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

related.In factaceram ic(stiffm aterial)willexpand lessthan apolym er.Thisgeneral
trend is observed in the a–E chart (Fig.2.8) where allclasses of m aterials are
considered.This 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 s.The con-
tinuouslineisforam orerigidm aterialsinceitshowsadeeperpotential.Param eterro
corresponds to the equilibrium distance atT ¼ 0K.This tem perature cannotbe
produced,so for clarity we take this tem perature as a reference point.AtT > 0K,
atom s oscillate around their equilibrium position.Itis 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 onicpotential.Force 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 Technology.Eric Le Bourhis

Copyrightß 2007 W ILEY-VCH Verlag G m bH & Co.KG 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 alexpansion.In 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).