271
Appendix 3
Therm alExpansion and Elasticity
A3.1
The a–E Trend
M aterials’therm alexpansion coefficient a and stiffness (elastic m odulus E) are
[Link] factaceram ic(stiffm aterial)willexpand lessthan apolym [Link]
trend is observed in the a–E chart (Fig.2.8) where allclasses of m aterials are
[Link] trend is m athem atically form ulated as
gGr cv
a¼
3E
where the G rüneisen ‘constant’gG is nota constantbutvarieswithin one orderof
m agnitude (0.4< gG < 4),r is the density and cv the specific heatcv cp.
A sim ple approach to therm alexpansion isproposed byZarzycki1982 and Kittel
1983.W e shallreview briefly here theirapproaches.
A3.2
Q ualitative Approach
Figure A3.1 shows schem atically the potentialenergy ofbonded atom [Link] con-
tinuouslineisforam orerigidm [Link] eterro
corresponds to the equilibrium distance atT ¼ [Link] tem perature cannotbe
produced,so for clarity we take this tem perature as a reference [Link] > 0K,
atom s oscillate around their equilibrium [Link] im portantto note thatthe
potential is not sym m etric. For sm all oscillations, one generally neglects this
phenom enon and takes a parabolic function in the form Ep ¼ (1/2)k(r ro)2 also
called the harm [Link] isthen F ¼ k(r ro).U ndersuch an assum p-
tion,no therm alexpansion is found (Fig.A3.2).
N ow considering thefactthatthepotentialisnotsym m etric,theaveragedistance
between atom s shifts towardsthe right-hand side ofFig.A3.1,orthe m aterialsare
expected to expand when they are heated.H ere,we do not consider any phase
Glass; Mechanics and [Link] Le Bourhis
Copyrightß 2007 W ILEY-VCH Verlag G m bH & [Link] aA,W einheim
ISBN :978-3-527-31549-9
272 Appendix 3:Therm alExpansion and Elasticity
Fig.A3.1 Potential energy as a function of distance for weak
(dashed line) and strong (continuous line) bonds.
changes which either yield contraction or expansion.M aterials showing a deeper
potential(stifferm aterials)show lesspotentialasym m etry (forthe sam e additional
therm alenergy kT ).H ence,these m aterials present a lower therm alexpansion
coefficientthan m aterials having a shallow potential(softm aterials).
Considering now silicate glasses,when m odifiers are introduced in the silicate
glass,N BO sareform ed and yield Si–O potentialasym m etryand hencelead to large
therm [Link] contrast,in borosilicate glasses,B atom sparticipate in glass
network form ation and no N BO s are form ed m aintaining the potentialsym m etry
and hence less therm alexpansion is observed forthese glasses.
A3.3
Expansion M odelling
In afirstapproxim ation wem ayadd oneasym m etricterm to theharm onicpotential
thatwe have defined above:
Ep ¼ ð1=2Þkðr roÞ2 þ gðr roÞ3 ¼ cx 2 þ gx 3
with c¼ ½ k,x ¼ r ro,g< 0 and we assum e gx3 kT.W hen g¼0,we getagain a
harm onic orparabolic potential.
Fig.A3.2 Potential energy as a function of distance curve
showing the harmonic approximation.
A.3.4 D ifferentialExpansion M easurem ent 273
Following Kittel1983,we consider a Boltzm ann distribution and the average
distance shiftattem perature T is
R1
xexpð Ep=kTÞ
hxi ¼ R11
1 expð Ep=kTÞ
W ith the following approxim ation:
Ep cx 2 þ gx 3 cx 2 gx 3
exp ¼ exp ¼ exp 1
kT kT kT kT
a series ofcalculationsyields
3g
hxi ¼ kT
4c2
This sim ple approach then yields a constant therm al expansion coefficient
proportionalto g (asym m etric term ):
3g k
a¼
4c2 r0
W e find thatstronger binding (larger value ofc,stiffer m aterials)yields indeed
lower therm alexpansion while larger asym m etry (larger value of g)yields larger
therm alexpansion.
A3.4
D ifferentialExpansion M easurem ent
A dilatom eterisused to determ inethetherm alexpansion coefficientofaspecim en
subm itted to a therm alram p (constantheating rate).N otonly does the specim en
expand but also the dilatom eter (Fig. A3.3). H ence, differential expansion is
Fig.A3.3 Schematic representation of thermal expansion of both sample and dilatometer.
274 Appendix 3:Therm alExpansion and Elasticity
m easured and correction is necessary to include the dilatom eterexpansion in the
experim ental data. Consider for instance an alum ina specim en in an alum ina
cylindricalsupport:the apparentexpansion would be zero because allexpand the
sam erelativelength.A diagram can beconstructed showingthem easured andactual
(and superior)expansion (Fig.A3.3).