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Giulio C. Sarti
From Bologna: diffusion of tortellini
diffusion of mortadella
22
Alma Mater Studiorum - Universit di Bologna,
Bologna, ITALY
Fickian diffusion
non swelling penetrants no relevant deformations and no stresses
swelling penetrants deformations and stresses are induced
a) how to measure stress effects
b) how to calculate the stress field
Ruben G. Carbonell-NCSU
Ferruccio Doghieri
Marco Giacinti Baschetti
Maria Grazia De Angelis
Maria-Chiara Ferrari
Jacopo Catalano
and to the group
Penetrants can generate swelling
and stresses
In gases and in liquids diffusion does not build up a stress field
In solids in general and in polymeric solids in particular stresses are
generated by swelling penetrants
Crazes and even cracks can be produced
Morphological changes are induced
Methanol in PMMA
After Tomas & Windle, Polymer 1982
Effects of swelling and stresses
c 2c
=D 2
t z
c = ceq P ( x, y,z ) S f , t
c n = 0 P ( x, y,z ) S I , t
c=0 P ( x, y,z ) V f , t=0
Swelling condition
ic = ( c ) c
How can they be described
c 2c
=D 2
t z
c = ceq P ( x, y,z ) S f , t
c n = 0 P ( x, y,z ) S I , t
c=0 P ( x, y,z ) V f , t=0
Independent measurements
Solubility Isotherms in Glassy Polymers
observed behaviors
Swelling condition
ic = ( c ) c
How it can be described - mechanics
-0.1
Deflection (mm)
i) the mechanical properties -0.15
D
(Young modulus and Poisson -0.2
ratio),
-0.25
-0.3
-0.4
0 20 40 60 80 100
iii) the concentration profile and t^0.5 (s^0.5)
-0.05
-0.15
-0.2
Layers model (costant D)
-0.25
-0.3
-0.35
-0.4
0 10 20 30 40 50 60 70 80 90 100
t^0.5 (s^0.5)
9 cm 2
D = 0.9 e D = 1.9e 9 e ( C 28 )
s
Model predictions vs exp. data
Yield 62 MPa
-0.4
-0.6 polymer.
-0.8
-1
-1.2
0 2 4 6 8 10 12
time^0.5 (h^0.5)
EB in PS
Plot of M,/M, vs t for (1 =0.1181), circles, (1 = 0.1308 squares),
and (1 = 0.1425 triangles); all three uptake curves show Fickian
characteristics (Billovitis et al Macromol 1994)
Different behaviors observed
EB in PS
Plot of M,/M, vs t for (1 = 0.0276), Fickian 1 = 0.0600 delta P (torr): 4.0-4.9
characteristics (Billovitis et al Macromol 1994) glass ; two-stage
Different behaviors observed
Me-OH in PMMA
Tomas & Windle Polymer 1980
Different behaviors observed
Different behaviors observed
Fractional residual core thickness for n-propanol sorption in Fractional residual core
thickness for ethanol sorption in PMMA sheets; 1 mm nominal thickness; as-received
samples: 50, 55, 60 C; and samples annealed 24 hr at lOO C, penetrated at 50C.
Different behaviors observed
Different behaviors observed
Penetrants can generate swelling
and stresses
Effects of prehistory
Higher : no accel
Lower : larger acceleration
Modeling
A A NEq (T , p, 1 , 2 ) = A Eq (T , 1 , 2 )
mG A Eq
( GP )
=
m1 T , p ,m2 , 2 1
1
T , 2
Doghieri & Sarti JMS 1996, Chem. Eng. Sci 1998
Solubility Isotherm from
Dilation Data ......
Assume lattice fluid model (SL):
The SL Parameters (P*,T*,*) for
both penetrant and polymer The NELF gives the
The density of the polymer during the Sorption Isotherm
Sorption (e.g Dilation data)
8 0.12
7 exp.data
0.1 (CO2-PC 35C)
Volume Dilation %
6 exp.data
(CO2-PC 35C) 0.08 NELF
C(g/g_pol)
5 prediction
4 0.06
3 0.04
2
0.02
1
0
0
0 2 4 6 8
0 1 2 3 4 5 6 7
p(MPa) p(MPa)
(data from Fleming and Koros, 1990) (data from Fleming and Koros, 1990)
Effect of relaxation processes on gas/vapor solubility in glassy
polymers: volume swelling model (VS)
0.015
0.010
0.005 0.001
1 10 100 1000 10000 1 10 100 1000 10000
time (s) time (s)
Kinetics of CO2 sorption in PMMA film for Kinetics of CO2 sorption in PMMA film for
sorption step from 12.4 bar to 23.4 bar. sorption step from 25.4 bar to 33.1 bar.
Comparison of experimental values with model Comparison of experimental values with model
results. results.
472
Rate-Type (RT) lumped models for viscoelatic diffusion
sol
= J Hyperbolic problem accounting for
t
J a relaxation time in the flux
+ J + D sol = 0
t
relaxation phenomena in volume swelling
1 pol p EXT p EQ ( , pol ) and in relax in BC
=
pol t
Thermodynamic Analysis for the development of
shock concentration waves in the system
Examples of concentration
profiles from simulation of
sorption process for ethanol in
PMMA (De = 30)
More general models
Mass balance
+
Mechanical problem
with viscoelastic response