Mat E 423

Physical Properties of Glass 2: Thermal Expansion Coefficient

Understand how the thermal expansion coefficient depends upon temperature,
cooling rate, interatomic bonding, and composition
Understand and be able to use relative order of magnitude values for the
thermal expansion coefficient for various oxide glasses
Be able to estimate thermal expansion coefficient for oxide glasses using
simple additive factors models
Thermal Expansion of Glass
 Thermal expansion determines
if a glass will be shock
resistant, able to withstand high
thermal stresses
 Thermal expansion also
determines if a glass will have
low thermal shock resistance
 Small thermal expansion
coefficient leads to high
thermal shock resistance
 Large thermal expansion leads
to low thermal shock resistance
 Tshock= E(1+)/

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Thermal Expansion of Glass

 Thermal Expansion
also determines
whether a glass can be
thermally “tempered”
to increase its strength
 High thermal
expansion leads to
high tempering ability
 Low thermal  Thermal tempering increases
expansion leads to low strength and reduces large
tempering ability dangerous shards to fine small
particles

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Thermal Expansion of Materials

 Most materials expand as they are heated

– Some more than others
 Refractory metals and ceramics
– Expand less
 Polymers
– Expand more
 Some materials expand very little
– SiO2 glass
– -spodumene, Li2O.Al2O3.4SiO2
 Complex systems with more than one material must
have matched or compensated thermal expansions

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Typical Thermal Expansion Coefficients of Materials

SLS

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Thermal Expansion Values of Materials

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Thermal expansion of Crystals

 Polycrystalline materials
under go phase
transformations
 Thermal expansion changes
at each phase transition
 c-SiO2 has numerous phase
changes and numerous
volume changes that must be
accounted for during heat up
of systems using SiO2

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Thermal Expansion of Crystals

g-SiO2

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Measurement of the thermal expansion
 Expansion dilatometer
 Thermal mechanical analyzer
 Measures the length of the sample
– Typically a glass rod
– 0.5 cm x 1 cm
 As a function of temperature
 Linear Variable Differential Transducer (LVDT) accurately
converts distance changes of microns into millivolts.
 T/C measures sample temperature
 Furnace provides sample heating and/or cooling
 Typically slow heating rate 3oC/min

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Typical Pushrod Dilatometer

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Thermal Expansion of Glass

1  L 
L   
L0  T  P
1  V 
V    V  3 L
V0  T  P
 For isotropic materials,
homogeneous in three directions,…
 Volume expansion coefficient is 3
times larger than linear expansion
 Glasses are isotropic
 Fine grained polycrystals are
isotropic

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Determination of Linear Thermal Expansion
1  L 
L   
L0  T  P
1  L(T2 )  L(T1 ) 
 L ~  
L0  T2  T1 P

 Determine L for
100 – 200,
 200 – 300,
 100 – 500oC
ranges

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Temperature Dependence of Thermal Expansion
 Glass undergoes glass
transition and transform to Ts
supercooled liquid at Tg Td = Tg liquid
 Liquid has a larger 
 At softening point, liquid
begins to be compressed by
force of applied
dilatometer, “dilatometric
hook”
 Tg measured by
dilatometry is called Td and
is often < than Tg measured glass
by DTA
 DTA scans at 10 –
20oC/min, dilatometry is
done at 3-5oC/min

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Temperature Dependence of Thermal Expansion
 Properties of glass depend
upon cooling rate
Ts
 Heating rate of dilatometry Td = Tg liquid
is slow and as such well
annealed samples, or those
cooled at the same slow
rate must be used
 Fast quenched glasses will
undergo “sub-Tg”
relaxations, i.e., they try to
relax to slower cooling rate
curve glass
 Eventually, glass undergoes
transition at Td(Tg)

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Temperature Dependence of Thermal Expansion
 As fast cooled glass is reheated glassy supercooled
and approaches Tg state liquid
 The structure begins to “loosen”

Molar Volume
 Structural relaxation time begins
to shorten
Fast cooling liquid
 Time is available for the glass to
try to relax “down” to the slow
cooled curve
 As glass glass shrinks, it exhibits a
negative thermal expansion
slow
 The greater the mismatch between
qc and qh, the greater the sub-Tg
relaxation event
Temperature

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Thermal Expansion Coefficients for Various Glasses

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Thermal Expansion of Alkali Silicate Glasses
 As alkali is added, thermal expansion
increases
 Tg decreases with added modifier Tg
 Lowest modifier shows anomalous
‘plateau” above Tg
 Liquid does not fully relax as it should
 Low soda silicate glasses exhibit Tg
phase separation
 Liquid phase separates into high silica
and high alkali glasses, two glasses
with different Tgs 100%
 High silica liquid does not undergo Tg SiO2

until higher temperatures

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Thermal Expansion of Alkali Silicates

 Thermal Expansion
coefficient increases with
alkali modifier
 Expansion coefficient is
larger for the the larger
alkali's
 K > Na > Li
 Taken as an average value
from 150 to 300oC

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Thermal Expansion of Alkali Borate Glasses
 Addition of alkali modifier
decreases thermal expansion
coefficient in alkali borate glasses
 Modifier in low alkali borate
glasses, cross links glass structure
 Creation of tetrahedral borons
 Adding bonds to boron, increasing
connectivity of network
 Strengthening the network
 Rigidity of the glassy network
increases
 Thermal expansion decreases with
modifier

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Ultra-low expansion (ULE) glass

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Correlation of Thermal Expansion with structure
 Materials expand by their average
bond length increasing
 Glasses are disordered, so
expansion is isotropic
 Expansion is governed by the
interatomic potential well that
binds the atoms and ions together
 Tightly bound atoms reside in
deep energy wells that are only
slightly affected by temperature
 More weakly bound atoms reside
in shallow energy wells that are
more affected by temperature
 NBOs increase thermal expansion,
Bos decrease thermal expansion

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Calculation of Thermal Expansion Coefficients
 Thermal expansion like many
properties are continuous with
glass composition
 Each oxide may have a predictable
affect on the thermal expansion
coefficient
 Assuming a linear relationship
between composition and thermal
expansion coefficient
 Thermal expansion can be
calculated within limited
composition ranges for many
different glasses
 For soda lime glasses
= [51.3 +210.864 Na2O + 275.584
K2O + 13.887 CaO –23.93 MgO –
88.638 Al2O3] x 10-7/oC
 Note most factors are +’ive
 Factor for Al2O3 is –’ve and
reflects decreasing NBOs
 Factor for K2O is larger than factor
for Na2O
 Which is much larger than factor
for CaO
 Calculate for 20Na2O + 10CaO
+70SiO2 glass

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Calculating Thermal Expansion Coefficients
 More general oxide
glasses
 Additive factors for
three different models
 Some model hold
factors constant
 Some models vary
factors with
composition
 Compare thermal
expansion of SLS
glass for all four
models

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