Thermodynamics of viscous flow and elasticity of glass forming liquids in the glass transition range

Tanguy ROUXEL
LARMAUR, ERL CNRS 6274, University Rennes 1, France

Elastic moduli, Poissons ratio and the short to medium range order in glass High temperature elastic behavior and the depolymerization of the atomic network The viscous flow process and the non-Arrhenian behavior
RISC-E octobre 2011

Elastic moduli, Poissons ratio and the short to medium range order in glass

J. Am. Ceram. Soc. 90 [10] 3019-3039 (2007)

There is no direct correlation between E and Tg Elastic moduli are expressed in Pascals, i.e. in J/m3 , and are thus governed by the volume density of energy

m he

ic

P a l-

hy

s s ic

of s c i s) an s w h a l l c M e t e r i a titiv e M a n s ti (c o

l ca and M , i r m e llin g (F E u N d e tio n M o u la S im S ) MD

in . g n l E s ig n a ic an al D e h c r M e u c tu r St

Silicate glasses: Glass formers (Si, Al, B, Zr) Modifyers and charge compensators (Li, Na, K, Ca, Ba) Anions: O, N or C

Cation substitution: modifyers ! Uo ; formers ! Cg Intermediate elements occupying former or interstitial sites: Hf, Be, Zr, Ti, Li and Th. Electronegativities: 1.25 to 1.75. Emax=145 GPa: magnesium aluminates + 25 mol.% de BeO.

Anionic substitutions: more efficient but Tg

Si O O O Si

Si Si O N O Si Si

Si Si C

Si

O Si Si

Si

E oxycarbides and E oxynitrides >> E oxides However: UoSiC(447) kJ/mol)~UoSi-N(437 kJ/mol)<UoSi-O(800 kJ/mol)

This is more the architecture (reticulation) of the network than the individual bond stiffnes that governs the glass elasticity

Elastic moduli and structural changes are correlated

General tendencies:

!cd<!bcc<!fcc,hcp
For a given crystalline structure and valency, Poissons ratio mostly increases with atomic number (Z) (Lead (!Pb=0.44) and thallium (!Tl=0.45) with high Z have remarkably high Poissons ratios) High melting points favor low Poisson's ratio (beryllium, combining a small Z and a melting point (Tm=1560 K) much higher than those of the other elements in the same column, exhibits a remarkably small Poissons ratio of 0.032)

Molecular scale:
0D: Clusters, litlle short to medium range ordering

1D: Chains and rings

Se

Se

Se

Se

Se

Se

Se

Se

Se

Se Ge

2D: Layers

Se Se Se Ge O

Se Se

Se Se

Se Ge Se Se

Se

Ge

Se

Substitution O of 3O2- for 2N3O O Si O O Si O Substitution of 2O2- for 1C4O O

Si O
O O Si Si O

Si

Si O
Si
Si O

O O
O O

O
C

3D: 3D units and crosslinking

O O O

O O

Poissons ratio and atomic network dimensionality a-Se Zr55Cu30Al10Ni5

a-SiO2

GeSe4

#& 0.15 3D
D L

#& 0.286 2D %
"L "D

#& 0.323 1D

#& 0.37 0D?

# = -$t/$l = - L/Dx"D/"L "V/V=Trace $=(1-2#)%/E

Poissons ratio and dimensionality

High temperature elastic behavior and the depolymerization of the atomic network

Measurement of elastic moduli by ultrasonic echography

Measurements at ambient temperature High temperature measurements
ArMagnetostrictive Transducer (100 400 7%H2 kHz) Tungsten guide Refractory cement Generator Receiver H Oscilloscop e Furnace Sample Thermocouple e L

Transmitter/recei ver

Signal Time synchronization

Piezoelectric transducer (5 to 20 MHz) L Sample Elastic wave in semi-infinite medium : (<<L and ( << )

Signal analyser (Fourier's analysis)

Long beam bar mode : e<<L and e << ( (10 to 100 mm)

E = ' Vl2

Small size specimens: Acoustic microscopy

When (L,H)<(, regular piezoelectric transducers are unable to efficiently promote the propagation of shear waves through the specimen. Focused piezoelectric transducers can be used to propagate surface-type waves, also called Rayleigh waves, which velocity is given by: VR=*Vt, where * is a function of Poissons ratio, or of the Vl/Vt ratio. VR and Vl are measured and Vt is optimised to satisfy the following equation: 2

E = ' (3Vl2-4Vt2)/((Vl/Vt)2 -1) G= ' Vt2 #=E/(2G)-1 Where: ': specific mass Vl: longitudinal wave velocity Vt: transverse wave velocity

VR =

Vt (0.715 - (Vt /Vl ) ) 0.750 - (Vt /Vl )

2

160

140

120

Oxynitride

Young's modulus (GPa)

100 SiOC 80 Bulk metallic Basaltic Soda-lime-silica (window) a-SiO2

60

Tg
40

20 Chalcogenides 400 600 800

SiOC Se Ge15Se85 Ge30Se70 YSiAlON(7.5 at% N) YSiAlON(Si/Al=1.5) YSiAlON(Si/Al=3.75) ZrCuAlNi Ge22As20Se58 Pd42.5Ni71Cu30P20 Diopside a-B2O3

Window glas s Ge10Se90 Ge25Se75 YSiAlO YSiAlON(11.2 at% N) YSiAlON(Si/Al=1.95) YMgSiAlON Glycerol a-SiO2 ZBLAN Gros sular

0 200

1000

1200

1400

1600

T (K)

For T>Tg, /(Tg)=(Tg/T)+ where + ranges between 0.07 (a-SiO2) and 10 (a-Se)

The viscous flow process and the non-Arrhenian behavior

Stress or strain-rate dependence Log ,

So-called equilibrium viscosity!

Log stress

Boltzmann-Arrhenius approach of thermally activated processes:

- = -o exp["Ga /(RT)]

-: the characteristic relaxation time -o: a constant T: temperature R: perfect gas constant "Ga: free activation enthalpy of the flow process Assuming a simple Maxwell relaxation model ,= -o exp["Ga /(RT)] , where is the shear elastic modulus.

Log ,/,(Tg)

Strong

, = ,o exp["Ga /(RT)]

Fragile

Tg/T
Observations: the heat for flow is temperature dependent, especially in the case of short glasses VFT, WLF, AM, MYEGA numerous empirical expressions

Adam and Gibb's (1965) approach of the viscous flow process:

- = -o exp[z"g /(RT)]
-: the characteristic relaxation time; -o: a constant; T: temperature; R: perfect gas constant; z: number of molecules or monomeric segments; "g: height of the potential energy hindering the cooperative rearrangement of the elementary structural units involved in the process Assuming a simple Maxwell relaxation model ,= -o exp[z"g /(RT)] , where is the shear elastic modulus. z is inversely proportional to the configurational entropy Sc and "g is taken as temperature independent

, = ,o exp["G /TSc]
The configurational entropy is a temperature dependent parameter (especially for T>Tg) which is commonly assimilated to the excess entropy
Liq Glass Cp " Cp Sc (T ) = Sc (Tg ) + # dT Tg T T

Good fit of experimental data in the few cases where actual calorimetric data are available (Richet, Botinga)

But fundamentals uncertainties remain ( excess versus configurational entropy; Configurational versus vibrational entropy )

Present analysis:

,= -o exp["Ga /(RT)]
i) As in the case of plasticity in crystalline materials, the energy barrier for viscous flow chiefly depends on the shear elastic modulus. Therefore comes into play both in the prefactor and implicitly in "Ga Glassy materials differ from crystalline ones by a rapid softening in the supercooled liqui range (i.e. for T>Tg), so that is mostly very sensitive to temperature. Consequently, "Ga depends much on temperature and this can be analyzed within the classical framework of thermodynamics, recalling that the entropy change writes

ii)

"S = #

$"G $T
%

The problem of concern reduces to the determination of the temperature dependence of !Ga, !Sa and the heat for flow !Ha !

ACTIVATION ENTROPY OF THE VISCOUS FLOW PROCESS

("Wa = - Va)

& ( %Gb $ %W a ) ) (1) " # exp($ + RT ' *

(2) "Gb = "Ga + "Wa

& ( %Ga ) ) " # exp($ + (3) ' RT *

(4)

" = # / $

" ln # 1 "%Ga = % G + a ! 1 T "1 " T $ , stru T $ , stru

(5) "

!
(2)+(5)

#$Ga = $Sa #T % , stru

" ln # (6) = %Ga + T%Sa = %H a 1 " T $ , stru

"Sa = #

"#Gb #Gb " $"Gb $V +% a ! = $T % , stru $T % , stru "T $ , stru "T !

$ , stru

"Sa = #
!

$ &V ( "G a + %Va ) + % a T &T

"S a

!"S#

T # " = #T

"H a = R

+(6)

"Sa

# ln $ 1 # T % , stru $ = # "H a (1 # $ )T

For -=10 MPa and Va=50 -Va=500 -1 ! J.mol , to be compared ! with the order of ! activation energies, 100 to 1000 kJ.mol-1

cm3.mol-1,

"Ga =

1 "H a (1 # $ )

"H a

# ln $ = R # (1/ T ) % , stru

"#$%&,"#$%&...
This is where entropy comes into play

"#Ga #Ga " = "T $ , stru "T $ , stru

/(Tg)=(Tg/T)+
!

"Ga = "Ga(Tg)(Tg/T)+

% #Ga (Tg )(Tg / T )$ ( " = " o exp' * RT & )

"Ga (Tg ) = "H a (Tg ) % T $ '1 # g ' (T ) $T g & ( * * Tg )

with

,o = (T),(Tg)/(Tg)
!

Equivalent to AvramovMilchev equation

with: (T)=.exp(E/T)
Equivalent to MYEGA equation