/cleavage. The lowest surface energy for the (110) and (111) directions are 2.44 and
3.06 J m-2, respectively, for (110)a and (111)b. In general, the surface energy is low when zinc
cations are on top as e.g. for (100)b, due to its much smaller charge density compared to alu-
minium cations. However, many cleavage planes contain aluminium cations on top. The surface
energy is lowered by relaxation, where the aluminium cations are embedded in the oxygen layer
and zinc cations from the subsurface layer become exposed on the surface. For instance, the
(110)a and (111)b planes have a hill and valley structure, where the hills contain the aluminium
cations and oxygen anions and the valleys consist out of zinc cations and oxygen anions.
115
Chapter 7
DRIFTS measurements have indicated that hydroxyl groups are exclusively located on the zinc
cations indicating that zinc cations must be present at the surface. However, reported LEIS
measurements indicated that zinc is not present at the surface. Therefore, using the model of
Knözinger and Ratnasamy, tetrahedral interstices are not present at the surface of spinel oxides.
On the other hand, reported XPS measurements show a deficiency of zinc in the outmost atomic
layers, which is due to evaporation during synthesis, and might explain the absence.
The computer simulations show that zinc cations are present on the surface, but not necessary
at the outmost atomic layer. This can explain the absence of zinc in the LEIS measurements.
Furthermore, the oxygen anion of the hydroxyl group can screen the zinc cation during the LEIS
measurements. However, both options show that the assumption of an absence of tetrahedral in-
terstices on the surface might not be hold resulting in a possible reconsideration of the model of
Knözinger and Ratnasamy.
C.M. Fang (Eindhoven University of Technology) is acknowledged for the many fruitful dis-
cussions about the simulations and surfaces in general and for assistance with the usage of
Metadise. B.G. Anderson (Eindhoven University of Technology) is acknowledged for the
DRIFTS measurements.
7.7 References
[1] A. Navrotsky and O.J. Kleppa, The thermodynamics of cation distributions in simple
spinels, J. Inorg. Nucl. Chem., 29 (1967), 2701-2714
[2] A.N. Cormack, G.V. Lewis, S.C. Parker and C.R.A. Catlow, On the cation distribution of
spinels, J. Phys. Chem. Solids, 49 (1988), 53-57
[3] R.W. Grimes, A.B. Anderson and A.H. Heuer, Predictions of cation distributions in
AB2O4 spinels from normalized ion energies, J. Am. Chem. Soc., 111 (1989), 1-7
[4] L.J. Alvarez, P. Bosch and M.A. Valenzuela, Molecular dynamics studies of ZnAl2O4
spinel, Catal. Lett., 22 (1993), 361-372
[5] R. Pandey, J.D. Gale, S. K. Sampath and J.M. Recio, Atomistic simulation study of spi-
nel oxides: zinc aluminate zinc gallate, J. Am. Ceram. Soc., 82 (1999), 3337-3341
[6] S.K. Sampath, D.G. Kanhere and R. Pandey, Electronic structure of spinel oxides: zinc
aluminate and zinc gallate, J. Phys.: Condens. Matter, 11 (1999), 3635-3644
[7] C.M. Fang, C-K-Loong, G.A. de Wijs and G. de With, Phonon spectrum of ZnAl2O4 spi-
nel from inelastic neutron scattering and first-principles calculations, Phys. Rev. B, 66
(2002), 144301
116
[8] G.W. Watson, E.T. Kelsey, N.H. de Leeuw, D.J. Harris and S.C. Parker, Atomistic simu-
lation of dislocations, surfaces and interfaces in MgO, J. Chem. Soc. Faraday Trans., 92
(1996), 433-438
[9] P.W. Tasker, The surface energies, surface tensions and surface structure of the alkali hal-
ide crystals, Phil. Mag. A, 39 (1979), 119-136
[10] G.V. Lewis and C.R.A. Catlow, Potential models for ionic oxides, J. Phys. C: Solid State
Phys., 18 (1985), 1149-1161
Chem. Miner., 4 (1979), 317-339
[12] S. Lucchesi, A. Della Guista and U. Russo, Cation distribution in natural Zn-aluminate
spinels, Miner. Mag., 62 (1998, 41-45
[13] N.J. van der Laag, this thesis, chapter 6
[14] M.J. Davies, S.C. Parker and G.W. Watson, Atomistic simulations of the surface struc-
ture of spinel, J. Mater. Chem., 4 (1994), 813-816
[15] C.M. Fang, S.C. Parker and G. de With, Atomistic simulation of surface energy of spinel
MgAl2O4, J. Am. Ceram. Soc., 83 (2000), 2082-2084
[16] P.J. Dunn, Franklin and Sterling Hill, New Jersey: the world’s most magnificent mineral
deposits; also (partly) available at: www.simplethinking.com/dunn/
[17] C.M. Fang, G. de With and S.C. Parker, Computer simulation of dissociative adsorption
of water on the surfaces of spinel MgAl2O4, J. Am. Ceram. Soc., 84 (2001), 1533-1558
[18] G. Busca, V. Lorenzelli, G. Ramis and R.J. Willey, Surface sites on spinel-type and
corundum-type metal oxide powders, Langmuir, 9 (1993), 1492-1499
[19] P.F. Rossi, G. Busca, V. Lorenzelli, M. Waqif, O. Saur and J.-C. Lavalley, Surface basic-
ity of mixed oxides: magnesium and zinc aluminates, Langmuir, 7 (1991), 2677-2681
[20] N.J. van der Laag, this thesis, chapter 5
[21] J.P. Jacobs, A. Maltha, J.H.G. Reintjes, J. Drimal, V. Ponec and H.H. Brongersma, The
surface of catalytically active spinels, J. Catal., 147 (1994), 294-300
[22] M.A. Valezuela, J.P. Jacobs, P. Bosch, S. Reijne, B. Zapata and H.H. Brongersma, The
influence of the preparation method on the surface structure of ZnAl2O4, Appl. Catal. A:
General, 148 (1997), 315-324
[23] A. Maltha, H.F. Kist, B. Brunet, J. Ziolkowski, H. Onishio, Y. Iwasawa and V. Ponec,
The active sites of manganese- and cobalt-containing catalysts in the selective gas phase
reduction of nitrobenzene, J. Catal., 149 (1994), 356-363
[24] H. Inaba and T. Matsui, Vaporization and diffusion of manganese-zinc ferrite, J. Sol.
State Chem., 121 (1996), 143-146
[25] K. Kodera, I. Kusunoki and S. Shimizu, Dissociation pressures of various mettalic
oxides, Bull. Chem. Soc. Jpn., 41 (1968), 1039-1045
[26] V.L.K. Lou, T.E. Mitchell and A.H. Heuer, Graphical displays of the thermodynamics of
high-temperature gas-solid reactions and their application to oxidation of metals and
evaporation of oxides, J. Am. Ceram. Soc., 68 (1985), 49-58
[27] J.A. Hedvall and R. Jagitsch, Hochtemperatursflüchtigkeit und Festdiffusion bei Pulver-
reaktionen, Z. Anorg. Allg. Chem. 262 (1950), 49-53
117
Chapter 7
[28] H. Knözinger and P. Ratnasamy, Catalytic aluminas: surface models and characterization
of surface sites, Catal. Rev.-Sci. Eng., 17 (1978), 31-69
118
-8-
Predictive calculation of intrinsic thermo-

physical properties from ab-initio phonon
density of states: a case study for oxide
ceramics
8.1 Introduction
The exact mathematical formalism of a number of thermophysical phenomena in solids is
known since the early years of the twentieth century. However, this mathematical formalism
was too complex to deal with in those times. Therefore, approximations have been made. An
example of such a relative simple approximation is the Debye model, which describes a number
of thermophysical properties with only long waves. The Debye model performs (surprisingly)
rather well for different solids and is widely used for many years.
However, the improvements in memory and speed of processors of computers in the recent dec-
ades in combination with improvements of computational methods for quantum mechanics
have it made possible to tackle the exact mathematical functions, without far-reaching simpli-
fications. The question addressed here is: are these improvements to obtain a more accurate
physical description of solids, really necessary for engineering purposes or can we still use the
simple approximation?
The thermophysical properties determined from the Debye model and the phonon density of
states calculated with a recent ab-initio computational method are compared with experimental
119
Chapter 8
a b c
→ω
→ω
→ω
ωD
Γ KX Γ L X W L → F(ω) → FD(ω)
Figure 8.1: a) Ab-initio calculated dispersion curves of magnesium aluminate along different
symmetry directions. b) Phonon density of states of magnesium aluminate determined from the
dispersion curves. c) Debye spectrum of magnesium aluminate with the Debye frequency.
data in order to investigate the necessity for practical applications of the phonon density of
states.
8.2 Theory
8.2.1 Phonons
In a crystal lattice, the atoms vibrate around their equilibrium position like a harmonic oscillator
due to thermal excitation. These lattice vibrations can be described by elastic waves with wave
vector k. Although the wave vector can have all values, those between -π/a and π/a (First
Brillouin Zone) have physical significance, where a is the lattice constant of cubic structures.
Furthermore, the atoms can vibrate in three independent directions called modes (λ), which for
high symmetry directions in a crystal structure can be separated in one longitudinal and two
transversal modes.
A phonon is the quantum of the (quantizised) energy of the lattice vibration, in analogy with the
photon of the electromagnetic energy. Each phonon state has a phonon frequency unambigu-
ously coupled to the wave vector and mode: ω(k,λ). By determining the number of phonon
states in the interval [ω,ω+∆ω] the phonon density of states (F(ω)) is obtained, see figure 8.1.
By defining the normalisation of F(ω) as
120
Thermophysical properties of oxide ceramics
ω max
∫ F ( ω ) dω = 3 , (8.1)
0
the phonon density of states can be obtained from the dispersion relations ω(k,λ) as:
V 3
F ( ω ) = ----------------3- ∑ ∫ δ( ω ( k, λ ) – ω ) d k , (8.2)
n ( 2π ) λ
where V is the crystal volume, n is the number of atoms in the unit cell and δ(x) is the Dirac
delta-function. For low frequencies the density of states can be described by:
2 4
F(ω) = [ a 1 ω + a 2 ω + … ] . (8.3)
The phonon density of states can be obtained from experiment or from ab-initio computer sim-
ulations. From now on the labels k and λ are omitted.

The total value of a thermophysical property (X(T)) is the integral over all the states of the con-
tribution of each state (X(ω,T))1:
ω max
X har(T) = n ∫ X ( ω, T )F ( ω ) dω . (8.4)
0
As a result, in thermal equilibrium, the energy associated with a phonon state (X=E) is:
1 "ω
E(ω, T) = --- "ω + -------------------------------------------
-, (8.5)
2 exp ( "ω ⁄ kB T ) – 1
where the first term on the right hand side is the zero-point vibration at T = 0 K.
The expressions for the Helmholtz energy and the entropy are, respectively, given by:
A ( ω, T ) = E ( ω, T ) – TS ( ω, T ) = kB T ln ( 2 sinh ( "ω ⁄ 2kB T ) ) , and (8.6)
"ω "ω "ω

S ( ω, T ) = kB ------------ coth  ------------ – ln  2 sinh  ------------  . (8.7)
2kB T 2kB T 2kB T
Since only strictly harmonic vibrations are used, the heat capacities at constant pressure (Cp)
and at constant volume (Cv) are equal (= C). The contribution of a single phonon state to the
heat capacity is:
1. The temperature dependence is solely incorporated in the description of the thermophysical properties,
although in principle the phonon density of states are also temperature dependent.
121
Chapter 8
"ω 2 exp ( "ω ⁄ kB T ) -

C(ω, T) = kB  -------- ------------------------------------------- . (8.8)
kB T exp ( "ω ⁄ kB T ) – 1
8.2.3 Debye model

The frequency of a phonon state in the Debye model can be rewritten to ω(k, λ) = C(k, λ) k .
In the simplest Debye-model [1] the frequency is assumed to be linear in k for all wave vectors
k and a constant value for C ( k, λ ) = CD . The maximum frequency in this model is called the
Debye frequency ( ωD ), see figure 8.1c. Applying these approximations to equation 8.2, the De-
bye density of states from 0 to the Debye frequency is given by:
9 2
F D(ω) = --------3- ω . (8.9)
ωD
In thermophysical applications it is common practice to use the Debye temperature (ΘD) as a
measure of the maximum Debye frequency, see figure 8.1c. They are related to each other via:
"ωD = kB ΘD . (8.10)
Applying equation 8.9 to equation 8.4 with equations 8.5, 8.7 and 8.8, the Debye model equiv-
alents for energy, entropy and heat capacity, respectively, are obtained:
ΘD ⁄ T
9 T 3 x
E D ( ΘD, T ) = --- nkB ΘD + 9nkB T  ------- ∫ -------------------------
- dx , (8.11)
8  ΘD exp ( x ) – 1
0
ΘD ⁄ T
T 3 x ΘD- 
S D(ΘD, T) = 3nkB 4  ------- ∫ - dx – ln  1 – exp  –
------------------------- ---------
 T  ,
(8.12)
ΘD exp ( x ) – 1 
0
ΘD ⁄ T
4
T 3 x exp ( x )-
C D(ΘD, T) = 9nkB  ------- ∫ ------------------------- dx . (8.13)
 ΘD exp ( x ) – 1
0
The "heat capacity Debye temperature" (ΘDC), "entropy Debye temperature" (ΘDS) and "zero-
point energy Debye temperature" (ΘDH) can be obtained from:
C
C har ( T ) = C D ( ΘD , T ) , (8.14)
S
S har ( T ) = S D ( ΘD , T ) and (8.15)
H
E har ( T ) = E D ( ΘD , T ) . (8.16)
The "elastic constants Debye temperature" (ΘDE) can be determined by:
122
Table 8.1: Vibrational properties described by a single parameter

Physical property Debye temperature
C
Heat capacity; low T ΘD ( T → 0 ) = ΘD ( – 3 )
S
Entropy; low T ΘD ( T → 0 ) = ΘD ( – 3 )
E
Elastic constants; any T ΘD ( T ) = ΘD ( – 3 )
H
Zero-point energy (T=0) ΘD ( T = 0 ) = ΘD ( 1 )
S
Entropy; high T ΘD ( T > ΘD ) = ΘD ( 0 )
C
Heat capacity; high T ΘD ( T > ΘD ) = ΘD ( 2 )
2 1⁄3
E "  6π nN A ρ
ΘD = -----  ----------------------- CD , (8.17)
kB  M 
where n is the number of atoms in the unit cell, NA is Avogadro’s number, ρ is the mass density,
M is the weight of a mole of the material and CD is the Debye sound velocity. The Debye sound
velocity is given for isotropic (polycrystalline) materials by:
1 1 – 2ν 3 ⁄ 2 –1 ⁄ 3
C D = C T  2
--- + --- --------------------  , (8.18)
3 3 2( 1 – ν ) 
where CT is the experimental transversal sound velocity and ν is the Poisson’s ratio. The trans-
versal sound velocity is related to the shear modulus G by C T = G ⁄ ρ.
8.2.4 Moment representation of phonon density of states

In the limit of low or high temperatures, a thermophysical property can be calculated from a cer-
tain average of F ( ω ) , a frequency moment, or its related Debye temperature moment (see
table 8.1). The n-th moment of F ( ω ) is defined as:
ω max ω max
n n n
〈ω 〉 = ∫ ω F ( ω ) dω ⁄ ∫ F ( ω ) dω = ω ( n )
0 0 . (8.19)
and for n = 0 as:
ω max ω max
ln [ ω ( 0 ) ] = ∫ ln ( ω )F ( ω ) dω ⁄ ∫ F ( ω ) dω . (8.20)
0 0
The Debye temperature is related to the frequency moment in case of a strict Debye density of
states as:
123
Chapter 8
3 1⁄n k 3 1⁄n
ω ( n ) =  ------------ ωD = ----B-  ------------ ΘD ( n ) . (8.21)
n+3 " n+3
For n = 0 and n = -3 the relation is defined as:
k
ω ( 0 ) = ----B- exp ( – 1 ⁄ 3 )ΘD ( 0 ) (8.22)
"
and
a1 " 9 1⁄3
ω ( – 3 ) = ----- → ΘD ( – 3 ) = -----  ----- . (8.23)
3 kB a 1
In a strict Debye model ΘD(n) are equal for all n. A large deviation in Debye temperatures for
different moments would indicate that the Debye model is not applicable to the compound in-
vestigated. For a more elaborate treatment of this type of theory, see the book by Grimvall [2].
8.3 Criteria for comparison

The entropy and the heat capacity can easily been obtained from the density of states for every
temperature. The values at 298.15 K and 1 atm (standard conditions) are compared to the ex-
perimental data in literature. For the calculation of the entropy and the heat capacity at standard
conditions from the Debye-model, also the Debye-temperature should be known. The Debye
temperature derived from the elastic constants at room temperature is chosen, since this temper-
ature is generally used due to the large availability of experimental data. However, it should be
noted that in general it is wrongly assumed that the Debye temperature from elastic constant is
temperature independent, despite the knowledge of the temperature dependency of the elastic
constants. The corresponding Debye temperature is shown in table 8.2.
Another way to validate the phonon density of states is to determine the Debye-temperature at
different temperatures from the calculated thermophysical properties and compare their values
with those obtained from the moments of the density of states, as shown in table 8.1.
Table 8.2: Debye temperature of elastic bulk properties
Material νa Ga CD ΘDE
[-] [GPa] [m s-1] [K]
MgO 0.175 128 6580 981
Al2O3 0.233 163 7082 1089
MgAl2O4 0.268 107 6078 903
a. from ref. [3]
124
8.4 Computer simulation

The phonon spectra of MgO [4], Al2O3 [5], MgAl2O4 [6] and ZnAl2O4 [7] have been reported
in literature. These phonon spectra were calculated using Density Functional Theory within the
Local Density Approximation with the computer code VASP (Vienna ab-initio simulation pro-
gram) [8-11]. Subsequently, the interatomic forces were calculated using the Hellmann-Feyn-
man theorem by slightly displacing (0.01-0.05 Å) some selected atoms from their equilibrium
positions. Next, the phonon spectra, including phonon frequencies and eigenvectors along some
high-symmetry points in the First Brillouin Zone (see figure 8.1a), were obtained by straight-
forward diagonalisation of the dynamical matrix which was acquired from the force constants
of the interatomic forces. Finally, the phonon density of states was obtained by linear tetrahe-
dron integration of the phonon frequencies.
The calculated infrared- and Raman frequencies at the Γ-point in these phonon spectra are in
excellent agreement with experimental data in literature [4-7]. Recently, Fang et al. also per-
formed neutron inelastic scattering experiments for ZnAl2O4, where the measured generalised
phonon density of states exhibits a gapless spectrum agreeing with the theoretical calculations
[7].
8.5.1 Density of states

The phonon density of states of the investigated materials are shown in figure 8.2. The density
of states of all the materials does not show any band gap. Furthermore, the width of the density
of states is approximately the same for aluminium oxide, magnesium aluminate and zinc alumi-
nate. The width for magnesium oxide is smaller than of the others.
The contribution of the magnesium and zinc atoms is primarily in the low frequency range. The
contribution of the aluminium atoms is influenced by the presence these atoms, since in the alu-
minates the centre of gravity of the aluminium contribution is shifted towards higher frequen-
cies. The contribution of the oxygen atoms is in a first approximation the same in alumina and
the aluminates. In this first approximation it can be concluded the contribution of the oxygen
atoms does not depend on whether they form a bcc- or fcc-sublattice.
125
Chapter 8
a b c d
Mg/
Zn
Intensity [arb. units]
Al
Total
0 200 0 200 0 200 0 200

Frequency [Trad s-1]
Figure 8.2: Phonon density of states of a) MgO; b) Al2O3; c) MgAl2O4 and d) ZnAl2O4.
8.5.2 Heat capacity

The heat capacity of the investigated materials is shown in figure 8.3. All curves of the heat ca-
pacity approach in the high-temperature limit (T > ΘD) the Dulong-Petit limit of 3nR, where
R is the gas constant.
The harmonic heat capacity can be obtained from the experimentally accessible anharmonic
heat capacity at constant pressure via:
C p = ( 1 + 3αγT )C , (8.24)
where α is the linear thermal expansion coefficient, γ is the thermodynamical Grüneisen pa-
rameter and T is the temperature. The experimental heat capacities of the investigated materials
are listed in table 8.3 and are compared with the calculated values from the phonon density of
states and from the Debye model in table 8.4. The difference for the heat capacity from the den-
sity of states is within ~2 %. However, for the simple oxides large relative differences are found
for the Debye model.
126
a) 60 b) 140
120
50
Heat capacity [J mol K ]

-1
-1
100
40
-1
-1
80
30
60
20
40
10 20
0 0
0 500 1000 1500 2000 0 500 1000 1500 2000
Temperature [K] Temperature [K]
c) 200 d) 200
160 160

-1
-1
-1
-1
120 120
80 80
40 40
0 0
0 500 1000 1500 2000 0 500 1000 1500 2000
Figure 8.3: Heat capacity calculated from phonon density of states of a) MgO, b) Al2O3, c)
MgAl2O4 and d) ZnAl2O4.
Table 8.3: Heat capacity at constant volume at T = 298.15 K

Material Cp(exp)a αb γc C(exp)
-1 -1
[J mol K ] [10-6 K-1] [K T-1] [J mol-1 K-1]
MgO 37.23 11.88 1.53 36.63
Al2O3 79.76 5.60 1.27 79.26
MgAl2O4 115.88 7.02 1.28 114.96
a. from ref. [12]
b. from ref. [13]
c. from ref. [14]
Table 8.4: Heat capacity comparison at T = 298.15 K

Material C (exp) C (DOS) Difference C (Debye) Difference
[J mol-1 K-1] [J mol-1 K-1] [%] [J mol-1 K-1] [%]
MgO 36.63 36.06 -1.55 30.65 -16.3
Al2O3 79.26 78.95 -0.39 69.35 -12.5
MgAl2O4 114.96 112.49 -2.15 114.82 -0.12
127
Chapter 8
Table 8.5: Entropy at T = 298.15 K

Material S (exp)a S (DOS) Difference S (Debye) Difference
[J mol-1 K-1] [J mol-1 K-1] [%] [J mol-1 K-1] [%]
MgO 26.94 25.98 -3.5 18.15 -32.6
Al2O3 50.89 51.46 +1.1 38.51 -24.3
MgAl2O4 80.63 76.72 -4.8 73.79 -6.84
(no inversion)
MgAl2O4 80.63 82.72 +2.6 79.79 -1.09
(with inversion)
a. from ref. 15
8.5.3 Entropy
The experimentally determined entropy values are shown in table 8.5 together with the calcu-
lated values from the ab-initio phonon density of states. The difference in entropy values is
somewhat higher than the difference in heat capacity. Furthermore, a large difference is ob-
served with the calculated values from the Debye model, as in the case for the heat capacity.
The absence of configurational entropy in the simulations can explain the relative large differ-
ence for magnesium aluminate since aluminates show inversion, where divalent cations have
migrated from tetrahedral interstices to octahedral interstices and trivalent cations visa versa.
The entropy term related to this configurational contribution is given by:
x
S conf = – R x ln ( x ) + ( 1 – x ) ln ( 1 – x ) + x ln  --- + ( 2 – x ) ln  1 – --x- , (8.25)
 2  2
where R is the gas constant and x is the fraction of bivalent cations in octahedral interstices (in-
version parameter). The configurational entropy is +6.00 J mol-1 K-1 for magnesium aluminate
which has an inversion parameter of ~0.10 [16]. Adding the configurational entropy to the vi-
brational entropy from the ab-initio density of states gives 82.72 J mol-1 K-1, which decreases
the error to +2.6 %, and to the entropy from the Debye model gives 79.79 J mol-1 K-1 resulting
in an error of -1.04 %.
8.5.4 Debye temperature

The Debye temperature (ΘDC) of the materials investigated is shown in figure 8.4. The Debye
temperature of all the materials shows a substantial drop in the low temperature range
(0 - 100 K), but the Debye temperature of magnesium oxide remains relative constant from the
minimum onwards, see table 8.6. Furthermore, the increasing molar weight of the cations caus-
128
a) 1200 b) 1200
Debye temperature [K]

1000 1000
800 800
600 600
0 500 1000 1500 2000 0 500 1000 1500 2000
c) 1200 d) 1200
1000 Debye temperature [K] 1000
800 800
600 600
0 500 1000 1500 2000 0 500 1000 1500 2000
Figure 8.4: Debye temperature (ΘDC) dependence on temperature for a) MgO, b) Al2O3, c)
MgAl2O4 and d) ZnAl2O4.
Table 8.6: Debye temperature

C C C
Material Tmin ΘDmin ΘD ( 298.15 ) ΘD ( 1000 )
[K] [K] [K] [K]
MgO 114 775 786 790
Al2O3 88 883 947 970
MgAl2O4 58 816 927 951
ZnAl2O4 40 616 896 925
ing an increase of density of states at lower frequencies manifests itself in the decrease of the
temperature (Tmin) where the minimum Debye temperature is located.
The Debye temperature depends on the summation over the contributing density of states. Since
at high temperatures this integral approaches the Dulong-Petit limit for all materials, the width
of the density of states is a measure for the maximum Debye frequency and thus the Debye tem-
perature. The similar width of aluminium oxides and both the aluminates reflects in the similar
Debye temperature and the small width for magnesium oxide reflects in the relative low Debye
temperature.
129
Chapter 8
8.5.5 Moments of density of states

Several thermophysical properties in the low or high temperature limit are related to the fre-
quency moments of the density of states. The Debye temperature in these limits calculated from
the entropy, heat capacity and zero-point energy are compared to the Debye temperature equiv-
alent of the frequency moments for these properties (via equation 8.10) and are shown in table
8.7
All calculated Debye temperatures from the thermophysical properties are almost equal to the
Debye temperature from the moment of the density of states. The only exceptions are the Debye
temperatures in the low temperature limit, which are due to the numerical instabilities at low
temperatures of the calculation of the Debye temperature of the entropy and heat capacity.
8.5.6 Debye temperature from elastic constants

The Debye temperature as derived from the elastic constants is for every temperature equal to
the Debye temperature of the -3rd frequency moment of the phonon density of states and can be
calculated by equations 8.17 and 8.18. The results are shown in table 8.8.
The Debye temperature of magnesium and aluminium oxide are approximately equal to the val-
ue as obtained from the -3rd moment Debye temperature. However, the -3rd moment Debye tem-
Table 8.7: Comparison Debye temperatures from thermophysical properties and

frequency moments
ΘD MgO Al2O3 MgAl2O4 ZnAl2O4
Ca
ΘD [K] 1060 1112 1120 855
Sa
ΘD [K] 1032 1068 1081 817
ΘD ( – 3 ) [K] 984 1058 1170 885
S
ΘD [K] 785 935 899 831
ΘD ( 0 ) [K] 784 932 902 833
C
ΘD [K] 789 970 952 927
ΘD ( 2 ) [K] 792 973 955 929
Evibb [kJ mol ] -1
14.70 44.40 60.83 58.22
H
ΘD [K] 786 950 930 890
ΘD ( 1 ) [K] 786 952 929 889
a. determined at 12 K
b. at 0 K
130
Table 8.8: Debye temperature of elastic constants

E
Material ΘD ΘD ( – 3 )
[K] [K]
MgO 981 984
Al2O3 1089 1058
MgAl2O4 903 1170
ZnAl2O4 760 885
perature of the aluminates is different from the experimental observed value. This possibly can
be explained by the absence of inversion in the simulations, giving an incorrect acoustic part of
the phonon density of states.
8.6 Conclusions
The experimental values of several thermophysical properties of several oxide ceramics are
compared with the results of two theoretical models: an ab-initio phonon density of states from
density functional theory calculations using local density approximation and the Debye model.
However, the calculations do not include (structural) disorder, like e.g. the inversion in alumi-
nates, which possibly results in an improper description of the acoustic part of the density of
states leading to an improper prediction of the Debye temperature from elastic constants. On the
other hand, the absence of inversion in the calculation of entropy can easily be solved by adding
a configurational term.
The ab-initio phonon density of states gives much more accurate results for heat capacity and
entropy than the Debye model using the experimentally observed Debye temperature from elas-
tic constants. The typical error from phonon density of states is ~1-4 % whilst the typical error
from the Debye model is larger than 10 % for simple oxides. Moreover, the phonon density of
states predicts also correctly the behaviour of the thermophysical properties in the low and high
temperature limit. Therefore, the usage of the ab-initio phonon density of states should be pre-
ferred over the usage of the Debye model.
C.M. Fang (Eindhoven University of Technology) is acknowledged for the many fruitful dis-
cussions about phonon spectra and the underlying theory.
131
Chapter 8
8.8 References
[1] P. Debye, Theory of specific heats, Ann. Physik, 39 (1913), 789-839
[2] G. Grimvall, Thermophysical properties of materials, 1st Ed, North Holland, Amster-
dam, The Netherlands, (1986)
[3] D.J. Green, An introduction to the mechanical properties of ceramics, 1st Ed., Cam-
bridge University Press, Cambridge, UK, (1998), 25
[4] G.A. de Wijs and C.M. Fang, unpublished results
[5] R. Heid, D. Strauch and K.-P. Bohnen, Ab-initio lattice dynamics of sapphire, Phys. Rev.
B, 63 (2000), 8625-8627
[6] G.A. de Wijs, C.M. Fang, G. Kresse and G. de With, First-principles calculation of the
phonon spectrum of MgAl2O4 spinel, Phys. Rev. B, 65 (2002), 094305/1-5
[7] C.M. Fang, C-K. Loong, G.A. de Wijs and G. de With, Phonon spectrum of ZnAl2O4
spinel from inelastic neutron scattering and first-principles calculations, Phys. Rev. B, 66
(2002), 144301
[8] G. Kresse and J. Hafner, Ab-initio molecular dynamics of liquids, Phys. Rev. B, 47
(1993), 558-561
[9] G.Kresse and J. Hafner, Ab-initio molecular-dynamics simulation of the liquid-metal-
amorphous-semiconductor transition in germanium, Phys. Rev. B, 49 (1994), 14251-
14269
[10] G. Kresse and J. Furthmueller, Efficiency of ab-initio total energy calculations of metals
and semiconductors using a plane-wave basis set, Comput. Mater. Sci., 6 (1996), 15-50
[11] G. Kresse and J. Furthmueller, Efficient iterative schemes for ab-initio total energy cal-
culations using a plane-wave basis set, Phys. Rev. B, 54 (1996), 11169-11186
[12] Y.S. Touloukain and E.H. Bayco, in: Thermophysical properties of matter, Volume 5:
Specific heat of nonmetallic solids, New York, USA, (1977)
[13] Y.S. Touloukain, R.K. Kirby, R.E. Taylor and T.Y.R. Lee, in: Thermophysical properties
of matter, Volume 13: Thermal expansion of nonmetallic solids, New York, USA, (1977)
[14] O.L. Kuskov and V.A. Kronrod, Core sizes and internal structure of Earth’s and Jupiter’s
satellites, Icarus, 151 (2001), 204-227
[15] CRC Handbook of Chemistry and Physics: 1’st student edition, R.C. West (Ed), CRC
Press, Boca Raton, Fl, USA, (1988)
Chem. Minerals, 4 (1979), 317-339
132
-9-
Epilogue: overview, conclusions & future

work
9.1 Introduction
The primary aim at the start of this Ph.D. research was to understand the influence of water ad-
sorption on the fracture process and further assess the theory derived by Donners et al. [1] for
MnZn ferrites. Therefore, a three step approach was pursued. Firstly, investigative experiments
were performed on several oxide ceramics to determine whether the influence of adsorption was
not limited to hexaferrite and MnZn ferrites only. Secondly, magnesium aluminate (spinel) was
chosen as a model material to investigate in more detail the influence of adsorption using sur-
face analysis techniques, since the cation stoichiometry in MnZn ferrites is rather complex
(Mn2+Fe2+Zn2+, Mn3+Fe3+O4) and both polycrystalline ceramics and single crystals are avail-
able. However, inversion -the process where magnesium and aluminium cations swap tetrahe-
dral and octahedral interstices- is still present in magnesium aluminate, possibly disrupting a
clear interpretation. Therefore, zinc aluminate ceramics were manufactured, since zinc alumi-
nate does not show inversion.
Finally, computer simulations of fracture surfaces were performed for magnesium aluminate
and zinc aluminate. The results were compared to the experimental data. Furthermore, within
the framework of expanding the process zone to meso-scale level, computer simulations using
density functional theory methods were used to obtain the phonon spectra. The thermophysical
133
Chapter 9
properties were calculated from these phonon spectra and compared to those obtained via the
Debye model and experimental data.
9.2 Overview and conclusions
9.2.1 Fracture and adsorption

The (apparent) fracture toughness as a function of the stressing rate and humidity was measured
for several materials revealing two groups. Type I materials (alumina, translucent alumina,
PZT, zirconia and floor tiles) are characterised by a sharp decrease in fracture toughness be-
tween 0 and ~10 % relative humidity and constant fracture toughness from 20 % onwards. Type
II materials (MnZn ferrites, calcium hydroxyapatite and magnesium aluminate) are character-
ised by the absence of a sharp initial decrease and have a more smooth decrease of fracture
toughness over the complete range of relative humidity. Accordingly, Type II materials have to
be treated with care, since documented fracture toughness values in literature are dependent on
the applied humidity during measuring, which is not the case for Type I materials.
The exact reason for this distinction is still unclear, but some conclusions can be drawn from
comparisons of structural, microstructural and fracture aspects.
Structural aspects:
• The crystal structure is not an explanation since both calcium hydroxyapatite and alumina
have a hexagonal structure and PZT and MnZn ferrites a cubic structure.
• The presence of cations in different oxidation states as e.g. Mn2+ and Mn3+ in MnZn ferrites
can also be excluded as an explanation, since for example, magnesium and aluminium in
magnesium aluminate do not have several oxidation states.
• Charge displacement might play a role as it is occurring in all Type II materials as e.g.
inversion in spinels, but not in Type I materials. Therefore, the adsorbated hydroxyl groups
can relax the structure of Type II materials more than of Type I materials. A further investi-
gation into this matter is required, where also the nature of the bonds (ionic-covalent char-
acter ratio) should be taken into account.
Microstructural and fracture aspects:
• Pores have an influence on the adsorption during fracture as porous magnesium aluminate
ceramics shows Type I behaviour and dense Type II behaviour. This can partly be explained
134
Epilogue
by the reduction of fracture surface. Additionally, the instantaneous progression of the

crack front might deny the adsorption to contribute.
• The difference in behaviour between dense and porous magnesium aluminate might also be
partly explained by the different grain sizes requiring further research.
• The fracture mode seems not to play an important role. Both PZT and Mg-PSZ show a Type
I behaviour, but have an intergranular and transgranular fracture mode, respectively.
Most ceramic materials investigated were (commercially) obtained except for calcium hy-
droxyapatite and zinc aluminate ceramics. Unfortunately, fully dense zinc aluminate ceramic
could not be manufactured due to processing imperfections, which could be solved in future
work. Although several (thermophysical) properties of zinc aluminate ceramics could be meas-
ured, measuring the influence of adsorption on the fracture toughness was not possible due to
the large porosity.
9.2.2 Surface and computer modelling

Single crystals of magnesium aluminate have been broken at low humidity and in air along the
(100) and (111) planes. The fracture toughness of these single crystals were smaller than the
polycrystalline specimens and those in air were lower than those at low humidity. The fracture
surfaces of these single crystals were investigated using Low Energy Ion Scattering (LEIS) in
order to determine the composition.
Different surface compositions for (100) fracture surfaces were predicted by computer model-
ling. The most likely fracture surface composition would contain magnesium cations, while an-
other fracture surface composition would contain aluminium cations. LEIS measurements
indicated a surface composition with both cations present with an Al/Mg ratio of ~1.0-1.5. This
could partially be explained by the inversion process, which is not taken into account in simu-
lations. Furthermore, the composition did not alter much when fractured in air or at very low
humidities.
Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) measurements in the

hydroxyl stretching region on magnesium aluminate powder could not distinguish whether hy-
droxyl groups are solely located on aluminium, on magnesium or on both making an atomistic
description of adsorption during fracture more difficult. However, DRIFTS measurements on
zinc aluminate revealed that hydroxyl groups are solely located on zinc cations and on cobalt
aluminate solely on the alumina cations [2]. Computer modelling should point out whether this
135
Chapter 9
preference will have also an effect on the preferred fracture surface, which could then be more
easily detected by LEIS studies on fracture surfaces of these single crystals. Although, a com-
putational study to the fracture surfaces of zinc aluminate was conducted, hydration studies of
these surfaces were not possible due to lack of good potentials (garbage in = garbage out). Fi-
nally, the computer modelling of fracture surfaces should be extended to other than low-index
planes, since these do occur often.
As fracture is often treated on either an atomistic level or on a continuum level, a number of

phenomena, as e.g. microstructure, are generally not taken into account. Therefore, the process-
zone must be scaled up from an atomistic level to a meso-level requiring, among others, ther-
mophysical properties to be taken into account. As a first attempt, a comparison was made be-
tween thermophysical properties determined from phonon spectra calculated using density
functional theory methods, from the Debye model and experimental data. It is found that the
phonon spectra gave much better predictions (~1-4 % deviation) than the Debye model (~10 %
deviation).
9.3 Thoughts for future work

Two questions considering the role of adsorption on the fracture process have not been ad-
dressed in this thesis, but are to be answered to fully understand the effects of adsorption. What
is the influence of adsorption on the fracture toughness relative to other toughening mechanisms
and how is adsorption involved in the process zone mechanisms, since adsorption operates in
the wake of the advancing crack?
9.3.1 Toughening
It is assumed that the intrinsic work of fracture R is solely dependent on the surface energy,
when applied under same experimental conditions (i.e. same temperature, same loading rate,
etc.) However, many materials show so-called R-curve behaviour, where the fracture toughness,
and thus the intrinsic work of fracture, is increasing with the advancing crack. Several explana-
tions for this effect have been given:
• Bridging effects (occurring in e.g. alumina [3]) caused by crack-border interaction in the
wake of the advancing crack. These bridging effects can be subdivided in intact bridges
(e.g. unbroken fibres or whiskers) and interlocking bridges (e.g. broken grains, but remain
wedged), which restrain crack opening, and frictionally sliding bridges, which transfer fric-
tion stresses.
136
Epilogue
• Stress-induced phase transformation, as in e.g. zirconia [4].

• Domain switching in piezoelectric materials as e.g. PZT [5].
• Microcracking or crack branching generating more surfaces with increasing crack length
increasing the resistance to fracture.
A more elaborate overview is given in e.g. [6].
It is surprising to see that the Type I materials investigated show an R-curve behaviour. An ex-
planation for this coincidence might be that several processes prevent adsorption to happen suf-
ficient near the crack tip. For example, interlocking grains can block the transport towards the
crack tip. The remaining question whether the Type II materials do not show an R-curve behav-
iour needs to be answered. Therefore, further (theoretical) research is required into this subject.
Especially, since it is shown that bridging stresses influence the subcritical crack growth in alu-
mina and can even arrest advancing cracks [7].
9.3.2 Wake field

Adsorption is a process which takes place in the wake of the advancing crack implying the ex-
istence of some kind of connection between the process zone around the crack tip and the ad-
sorption site. However, the nature of this connection is unknown. Therefore, some fundamental
theoretical research must be performed to understand the energetic balancing inside the process
zone in relation to the released energy due to adsorption near the crack tip. This includes also
an investigation to the size of the process zone and to distance of the adsorption site to the crack
tip in order to determine when adsorption will contribute to the decrease of the fracture tough-
ness.
Not only the process zone processes are of importance, but also the transport of gaseous mole-
cules to the adsorption sites, since this will influence the adsorption. Although it is assumed that
adsorption will take place in the same way as on powders, this is not the case inside a crack due
to the presence of an opposite surface in very close proximity. The effect of these two near sur-
faces on the transport of gaseous molecules towards the crack tip/process zone is up for a fun-
damental (computational) research. However, not only perfect surfaces should then be
considered, but also rough surfaces and grain boundaries.
Future work should point out the relevance of both the energetic balancing and the transport of
gaseous molecules and their respective contributions to the process zone.
137
Chapter 9
9.4 References
[2] G. Busca, V. Lorenzelli and V. Bolis, Preparation, bulk characterisation and surface
chemistry of high-surface-area cobalt aluminate, Mater. Chem. Phys., 31 (1992), 221-
228
[3] L. Llorca and R.W. Steinbrech, Fracture of alumina: an experimental and numerical
study, J. Mater. Sci., 26 (1991), 6383-6390
[4] A.H. Heuer, Transformation toughening in ZrO2-containing ceramics, J. Am. Ceram.
Soc., 70 (1987), 689-698
[5] S. Baik and S.M. Lee, R-curve behaviour of PZT ceramics near the morphotropic phase
boundary, J. Mater. Sci., 29 (1994), 6115-6122
[6] D. Munz and T. Fett, Ceramics, Mechanical properties, Failure behaviour, materials
selection, Springer-Verlag, Berlin, Germany, (1999), chapter 4
[7] T. Fett and D. Munz, Influence of bridging interactions on the lifetime behaviour of
coarse-grained Al2O3, J. Eur. Ceram. Soc., 12 (1993), 131-138
138
Summary
The chemical environment plays an important role in the fracture process of many materials and
in particular of inorganic materials. Water molecules from the environment can enter a crack
through diffusion and, when a load is applied, can react with the stretched bonds near the crack
tip. Subsequently, a transition complex is formed lowering the activation energy for the break-
ing of the bond. This kinetic mechanism results in so-called subcritical crack growth limiting
the time-to-failure of a ceramic component. However, since new surfaces are created during
fracture, the surface energy - an opposing force to fracture - increases. Adsorption of water mol-
ecules on the newly created surfaces lowers the surface energy, rendering crack growth again
depending on relative humidity. The question is raised whether the adsorption mechanism has
a significant contribution to subcritical crack growth like the kinetic mechanism.
The first approach to answer this question was to obtain an overview of the fracture behaviour
of several oxide ceramics. Commercially applied oxide ceramics such as e.g. (translucent) alu-
mina, PZT, zirconia and spinel, were subjected to Single Edge Notched Beam (SENB) meas-
urements at different loading rates and different relative humidities. Two distinctive types of
behaviour were found: Type I materials showing a rapid decrease in fracture toughness with in-
creasing humidity between 0 and 10 %, but remaining constant at higher humidities than 10 %
(aluminas, PZT, zirconia) and Type II materials showing a continuous decrease of the fracture
toughness over the whole range of humidities (spinel, calcium hydroxyapatite). The materials
showing the latter property have to be treated with care, since the fracture toughness data report-
ed in literature depend on the relative humidity.
The second approach was to understand the atomistic origin of the distinction between Type I
and Type II materials by studying a model material. The ternary oxide spinel (MgAl2O4, mag-
139
Summary
nesium aluminate) was chosen, since its constituent magnesia does not show subcritical crack
growth, but alumina does and both polycrystalline ceramics and single crystals were available.
Firstly, the emphasis was laid on the fracture process itself. Fracture experiments on polycrys-
talline materials with different densities revealed Type II behaviour. Electron Backscattering
Diffraction (EBSD) measurements on a polycrystalline sample with a crack induced by inden-
tations did not reveal a preferred plane for fracture. Therefore, single crystal samples were frac-
tured at different orientations and humidities showing subcritical crack growth. This implies
that the effect of water on the fracture could be studied on the fracture surfaces of these crystals.
Subsequently, the focus was directed to the atomistic aspects of fracture. The composition of
(100) fracture surfaces was studied using Low Energy Ion Scattering (LEIS) revealing both
magnesium and aluminium cations present on the surface. This is rather surprising, since com-
puter simulations have predicted that a surface with only magnesium cations on top is the most
stable surface. However, the presence of aluminium cations on top can partially be explained by
the occurrence of the inversion process, where divalent (magnesium) cations in tetrahedral in-
terstices swap lattice positions with trivalent (aluminium) cations in octahedral interstices,
which could not be taken into account during simulations. Diffuse Reflectance Infrared Fourier
Transform Spectroscopy (DRIFTS) measurements of hydroxyl groups on the surface of pow-
ders indeed confirmed the presence of aluminium cations on the tetrahedral interstices. Howev-
er, the DRIFTS measurements could not provide information whether the adsorption took place
solely on aluminium cations, solely on magnesium cations or on both. The inversion prevented
a clear atomistic interpretation.
In order to avoid inversion complicating a clear interpretation, focus was laid on zinc aluminate
spinel (ZnAl2O4) ceramics. First, the possible influence of the synthesis route (solid state, co-
precipitation and sol-gel) of the zinc aluminate powders on the inversion was investigated using
27
Al MAS-NMR. Only a small amount of inversion was present, in comparison with magnesi-
um aluminate, with the solid state and coprecipitation route and a considerable amount with the
sol-gel route. The latter could be explained by a lack of zinc, as determined by Atomic Absorp-
tion Spectroscopy (AAS), due to the evaporation of zinc oxide during firing. Second, zinc alu-
minate ceramics were made using powder from the solid state route. Unfortunately, processing
problems prevented the synthesis of fully dense ceramics required for fracture experiments.
However, several (thermo)physical/mechanical properties were determined, which were com-
pared to results of computational simulations and those reported in literature.
140
Summary
Although fracture experiments could not be performed, computational simulations of fracture

surfaces indicated that a (100) fracture surface with zinc cations on top would be the most stable.
Furthermore, DRIFTS measurements on zinc aluminate powder showed that hydroxyl groups
are only present on zinc cations. This all indicates that zinc aluminate would be an ideal material
to investigate in future studies.
Finally, since adsorption takes place in the wake of the advancing crack, a mechanism of ther-
mophysical interactions must be present inside the process zone. In a first attempt, two theoret-
ical models describing these interactions are compared. It is found that thermophysical
properties calculated from phonon spectra from Density Functional Theory (DFT) simulations
are more accurate than those calculated from the Debye model using experimental (mechanical)
data when compared to experimental thermophysical data. The main discrepancy of the Debye
model is mainly due to the incorrect description of the distribution of the lattice vibrations re-
sulting clearly in a wrong description.
The adsorption mechanism has a large influence on the fracture properties of some materials,
but the exact origin of this influence is still unrevealed. However, several causes such as e.g.
fracture mode, crystal structure and oxidation state of the cations can be ruled out as possible
explanations. The results from the experiments indicate that local charge disturbances in the lat-
tice, e.g. due to inversion, might play an important role, which could be further investigated with
zinc aluminate. Furthermore, the knowledge of the exact (thermophysical) interactions between
adsorption site and the process zone should be extended.
141
Summary
142
Samenvatting
De chemische omgeving speelt een belangrijke rol in het breukproces van materialen en in het
bijzonder van anorganische keramische materialen. Het is bekend dat watermoleculen uit de
omgeving in de scheur naar de scheurtip kunnen diffunderen. Als het voorwerp waarin de
scheur zit ook nog eens belast wordt, dan kunnen deze watermoleculen reageren met de opge-
rekte bindingen aan de scheurtip. Zij vormen daarmee een transitie-complex, dat de activering-
senergie voor het breken van de verbinding verlaagt. Dit kinetische proces noemt men langzame
of subkritische scheurgroei en resulteert in een verkorte levensduur van de keramische compo-
nent.
Er speelt echter ook nog een ander mechanisme een rol. Bij het breken ontstaan nieuwe opper-
vlakken, waardoor de oppervlakte-energie zal toenemen. Deze toename kan verminderd worden
door adsorptie van watermoleculen, waardoor het oppervlak relaxeert. Aangezien een hoge op-
pervlakte-energie het breukproces tegenwerkt, resulteert een verlaging van deze energie door
adsorptie in een versnelling van het breukproces door subkritische scheurgroei, welke afhanke-
lijk is van de vochtigheid. De vraag is nu of het adsorptiemechanisme, naast het kinetische me-
chanisme, een significante bijdrage levert aan de totale subkritische scheurgroeisnelheid.
In eerste instantie is gekeken naar het breukgedrag van verscheidene oxidische keramische ma-
terialen. Deze commercieel toegepaste materialen, zoals alumina, PZT, zirconia en spinel, wer-
den onderworpen aan SENB experimenten bij verschillende belastingssnelheden en
vochtigheden. Twee verschillende typen breukgedrag werden gevonden: Type I materialen,
waarbij de breuktaaiheid tussen 0 en 10 % relatieve vochtigheid drastisch afnam, maar bij ho-
gere vochtigheden constant bleef (alumina’s, PZT, zirconia) en Type II materialen, waarbij de
breuktaaiheid over de gehele vochtigheidsrange bleef dalen (spinel, calcium hydroxyapatiet).
143
Samenvatting
Bij Type I materialen is de rol van adsorptie net name aanwezig voor relatieve vochtigheden
lager dan 10 %, maar bij Type II materialen speelt adsorptie een duidelijke rol bij alle vochtig-
heden. Deze laatste materialen moeten dan ook met een zekere voorzichtigheid worden behan-
deld, omdat de breuktaaiheidwaarden in de literatuur afhankelijk zijn van de relatieve
vochtigheid tijdens de meting.
In tweede instantie is op atomaire schaal gekeken naar de oorsprong van het verschil tussen
Type I en Type II materialen d.m.v. de bestudering van een modelmateriaal. Hiervoor is het ter-
nair oxidische spinel (MgAl2O4, magnesium aluminaat) gekozen, vanwege het feit dat een van
zijn bestandsdelen (magnesia) geen subkritische scheurgroei vertoont, maar het andere (alumi-
na) wel en dat zowel polykristallijn keramiek als éénkristallen verkrijgbaar zijn. Als eerste werd
gekeken naar het breukproces zelf. Breukexperimenten op twee soorten materiaal met verschil-
lende dichtheden toonde Type II gedrag aan. Electron Backscattering Diffraction (EBSD) me-
tingen op een polykristallijn proefstukje waarin een scheur gemaakt was m.b.v. indentaties
toonden aan dat er geen voorkeursorientatie was voor het breukvlak. Daarom werden éénkris-
tallen gebroken langs verscheidene kristallografische vlakken bij verschillende vochtigheden.
Hierbij vond subkritische scheurgroei plaats, wat inhield dat de rol van adsorptie bestudeerd kon
worden met de breukvlakken van deze éénkristallen.
Vervolgens werd gekeken naar de atomaire aspecten van het breukproces. De compositie van
(100)-breukvlakken werd bestudeerd d.m.v. Low Energy Ion Scattering (LEIS). Dit breukop-
pervlak bestond naast zuurstof zowel uit magnesium- als aluminiumkationen. Dit was enigzins
verrassend, omdat computersimulaties voorspelden dat een breukoppervlak met alleen magne-
siumkationen het meest stabiele breukoppervlak zou zijn. Echter, de aanwezigheid van alumi-
niumkationen kan gedeeltelijk verklaard worden door het in materialen met een spinelstructuur
vaak voorkomende proces van inversie, welke niet in computersimulaties meegenomen wordt.
Bij inversie verwisselen de bivalente (magnesium) en trivalente (aluminium) kationen onder-
ling hun respectievelijke tetraedrische en octaedrische omgeving. Diffuse Reflectance Infrared
Fourier Transform Spectroscopy (DRIFTS) metingen aan hydroxylgroepen op het oppervlak
van spinelpoeder bevestigden de aanwezigheid van aluminiumkationen in een tetraedrische om-
geving. De DRIFTS metingen konden echter geen uitsluitsel verschaffen, waar de adsorptie
exact plaatsvindt: alleen op de aluminiumkationen, alleen op de magnesiumkationen of op alle-
bei. De inversie voorkomt een eenduidige atomaire interpretatie.
144
Samenvatting
Derhalve is de aandacht gericht op zink aluminaat spinel (ZnAl2O4), waarbij geen inversie werd
verwacht. Als eerste is de mogelijke invloed van het poedersyntheseproces (vastestofreactie,
coprecipitatie en sol-gel) op de inversie onderzocht m.b.v. 27Al MAS-NMR. Slechts een kleine
mate van inversie (in vergelijking met magnesium aluminaat) was aanwezig in de poeders ge-
synthetiseerd via de vastestofreactie en de coprecipitatie route, maar een grote mate van inversie
in het sol-gel gesynthetiseerde poeder. Dit laatste is echter veroorzaakt door een tekort aan zink,
zoals vastgesteld met Atomic Adsorption Spectroscopy (AAS) t.g.v. verdamping van zinkoxide
tijdens het verhitten. Vervolgens werd polykristallijn zink aluminaat keramiek gemaakt van het
poeder gesynthetiseerd d.m.v. de vastestofreactie. Helaas, zorgden processingproblemen ervoor
dat een zeer dicht materiaal niet maakbaar was, wat wel noodzakelijk is voor breukexperimen-
ten. Met het gemaakte materiaal zijn enkele (thermo)fysische eigenschappen bepaald, welke
vergeleken zijn met voorspellingen van computersimulaties.
Hoewel er geen breukexperimenten gedaan konden worden, zijn de breukoppervlakken van

zink aluminaat gesimuleerd. Deze simulaties toonden aan dat het (100)-breukvlak met een ter-
minatie van zinkkationen het meest stabiele is. Verder toonden DRIFTS metingen op zink alu-
minaat poeder aan dat er inderdaad zinkkationen aan het oppervlak zitten en bovendien de
hydroxylgroepen uitsluitend hier op aanwezig zijn. Dit alles toont aan dat zink aluminaat een
ideale kandidaat is voor verdere bestudering.
Tenslotte, omdat adsorptie plaatsvindt achter de scheurtip moet er een mechanisme zijn van
thermofysische interacties in de proceszone. Als een eerste poging zijn twee theoretische mo-
dellen vergeleken die deze interacties beschrijven. Het blijkt dat de thermofysische eigenschap-
pen berekend uit phonon spectra verkregen uit Density Functional Theory (DFT)-simulaties
nauwkeuriger zijn dan de eigenschappen berekend via het Debye model vergeleken met expe-
rimentele thermofysische data.
Het adsorptiemechanisme heeft voor enkele materialen een grote invloed op de breukeigen-
schappen, maar de exacte reden is (nog steeds) onbekend. Enkele oorzaken, zoals trans- of in-
tergranulaire breukwijze, kristalstructuur en oxidatietoestand van de kationen, kunnen worden
uitgesloten. De experimentele resultaten doen vermoeden dat lokale ladingsverstoringen in het
rooster een grote rol spelen. Dit dient verder onderzocht te worden, zoals met zink aluminaat.
Verder dient ook de kennis over de exacte (thermofysische) interacties tussen adsorptie en mi-
crostructurele aspecten van de proceszone nader bestudeerd te worden.
145
Samenvatting
146
Samenvatting voor niet-wetenschappers
Woord vooraf
“Denkend aan een wetenschapper zie ik een suf persoon in een labjas die onbegrijpelijke war-
taal uitslaat”. Dit zou een beginregel kunnen zijn van een gedicht, maar het is een (overdreven)
voorbeeld van een beschrijving van het nerd-karakter van (natuur)wetenschappers1. Iedereen
weet wel dat het niet waar is, maar er zit wel een kern van waarheid in. Niet het suffe, maar wel
de onbegrijpelijke wartaal. Dit moet men hen echter niet zo aanrekenen, want dit is hun vakjar-
gon, zoals elk beroep dat heeft. Voeg bij dit onbegrijpelijke vakjargon ook nog het feit toe dat
vakken als natuur-, schei- en wiskunde op de middelbare school als moeilijk te boek staan, dan
heb je alle ingrediënten te pakken voor een negatief beeld van de natuurwetenschappen en de
techniek.
Dit negatieve beeld leidt tot gevaarlijke ontwikkelingen, zoals de jarenlange daling van het aan-
tal eerstejaars studenten in de technische en natuurwetenschappelijke studies. Deze studenten
zijn echter wel de uitvinders van de toekomst. De (Nederlandse) economie bestaat niet alleen
uit diensten & services, maar voor een groot deel ook uit het ontwikkelen en maken van “echte”
producten en daarbij zijn ze hard nodig. Deze daling van het aantal studenten zal op termijn ook
een grote impact hebben op de economie.
Een tweede gevaarlijke (en misschien wel de gevaarlijkste) ontwikkeling is dat met de afkeer
van de natuurwetenschappen men deze kennis ook niet tot zich neemt. Men kan nog wel lachen
als men antwoordt dat de Zon om de Aarde draait of dat er seizoenen zijn, omdat de Aarde soms
dichter bij de Zon staat en soms verder weg2. Het wordt ernstiger als men pseudo-wetenschap-
1. Chemici, wiskundigen, fysici.
147
pelijke stellingen niet meer kan doorzien en er dus maar in gaat geloven. Men moet hierbij den-
ken aan stellingen als "Er is een chemische stof ontdekt die dodelijk is bij inname en zij
verspreidt zich ook door de lucht. Dit chemische product is diwaterstofoxide. Uw regering doet
niets! Steun onze strijd financieel! Maak uw bijdrage over op rekening....3" of kretologie als
"Significant beter" of "Megaperls met microwaskracht".
Het is duidelijk dat beide groepen elkaar moeten naderen. De niet-natuurwetenschappers moe-
ten gaan begrijpen dat niet alles wat natuurwetenschappers doen per definitie gevaarlijk is en
verboden moet worden. Aan de andere kant moeten natuurwetenschappers ook hun best doen
om hetgeen wat ze doen voor iedereen begrijpbaar uit te leggen. In dit kader is hieronder een
samenvatting geschreven van dit proefschrift, waarbij de nadruk ligt op het hoe en waarom van
het onderzoek met aandacht voor de achtergrond.
Inleiding
Dit proefschrift gaat over keramische materialen4. Keramische materialen worden in het dage-
lijks leven zeer veel gebruikt, maar zijn niet altijd zichtbaar. Zo bestaat bijvoorbeeld een mo-
biele telefoon van Nokia voor 16 % uit glas/keramiek. Keramische materialen hebben naast veel
interessante eigenschappen ook enkele zwakke. Een van deze zwakke eigenschappen heeft te
maken met de mechanische eigenschappen. Zo treedt er bij veel keramische materialen het pro-
ces van subkritische scheurgroei op onder invloed van moleculen uit de omgeving. Dit proces
verzwakt in de loop der tijd het keramische materiaal, waardoor het op termijn zal breken. Voor
toepassing van keramische materialen is het van het allergrootste belang om te weten wanneer
het zal breken en dus dient subkritische scheurgroei zeer goed bestudeerd te worden.
Subkritische scheurgroei is reeds door veel wetenschappers onderzocht. De meest gegeven uit-
leg van subkritische scheurgroei is aan de hand van het kinetische mechanisme. Maar onderzoek
aan het keramische materiaal mangaanzinkferriet toonde aan dat er nog een tweede mechanisme
een rol speelt: het adsorptiemechanisme. De eerste vraag is nu of dit adsorptiemechanisme ook
bij andere keramische materialen een rol speelt. De tweede vraag is hoe dat adsorptiemechanis-
me zich op atomair niveau manifesteert. Deze twee vragen staan centraal in het proefschrift.
2. Bijna alle afgestudeerden van twee Amerikaanse top-universiteiten gaven dit antwoord op de vraag
waarom er seizoenen zijn. Dit antwoord is fout en derhalve aan de lezer de taak om wel het goede ant-
woord te vinden.
3. Flauw chemisch grapje, want het diwaterstofoxide is gewoon water.
4. Een eenduidige definitie van keramiek is zelfs voor wetenschappers niet makkelijk te maken. De beste
(wetenschappelijke) definitie van keramiek is een anorganisch niet-metallisch materiaal gevormd door
toepassing van hoge temperaturen. Een nadere uitleg volgt verderop in deze samenvatting.
148
In deze samenvatting zal op deze twee vragen worden ingegaan. Daarvoor zal eerst een beknop-
te uitleg gegeven worden over keramiek en subkritische scheurgroei dat als basis dient. Vervol-
gens wordt in drie stappen het onderzoek en de conclusies, die in dit proefschrift beschreven
staan, behandeld. Hierbij wordt getracht om vakjargon te vermijden.
Keramische materialen
Vaste materialen kunnen grofweg worden ingedeeld in drie klassen: metalen, polymeren en
keramiek, zie tabel 1. Deze verdeling is gebaseerd op de chemische samenstelling en de aard
van de onderlinge bindende krachten. De meeste materialen behoren tot een van deze klassen,
maar een tussenvorm is ook mogelijk.
Bij keramiek denkt men direct aan producten zoals porselein, kopjes, bordjes, baksteen en dak-
pannen. Deze producten zijn al duizenden jaren bekend bij de mens en daarom wordt het ook
wel traditionele keramiek genoemd. Dit keramiek wordt volgens een vaststaand procédé ge-
maakt. Allereerst wordt de grondstof, klei in het geval van het traditionele keramiek, in een mal
geperst om het een vorm te geven. Het object dat zo ontstaat heet groene keramiek. Vervolgens
gaat dit groene keramiek de oven in en wordt het gebakken, oftewel in vaktermen gesinterd,
waarbij de losse kleikorrels door de hoge temperatuur aan elkaar "gelijmd" worden, zoals weer-
gegeven in figuur 1. Hierbij kunnen nog loze ruimtes tussen de korrels overblijven, die poriën
genoemd worden. Tenslotte wordt het eindproduct soms nog wat nabewerkt, bijvoorbeeld door
slijpen of polijsten.
Het uiteindelijke product hangt af van vele variabelen in het productieproces. Zo hebben bij-
voorbeeld de korrelgrootte van de grondstoffen, de druk tijdens het persen en de oventempera-
tuur een grote invloed op het uiteindelijke resultaat. Een voorbeeld hiervan is het verschil in
kleur tussen rode en zwarte dakpannen dat ontstaat omdat in de laatste fase van het bakken er
wel of geen lucht in de oven wordt geblazen.
Tabel 1: Overzicht van materialen

Klasse Bindingstype Voorbeelden (toepassingen)
metalen metallisch goud (ringen), aluminium (blikje), staal (fietsframe)
polymeren covalent polyetheen (boterhamzakje), nylon (kousen), cellu-
lose (hout)
keramiek ionisch/cova- aluminiumsilikaten (porselein, mokken, baksteen),
lent aluminiumoxide (horlogeglas)
149
Figuur 1: Schematische weergave van het sinteren van de losse korrels tot één vast keramisch
materiaal. De overblijvende ruimtes tussen de korrels zijn poriën.
Keramische materialen hebben veel interessante eigenschappen. Zo kunnen sommige materia-

len bijvoorbeeld heel goed tegen grote temperatuursverschillen die optreden in een razend korte
tijd, waardoor ze kunnen worden gebruikt als hitteschild op de Space Shuttle. Verder kunnen ze
goede (electrische) isolatoren zijn en zijn ze in het algemeen stijf en hard, waardoor ze respec-
tievelijk minder doorbuigen en minder snel beschadigen. Helaas hebben ze ook een aantal min-
der goede mechanische eigenschappen. Allereerst breken ze op een brosse wijze5, waardoor er
geen waarschuwing vooraf is in de vorm van een verbuiging. Verder is er een relatief grote
spreiding in de belasting waaronder keramiek breekt. Tenslotte is er ook nog het subkritische
scheurgroeiproces, waarbij moleculen uit de omgeving ervoor zorgen dat een scheur kan
groeien, terwijl de kritische belasting waarbij het pas zou mogen gebeuren, nog niet bereikt is.
De combinatie van goede en zwakke eigenschappen is van wezenlijk belang voor het antwoord
op de vraag of men deze materialen daadwerkelijk kan toepassen.
In de afgelopen dertig jaar hebben wetenschappers in universitaire en industriële laboratoria on-

derzoek gedaan naar nieuwe methoden om zowel de goede als de zwakke eigenschappen van
keramiek te verbeteren. Dit werd bereikt door in plaats van klei zuivere poeders te gebruiken en
de verschillende variabelen in het productieproces, zoals de oventemperatuur, te optimaliseren.
Dit resulteerde in het zogenaamde geavanceerde of technische keramiek met sterk verbeterde
eigenschappen. Technisch keramiek is bijvoorbeeld veel sterker of is compleet doorzichtig.
Voorbeelden van toepassingen van dit technisch keramiek zijn de "natriumlampen" van de
straatverlichting (doorzichtig aluminiumoxide), de sensor die de airbag activeert (loodzircon-
aattitanaat) en de kernen van transformatoren (mangaanzinkferriet), zie figuur 2. Uit deze voor-
5. Het onderscheid tussen een brosse en een ductiele breuk kan getoond worden door het breken van een
potlood (brosse wijze) en een kauwgumpje (ductiele wijze). Een potlood zal in één klap breken, terwijl
het zijn oorspronkelijke vorm terug krijgt als men voor het breekt, stopt met belasten en een gekauwd
kauwgumpje zal eerst heel erg uit elkaar worden getrokken en vervormen voordat het breekt, maar zal
de oorspronkelijke vorm niet terugkrijgen als je in de tussentijd stopt met trekken.
150
Figuur 2: Enkele voorbeelden van toepassingen van traditioneel en technisch keramiek: een
kern van een transformator van mangaanzinkferriet (rechtsboven), een lagerring van silicium-
carbide (rechtsonder), een halogeen autolampje van siliciumdioxide en een vloertegel (onder-
op).
beelden blijkt wel dat het in de moderne samenleving belangrijke materialen zijn. Ze zijn echter
wel onttrokken aan het oog van de mensen, waardoor ze minder bekend zijn.
Subkritische scheurgroei in keramiek

Als een keramisch onderdeel breekt, dan gebeurt dat altijd op een bestaande onregelmatigheid,
zoals een scheurtje. Dit altijd aanwezige scheurtje, in vaktermen een defect, kan door verschil-
lende oorzaken ontstaan. Als men zo’n scheurtje gaat belasten, d.w.z. een kracht uitoefenen op
het onderdeel waar het in zit, dan kan zo’n scheurtje uitgroeien tot een grote scheur, wat uitein-
delijk leidt tot de breuk van het onderdeel. De belasting waaronder het onderdeel breekt, wordt
sterkte genoemd. Hoe groter de scheur, hoe lager de sterkte.
De sterkte is echter wel afhankelijk van de wijze waarop belast wordt. Trekken, buigen en op
druk belasten leveren respectievelijk de trek-, buigen compressiesterktes op. De term "een
sterk materiaal" moet dan ook met de nodige voorzichtigheid worden gebezigd, omdat meestal
slechts één enkele sterkte van de verschillende sterktes hoog is. Zo heeft cement een uitstekende
compressiesterkte, maar een uitermate geringe buigsterkte.
Bij subkritische scheurgroei wordt de scheur al groter voordat de kritische belasting bereikt is.
Dit kan beschreven worden door het kinetische mechanisme, waar watermoleculen uit de lucht
de scheur in zweven en reageren met de chemische bindingen, die nog net niet zijn gebroken.
Tijdens deze reactie breken de bindingen wel met als gevolg dat de scheur groter wordt en de
sterkte dus afneemt. De snelheid waarmee de scheur groeit, is verschillend voor verschillende
151
materialen, waardoor het uiteindelijke breken bij sommige materialen slechts een paar dagen
duurt, maar bij andere tientallen jaren. Kortom, als men wil voorspellen of een bepaald onder-
deel vandaag, morgen, over een maand, over een jaar of over tien jaar zal gaan breken, is het
dus van belang om enig inzicht te hebben in subkritische scheurgroei.
Naast het beschreven kinetische mechanisme is er echter ook nog een tweede mechanisme,
waarmee watermoleculen uit de omgeving de scheur kunnen laten groeien: het adsorptiemecha-
nisme. De watermoleculen kunnen adsorberen op het nieuwe oppervlak, wat ontstaat bij het bre-
ken, en kunnen daarmee de oppervlakte-energie verlagen. Aangezien een hoge oppervlakte-
energie de scheurgroei tegenhoudt, zal een verlaging door wateradsorptie scheurgroei bevor-
derd worden. Dit resulteert uiteindelijk in een lagere sterkte.
Onderzoek I: een overzicht

Het kinetische mechanisme komt veelvuldig voor en is door de wetenschappers geaccepteerd.
Het adsorptiemechanisme is daarentegen minder bekend en is tot voorafgaand aan dit promo-
tieonderzoek slechts alleen aangetoond voor het mangaanzinkferriet, wat een technisch kera-
misch materiaal is behorende tot het oxidische keramiek. Dit leverde de twee centrale vragen
op: Komt het adsorptiemechanisme bij elk oxidisch keramisch materiaal voor en wat is de exac-
te atomaire oorzaak van dit mechanisme?
De eerste vraag kan worden beantwoord door de breuktaaiheid6, de weerstand tot scheuren, van
een aantal verschillende oxidische technisch keramische materialen te meten bij verschillende
vochtigheden. De aanwezigheid van het adsorptiemechanisme kan namelijk worden aange-
toond door een verlaging van de breuktaaiheid met toenemende vochtigheid. In tabel 2 staan de
materialen vermeld die onderzocht zijn. Uit deze materialen, die commercieel verkrijgbaar zijn
of in het geval van calcium hydroxyapatiet zelf gemaakt zijn, zijn proefstukjes van ongeveer
3 mm breed, 4 mm hoog en 40 mm lang gemaakt. In deze zogenaamde SENB-proefstukjes is
kunstmatig een veel grotere scheur aangebracht dan dat er van nature aanwezig is om er zeker
van te zijn dat het proefstukje daar zal breken en om de zogenaamde breuktaaiheid in plaats van
de sterkte te meten. Vervolgens wordt het proefstukje in een zogenaamde vierpuntsbuigproef-
opstelling gelegd tussen vier gehard stalen rolletjes, zie figuur 3. Deze hele opstelling wordt
6. De reden om de breuktaaiheid te meten i.p.v. de sterkte is een technische en een economische. Omdat
de spreiding in de sterktemetingen veel groter is dan in de breuktaaiheidmetingen, moeten er voor een
betrouwbare sterktemeting minimaal vijfentwintig proefstukjes gebroken worden en voor de breuktaai-
heid ongeveer zes tot acht. Overigens zijn de sterkte en breuktaaiheid aan elkaar gerelateerd.
152
Tabel 2: Overzicht van onderzochte materialen

Materiaal Formule Toepassing
alumina Al2O3 lagers, kunstmatige tanden, electronisch isolerende
ondergrond
doorzichtig alu- Al2O3 lampjes, ruiten
mina
PZT Pb(Zr,Ti)O3 actuatoren, oscilatoren, sensoren
zirconia ZrO2 pantser, zwaar belastbare componenten
calcium Ca10(PO4)6(OH)2 biomateriaal, implantaat
hydroxyapatiet
spinel MgAl2O4 pantserglas, buffer materiaal in nucleaire installaties
vloertegels AlxSiyOz spreekt voor zich
weer in een tweede opstelling geplaatst, waarin de vochtigheid geregeld kan worden tijdens het
breken. Tenslotte wordt met een bepaalde snelheid de belasting (F) op de twee bovenste rollers
opgevoerd totdat het proefstukje breekt. De breuktaaiheid wordt berekend aan de hand van de
belasting bij breuk.
Alle materialen in ogenschouw genomen, zijn er twee typen van reacties te herkennen, zie fi-
guur 4. Type I materialen worden gekenmerkt door een scherpe daling in de breuktaaiheid bij
lage vochtigheden en Type II materialen worden gekenmerkt door een continu dalende breuk-
taaiheid bij alle vochtigheden. Dit betekent dat voor Type I materialen de rol van het adsorptie-
mechanisme alleen bij de lage vochtigheden een rol speelt, maar bij de hogere vochtigheden niet
meer, en voor Type II materialen speelt het adsorptiemechanisme wel degelijk een belangrijke
rol bij alle vochtigheden. Dit houdt in dat men moet oppassen met het toepassen van deze Type
II materialen, omdat de breuktaaiheid in de tropen bijvoorbeeld anders is dan in de woestijn. Ge-
Figuur 3: Zijaanzicht van een vierpuntsbuigopstelling met een SENB-proefstukjes tussen de

rollers.
153
Breuktaaiheid J
Breuktaaiheid J
80% 0%
0% Vochtigheid J Vochtigheid J 80%
Figuur 4: Typische breuktaaiheidafname bij verschillende vochtigheden voor Type I materialen

(links) en Type II materialen (rechts). De grafieken zijn niet op schaal.
lukkig zijn de meeste materialen van Type I, maar calcium hydroxyapatiet en spinel zijn, net
zoals mangaanzinkferriet, Type II materialen.
Onderzoek II: een modelmateriaal

De tweede vraag gaat over de oorzaak waarom bepaalde materialen wel of geen Type II gedrag
vertonen. Het antwoord op deze vraag is niet erg eenvoudig. Derhalve is het onderzoek gecon-
centreerd op één bepaald materiaal, dat als modelmateriaal dient om op atomair niveau nader
onderzocht te worden. Om verscheidene wetenschappelijke redenen is daarvoor het spinel
(MgAl2O4) gekozen.
Als eerste zijn natuurlijk weer de breuktaaiheidsmetingen gedaan op twee soorten spinelkera-
miek, die een verschillende dichtheid hebben. Deze experimenten toonden aan dat het dichte
spinelkeramiek Type II gedrag vertoonde en het poreuzere Type I gedrag. Bij het breken van
het spinelkeramiek ontstaat een breukvlak met vele korreltjes, waaruit het keramiek is opge-
bouwd. Er is gekeken of er een voorkeursoriëntatie van die korrels op het breukvlak aanwezig
is met behulp van een techniek genaamd Electron Backscattering Diffraction. Dit bleek niet het
geval te zijn, waardoor er voor is gekozen om twee oriëntaties, het (100)- en het (111)-breuk-
vlak, nader te bestuderen op éénkristallen. Éénkristallen zijn als het ware zeer grote, georiën-
teerde korrels met een diameter van enkele centimeters, terwijl een korrel in een keramisch
materiaal typische kleiner is dan ongeveer 20 micrometer. Uit breukexperimenten op deze één-
kristallen bleek dat het (100)-breukvlak het makkelijkst te maken is en ook nog eens het gevoe-
ligst is voor vochtigheid.
154
De vraag is nu of er aan de atomaire samenstelling van het breukvlak gezien kan worden wat
het Type II gedrag veroorzaakt. Misschien bestaat er een voorkeur voor een bepaalde plaats, dan
wel atoom, om op te adsorberen. Dit is onderzocht voor het (100)-breukvlak m.b.v. de Low
Energy Ion Scattering (LEIS) techniek7, waarmee de samenstelling van het breukvlak bepaald
kan worden. Hieruit bleek dat er naast zuurstof (O) ook veel magnesium (Mg) en aluminium
(Al) aanwezig was. Dit kwam niet geheel overeen met de voorspellingen die verkregen waren
uit computersimulaties. Zijn de computersimulaties fout of is het experiment niet goed uitge-
voerd?
De waarheid is wat gecompliceerder, want zowel de simulaties als het experiment zijn goed uit-
gevoerd. Er is bij materialen met de spinelstructuur bekend dat er een proces voorkomt met de
naam inversie. Bij inversie verwisselen de magnesium- en aluminiumatomen hun positie in het
kristalrooster. De computersimulaties voorspellen een (100)-breukvlak bestaande uit alleen
zuurstof- en magnesiumatomen, omdat in deze berekeningen inversie niet is meegenomen.
Maar in werkelijkheid kunnen een aantal van die magnesiumatomen door inversie vervangen
zijn door aluminiumatomen, wat inderdaad ook gemeten is.
De vraag is nu of het inversieproces problemen oplevert met de bepaling waar het water adsor-
beert op het oppervlak en dus een eventuele eenduidige interpretatie in de weg staat. Daarvoor
is er met een infrarood techniek (DRIFTS)8 gekeken naar de lokatie van de hydroxylgroepen
aan het oppervlak. Deze hydroxylgroepen zijn de overblijfselen van het geadsorbeerde water en
geven dus aan waar ze geadsorbeerd zijn. Het enige wat met zekerheid gezegd kan worden is
dat het water in ieder geval adsorbeert op aluminiumatomen, maar het is onduidelijk of ze ook
op magnesiumatomen adsorberen. De inversie staat dus een duidelijke interpretatie in de weg.
Onderzoek III: een nieuw modelmateriaal?

Omdat het inversieproces een duidelijke interpretatie bemoeilijkt, is er gezocht naar een mate-
riaal met dezelfde structuur als spinel, maar dat geen inversie vertoont. Dit materiaal is zink alu-
minaat (ZnAl2O4). Aangezien zink aluminaat niet een standaard keramisch materiaal is, is er
7. Met de LEIS techniek wordt het breukvlak als het ware bestookt met speciale atomen. Als deze atomen
een atoom op het breukvlak raken, verliezen ze iets van hun snelheid. Dit verlies kan gemeten worden
en is alleen afhankelijk van de massa van het atoom waarop het gebotst is. Aangezien de massa van het
atoom karakteristiek is voor dat atoom, kun je de samenstelling van het breukvlak bepalen.
8. Elke chemische binding kan trillen met een bepaalde karakteristieke frequentie. Met DRIFTS wordt
bepaald welke frequenties aanwezig zijn in het zogenaamde infrarode frequentiegebied. Aan de hand
van de gevonden frequenties kan bepaald worden welke chemische groepen, zoals hydroxylgroepen,
aan het oppervlak zitten.
155
eerst onderzoek gedaan naar de invloed van verschillende syntheseroutes van het startmateriaal
op de inversie. Het zink aluminaat keramiek is uiteindelijk gemaakt volgens de standaardme-
thode van persen en sinteren met het startmateriaal wat gemaakt is met de vastestofreactie. He-
laas is de kwaliteit van het zink aluminaat keramiek nog niet goed genoeg om er
breukexperimenten mee te doen. Dit kan in de toekomst wel gebeuren als het productieproces
geoptimaliseerd wordt.
Ondanks het feit dat er geen breukexperimenten gedaan konden worden met zink aluminaat,
zijn er wel een aantal onbekende (thermo-)fysische eigenschappen bepaald. Verder is er ook
nog met de DRIFTS-techniek gekeken naar de lokatie van de hydroxylgroepen aan het opper-
vlak. Deze hydroxylgroepen zijn alleen te vinden op zinkatomen en niet op aluminiumatomen,
in tegenstelling tot het spinel. Dit betekent dat het nu bekend is dat het water alleen adsorbeert
op de zinkatomen. Bovendien hebben computersimulaties aangetoond dat een (100)-breukvlak
met alleen zuurstof- en zinkatomen de voorkeur geniet. Dit alles maakt een toekomstige inter-
pretatie gemakkelijker.
Conclusies
Het adsorptiemechanisme speelt een rol tijdens het breukproces van het oxidische keramiek. Er
zijn echter twee soorten gedrag te onderscheiden. Bij Type I materialen is de rol van het adsorp-
tiemechanisme al heel snel bij lage vochtigheden uitgespeeld, terwijl het bij Type II materialen
bij alle vochtigheden een rol speelt. Om inzicht te krijgen in de exacte wisselwerking van het
adsorptiemechanisme en het breukproces is spinel als een modelmateriaal intensief onderzocht.
Hieruit bleek dat het inversieproces een eenduidige interpretatie van het adsorptiemechanisme
in de weg staat. Derhalve is aan zink aluminaat keramiek, dat geen inversie vertoont, gewerkt.
Hiermee zijn echter wegens productieproblemen nog geen breukexperimenten uitgevoerd, maar
additionele (computer) experimenten toonden wel aan dat het een potentieel zeer interessant
modelmateriaal is voor verder onderzoek.
Op dit moment kan nog geen eenduidig antwoord gegeven worden op de vraag wat de exacte
interactie tussen de adsorptie en het breukproces is. Er kunnen echter wel een aantal redenen
uitgesloten worden danwel een aantal redenen aangewezen worden als mogelijke oorzaak. Ver-
der onderzoek is en blijft dus noodzakelijk. Dit toont aan dat wetenschappelijk onderzoek een
proces is van kleine stapjes vooruit.
156
Dankwoord
Een collega van mij heeft het reeds gemeld. Met het afronden van een promotieonderzoek komt
er een einde aan je formele opleiding van bijna vijfentwintig jaar. Als je dan terug kijkt, dan zijn
er veel mensen geweest die daar in min of meerdere mate aan hebben bijgedragen. Het gaat te
ver om ze allemaal te bedanken, waar ze ook mogen zijn, maar ik zou graag van de gelegenheid
gebruik willen maken om enkelen van hen met naam te bedanken die hebben bijgedragen in de
fase van het promotieonderzoek.
Als eerste wil ik graag professor Bert de With bedanken voor de mogelijkheid tot het verrichten
van mijn promotieonderzoek in het laboratorium voor Vaste Stof en Materiaalchemie, waarbij
ik ook de mogelijkheid heb gekregen om mijn eigen chemische interesses in een ten dele inge-
nieurswerk in te passen. Verder wil ik je bedanken voor de vele discussies die we hebben gehad;
niet alleen over het onderzoek en de wetenschap, maar ook over onderwijs, popularisering van
de wetenschap en mineralogie.
Graag wil ik ook mijn begeleider Ardi Dortmans bedanken voor de vele discussies die we heb-
ben gehad over de meetresultaten en vooral hun implicaties. Furthermore, I would like to thank
ChangMing Fang for his assistance with and discussions about computer simulations and their
comparison with experiments. Tenslotte wil ik graag de leden van mijn leescommissie de pro-
fessoren R.C. Bradt, H. Brongersma en L. Van Poucke bedanken voor hun nuttige commentaar.
Met de teruglopende studentenaantallen is het niet meer vanzelfsprekend dat elke promovendus
de mogelijkheid krijgt om studenten te begeleiden tijdens hun stages. Ik mag me daarom geluk-
kig prijzen dat ik tot twee keer toe die mogelijkheid wel heb gehad en bovendien ook nog met
157
Dankwoord
twee uitstekende studenten: Joep van Dijk en Marcel Snel. Bedankt voor jullie bijdrage, dat ze-
ker terecht is gekomen in dit proefschift, en voor jullie aanwezigheid.
Een proefschrift maak je niet alleen is een veel gehoorde kreet. En dat is zo! Daarom wil ik
graag alle medewerkers van SVM (inclusief SVM-Coatings), aan wie ik stuk voor stuk persoon-
lijk een mooie herinnering bewaar, bedanken voor het "iets" maken, het "iets" typen, het "iets"
meten, het "iets" bepraten en domweg voor de gezelligheid binnen en buiten het werk. Met
name wil ik daarin ook graag mijn AiO-generatiegenoten noemen, waarmee ik door Europa ben
getrokken: Maru, Mark, Pascal en Dennis. Naturalemente, quiero agradecer también mi com-
pañero de oficina Emilio, por todas las discussiones, ayuda y "gezelligheid" en y fuera de STO
2.24 durante estos cuatro años.
Een proefschrift met experimenteel werk kan nooit tot stand komen zonder hulp van bereidwil-
lige en meedenkende technici. De TU/e mag zich dan ook gelukkig prijzen met de vakbekwame
technici zoals de medewerkers van Fijnmechanica o.l.v. Theo Maas en Jos de Laat en de Glas-
blazerij/Zagerij o.l.v. Frans Kuijpers, die ik hierbij ook bedank. Tenslotte, wil ik graag speciaal
Hans Onstenk bedanken voor het maken van de vele, soms lastige, proefstukjes.
Een leven op de universiteit kan niet zonder te ontspannen buiten de universiteit. Mijn twee gro-
te hobby’s stelden me gelukkig in staat om me af te leiden van het promotiewerk: volleybal (als
speler en scheidsrechter) en stijldansen. Allereerst wil ik alle Hajranen met wie ik (al dan niet)
heb samengewerkt, en, in het bijzonder, mijn teamgenoten van Hajraa H2/H3/H4/H3 hartelijk
bedanken voor de zeer leuke tijd met vele hoogtepunten (o.a. twee kampioenschappen). Verder
wil ik in het bijzonder ook mijn danspartner Yvet Beckers bedanken voor het zwevend over de
dansvloer doen vergeten van de problematiek gekoppeld aan werk.
Tenslotte wil ik Bart, Stieneke en Sigrid bedanken voor hun steun en toewijding tijdens mijn
opleiding in al die jaren.
158
Curriculum Vitae
Niels van der Laag is op 24 juni 1974 geboren te Boxmeer en getogen in Cuijk. Na het behalen
van het Atheneum diploma aan het Merletcollege te Cuijk in 1992 startte hij met de studie
Scheikunde aan de Katholieke Universiteit Nijmegen. In de doctoraalfase specialiseerde hij zich
in de afstudeerrichting Informatische Chemie, waarvoor hij in het kader van het hoofdvakstage
onderzoek deed bij de vakgroep Vaste Stof NMR o.l.v. prof. dr. B.H. Meier naar de performan-
ce van het NMR-simulatieprogramma GAMMA. Verder deed hij tijdens een extra bijvakstage
bij de vakgroep Vaste Stof Chemie o.l.v. dr. F.K. de Theije en dr. W.J.P. van Enckevort onder-
zoek naar het etsen van diamantoppervlakken met zuurstof. Dit alles resulteerde in 1998 in het
behalen van het doctoraalexamen (met genoegen).
Aansluitend is hij begonnen met promotieonderzoek bij de vak-/capaciteitsgroep Vaste Stof en

Materiaalchemie aan de Technische Universiteit Eindhoven. Onder leiding van prof. dr. G. de
With deed hij onderzoek naar de invloed van water op het breukgedrag van het oxidische kera-
miek. De resultaten van dit promotieonderzoek zijn weergeven in dit proefschrift.
Niels van der Laag is born on 24 june 1974 in Boxmeer and bred in Cuijk (The Netherlands).
After obtaining his Atheneum diploma (Dutch pre-university education) at the Merletcollege,
Cuijk in 1992, he commenced studying chemistry at the Catholic University of Nijmegen. Dur-
ing the final phase of his study, he specialised himself in computing chemistry and performed
an internship at the department of Solid State NMR under the guidance of prof. dr. B.H. Meier
on the performance of the NMR simulation package GAMMA. Furthermore, he did an extra in-
ternship at the department of Solid State Chemistry under the guidance of dr. F.K. de Theije and
159
Curriculum vitae
dr. W.J.P. van Enckevort on the etching mechanism of diamond surfaces by oxygen. He ob-
tained his Masters degree in 1998.
Subsequently, he started his Ph.D.-research project at the Laboratory of Solid State and Mate-
rials Chemistry at the Eindhoven University of Technology. Under the guidance of prof. dr. G.
de With, he investigated the influence of humidity on the fracture of oxide ceramics. The results
are published in this Ph.D. thesis.
160
UITNODIGING
U bent van harte welkom
bij de openbare
verdeding van mijn
Environmental effects on the fracture of oxide ceramics

Environmental effects proefschrift
Environmental
on the fracture of oxide ceramics effects on the
fracture of oxide
ceramics
De promotieplechtigheid
zal plaatshebben op
woensdag
18 december 2002
om 16.00 uur
in het Auditorium van de

Technische Universiteit
Eindhoven.
Aansluitend aan deze

plechtigheid zal een
receptie plaatsvinden
waarvoor U ook van
harte bent uitgenodigd.
Niels van der Laag Niels van der Laag

Niels van der Laag
F.D. Rooseveltlaan 239

5625 AZ Eindhoven
040-2486540
N.J.vanderLaag@tiscali.nl
± 170 pag. = 11mm rug

f.c.
glanslaminaat

Environmental Effects On The Fracture of Oxide Ceramics: Uitnodiging

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UITNODIGING

U bent van harte welkom

Environmental effects on the fracture of oxide ceramics

in het Auditorium van de

Aansluitend aan deze

Niels van der Laag Niels van der Laag

F.D. Rooseveltlaan 239

± 170 pag. = 11mm rug

ter verkrijging van de graad van doctor aan de

Niels Johan van der Laag

Druk: Universiteitsdrukkerij, Technische Universiteit Eindhoven

CIP-DATA LIBRARY TECHNISCHE UNIVERSITEIT EINDHOVEN

Laag, Niels J. van der

Trefwoorden: keramische materialen; breuk / vastestofchemie / spinel; magnesium

2 Theoretical and computational background . . . . . . . . . . . . . . . . . . 7

2.6 Experimental mechanical tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

3 Water vapour influence on the fracture of commercially applied

4 Subcritical crack growth in calcium hydroxyapatite . . . . . . . . . . . 51

5 Fracture of magnesium aluminate spinel (MgAl2O4) . . . . . . . . . . . 63

6 Structural, mechanical, thermophysical and dielectric properties

6.5.3 Thermophysical properties

7 Computational investigation of bulk and surface properties of

8 Predictive calculation of intrinsic thermophysical properties

8.5 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

9 Epilogue: overview, conclusions & future work . . . . . . . . . . . . . . . 133

Samenvatting voor niet-wetenschappers . . . . . . . . . . . . . . . . . . . . . 147

Curriculum Vitae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159

1.1 Galloping Gertie

Figure 1.1: Collapsing Tacoma Narrows Bridge (Galloping Gertie).

1.2 Ceramics and failure

1.3 Aim and lay-out of this thesis

Furthermore, as fracture is often treated on an atomistic (micro-)level, a number of phenomena,

dividually. As a consequence, repetitions of some parts (notably descriptions of experimental

In chapter 8, the predictions of thermophysical properties of ceramics in general by the Debye

Theoretical and computational background

2.2 Fracture mechanics: Stress intensity approach

2.2.1 Stress concentrators

2.2.2 Stress intensity factor

 σ xx   cos ( θ ⁄ 2 ) [ 1 – sin ( θ ⁄ 2 ) sin ( 3θ ⁄ 2 ) ] 

K tot = K I + K II + K III . (2.9)

2.3 Fracture mechanics: Energy approach

2.3.1 Griffith energy balance

2.3.2 Mechanical energy release rate

du = CdF + FdC . (2.20)

2.3.3 Intrinsic work of fracture

dUF = Rdc , (2.25)

2.3.4 Failure criterion

dU = dUM + d U F = – Gdc + Rdc = ( R – G )dc . (2.27)

2.4.1 Adsorption isotherm

where b is equal to k1 / k2.

where c is approximately given by:

2.4.2 Adsorption and fracture energy

2.4.3 Adsorption and fracture toughness

where σo is the applied stress at fracture.

K ads = Yσ ads c o , (2.39)

where σads is the applied stress at fracture.

K ads = K o 1 – φ ln ( 1 + bpX ) , (2.40)

with the constant φ given by:

K ads = Yσ SCG c c , (2.42)

2.5 Subcritical crack growth

KI,th KI,lim KIc

2.5.2 Constitutive model

2.5.3 Empirical power law