Mass Transfer Modeling in Gas Barrier Envelopes For Vacuum Insulation Panels - A Review

Energy and Buildings 55 (2012) 903920
Contents lists available at SciVerse ScienceDirect
Energy and Buildings

journal homepage: www.elsevier.com/locate/enbuild
Review
Mass transfer modeling in gas barrier envelopes for vacuum insulation panels:
A review
Mathias Bouquerel a,b, , Thierry Duforestel a , Dominique Baillis c , Gilles Rusaouen b
a
b
c
EDF R&D, Dpt EnerBAT, Av. des Renardires, Ecuelles, 77818 Moret-sur-Loing Cedex, France
CETHIL (Centre de Thermique de Lyon), UMR 5008, INSA de Lyon, Bt. Sadi CARNOT, 9 rue de la physique, 69621 Villeurbanne Cedex, France
LaMCoS (Laboratoire de Mcanique des Contacts et des Structures), UMR 5259, INSA de Lyon, Bt. Jean dAlembert, 18-20 rue des Sciences, 69621 Villeurbanne Cedex, France
a r t i c l e
i n f o
Article history:
Received 4 July 2012
Accepted 4 September 2012
Keywords:
Vacuum insulation panel (VIP)
Mass transfer modeling
Permeability
Gas barrier envelope
Multilayer membrane with metalized lms
a b s t r a c t
A vacuum insulation panel (VIP) is a very efcient thermal insulation system for buildings. It is constituted of an evacuated porous core material, enveloped in a gas barrier membrane. The total conductivity
measured is as low as 5 mW/(m K). The high performance is due to the low pressure inside the panel and
the gas barrier envelope plays a key role in maintaining the vacuum during the whole VIP service life.
Indeed, due to the permeation of atmospheric gases through the envelope, a slow increase of pressure and
humidity occurs over time, which involves a thermal conductivity increase in the mean time. This review
paper details the mass transfer models used to predict the permeation rates of gases through the VIP
envelope. The sorptiondiffusion model for gas permeation through polymer membranes is presented
as well as alternative permeation models. The parameters which play a key role for mass transfer are
detailed. The adaptation of the permeation models from homogeneous polymer membranes to multilayer
gas barrier membranes is then presented, including an important section about metal-coated polymer
lms. The conclusions of the works based on several approaches are reported.
2012 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1.
Vacuum insulation panels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2.
Membranes used as gas barrier envelope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mass transfer modeling: the linear sorptiondiffusion model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Introduction to the theory of gas permeation through membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Linear sorptiondiffusion model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.
Ficks law of diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2.
Henrys law of sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.3.
Spatial integration and permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Thermodynamics justication of the sorptiondiffusion model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.1.
Chemical potential as a driving force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.2.
Interface gas/membrane and sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.3.
Total mass transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.
Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.1.
Diffusion and solubility coefcients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.2.
Permeation measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.
Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alternative mass transfer modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Dual mode model in glassy polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.
Dual mode sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.2.
Diffusion coefcient and permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corresponding author. Tel.: +33 1 60 73 69 57; fax: +33 1 60 73 65 39.

E-mail address: mathias.bouquerel@ponts.org (M. Bouquerel).
0378-7788/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.enbuild.2012.09.004
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907
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M. Bouquerel et al. / Energy and Buildings 55 (2012) 903920
3.2.
4.
5.
6.
Brief review on other modeling concepts for mass transfer in polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.2.1.
FloryHuggins mode sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.2.
BET mode sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.3.
Gaspolymer matrix model in glassy polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.4.
Site distribution model for sorption in glassy polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.5.
Molecular models of transport in rubbery polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.6.
Free Volume theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Parameters inuence on transport coefcients for polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Inuence of the temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.1.
Arrhenius law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.2.
Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Inuence of the pressure and the concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.1.
Diffusion coefcient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.2.
Solubility coefcient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.3.
Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Inuence of the crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4.
Inuence of the orientation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5.
Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From polymer permeability to multilayer gas barrier membrane permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Multilayer gas barrier membrane morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
Analytical modeling for mass transfer through the barrier membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.1.
Permeation properties of the whole barrier membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.2.
Ideal laminate theory for a multilayer membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.
Apparent permeability of a coated polymer lm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.1.
Transport mechanisms in a coated polymer lm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.2.
Inuence of the coating layer and polymer substrate thicknesses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.3.
Roberts model for the permeability of a coated lm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.4.
Analytical modeling of the micro-defects permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.5.
Musgrave model for the permeability of a coated lm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.6.
Thorsell model for the permeability of a coated lm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.7.
Garnier model for the permeability of a coated lm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.8.
Inuence of temperature and transport mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4.
Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nomenclature
Indexes/exponents
aluminum
alu
amor
amorphous
app
apparent
coat
coating
center of panel
cop
crit
critical
D
Henrys mode
def
defect
dry
dry
elem
elementary
f
free volume
gas
g
glass
glass transition
H
Langmuirs mode
gas i
i
in
inside
ideal laminate theory
ILT
lin
linear
membrane
memb
min
minimum
out
outside
poly
polymer substrate
radiative
rad
saturation
sat
sol
solid
surf
tot
surface
total
Symbols

lin
surf

A
a
ATR
B
b
BIF
c
D
Ea
Naito equation parameter

enthalpic interaction parameter
layer thickness
activity coefcient
gaspolymer matrix model parameter
thermal conductivity
chemical potential
linear permeance
surface permeance
thermal bridge linear coefcient
tortuosity parameter
time lag
volume fraction
chain immobilization factor
area
chemical activity
air transmission rate
water conductivity coefcient
Langmuir afnity coefcient
barrier improvement factor
mass concentration
diffusion coefcient
activation energy
909
909
910
910
910
910
910
910
910
910
910
910
911
911
911
911
911
911
911
911
911
912
912
913
913
913
913
914
915
915
916
916
916
917
917
918
918
f
g
GTR
GTRlin
GTRsurf
Hs
K
kD
l
M
m
n0
P
p
Pesurf
R
r0
Rth
S
T
t
u
V
Vm
WVTR
X
x
free volume fraction

mass ow rate
gas transmission rate
linear gas transmission rate
surface gas transmission rate
sorption enthalpy
ad hoc coefcient
Henrys mode solubility
membrane thickness
molar mass
mass
pinhole density
perimeter
pressure
surface permeability
ideal gas constant
pinhole radius
thermal resistance
solubility coefcient
temperature
time
water content
volume
molar volume
water vapor transmission rate
molar fraction
coordinate in the orthogonal direction
905
Fig. 1. Constitution of a vacuum insulation panel [3].
1. Introduction
Fig. 2. Thermal performance of insulation materials: thermal conductivity and insulation thickness for a thermal resistance Rth = 5 m2 K/W.
1.1. Vacuum insulation panels

Super insulation materials are materials with a thermal conductivity below the conductivity of standing still air (25 mW/(m K)
at standard conditions of temperature and pressure). They are
intended to enable the design of very thin thermal insulation systems for buildings, as efcient as systems based on conventional
insulation materials, but with a much lower thickness. A vacuum
insulation panel (VIP) is one kind of super insulation material,
which was the topic of the Annex 39 of the International Energy
Agency [1,2]. It is constituted of an evacuated open porous material, most of the time a nanoporous silica, wrapped into a multilayer
gas barrier envelope (see Fig. 1). An apparent thermal conductivity
as low as 5 mW/(m K) has been measured [1]. For the same thermal
resistance, the thickness can be six to ten times smaller than for
conventional insulation materials (see Fig. 2).
Heat transfer studies have been conducted on VIPs [1,36],
the total heat transfer through a vacuum insulation panel is the
sum of four contributions and each contribution is associated to
an elementary thermal conductivity elem (see Eq. (1)): radiative
heat transfer rad , solid conduction through the porous matrix
sol , gaseous heat transfer g , and envelope thermal bridge memb .
The gaseous heat transfer appears to be a function of the internal pressure (see Eq. (2): is the core material porosity, 0g is the
non-conned gas conductivity at atmospheric pressure, p1/2 is an
empirical pressure that decreases the gaseous conductivity by 50%).
The total conductivity is also a function of the water content u (see
Eq. (3), B is an empirical coefcient), whose major part is adsorbed
on the silica matrix when nanoporous silica is used as core material.
tot (p, u) = rad + sol (u) + g (p) + memb
(1)
g (p) =
0g
(2)
1 + (p1/2 /p)
sol (u) = sol,dry + Bu
(3)
The initial low pressure and low humidity inside a VIP are
responsible for the very low thermal conductivity. However dry air
and water vapor can migrate through the envelope, which is not
an absolute barrier to atmospheric gases (see Fig. 3). Mass transfer is very low but never null, through the panel faces (membrane)
and through the edges (heat-sealed joint) [1]. These mass transfers dry air permeation, quantied by the air transmission rate
(ATR), and water vapor permeation, quantied by the water vapor
transmission rate (WVTR) are responsible for the pressure and
humidity increases over time. These increases are hardly measurable on a short time scale (few months) but of great importance
over the total service life of the panel. Indeed, the pressure and
Fig. 3. Gas transfer in a VIP.
906
humidity increases are responsible for the total thermal conductivity increase, which is the main mechanism of VIP aging [79].
This review paper is focused on mass transfer modeling through
the gas barrier envelope, at the scale of the membrane only, as a surface phenomenon. The issues of the permeation rates through the
heat-sealed joint and at the scale of a whole VIP are not addressed
here, they are in the scope of another review paper about aging
modeling in VIPs [10].
This paper details the background theory of mass transfer modeling through polymer membranes and the application of these
mass transfer models for multilayer barrier envelopes in VIPs. Mass
transfer modeling can be used to predict the atmospheric gases permeation through the envelope and thus the evolution of pressure
and humidity inside the panel. The usual approach is based on a
sorptiondiffusion model, a linear mass transfer model originally
developed to evaluate permeation through homogeneous polymer
membranes [11]. The permeance to a particular gas, which quanties the gas transmission rate, is a crucial property for a gas barrier
envelope. Several models have been proposed, in order to calculate the permeances to atmospheric gases of multilayer membranes
with metalized polymer lms. They may help the design of very efcient barrier envelopes. The inuence of external parameters on the
membrane permeances, mainly the climatic conditions (temperature and humidity), is also studied: depending on the climate and
on the building implementation, the climatic conditions experienced by several VIPs can be very different and thus the permeation
rates would vary a lot if the permeance is highly dependent on the
temperature and humidity.
1.2. Membranes used as gas barrier envelope
Two types of gas barrier membrane can satisfy the air and water
vapor tightness needed to ensure a long term performance [1]. The
constitution of each type is illustrated in Fig. 4.
AF membranes are made with a laminated aluminum foil (thickness 510 m). A cover layer is added on the outside (50 m of
PET) and a weld layer on the inside (50 m of PE). AF membranes
have very high gas barrier properties thanks to the continuous
metal barrier. However, the thermal bridge produced by an AF
membrane is very high and decreases dramatically the VIP thermal
performance [1214].
MF membranes are multilayer membranes made with several
metal-coated polymer lms (12 m of PET with 20100 nm of
aluminum) used as gas barrier layers. A cover layer and a weld
layer are also added. Unfortunately, the metallic layers contain a
high density of defects (mainly pinholes) [1517]. Because of this
defect distribution, barrier performance to atmospheric gases is not
as good as laminated aluminum foils [17]. This effect is attenuated
by the superposition of several metalized layers, so that the path
length and tortuosity are increased for the permeant molecules.
The polymers (PE, PET, PP, etc.) and thicknesses of the layers may
vary from one product to another. In both laminated aluminum foils
Fig. 4. Ultra gas barrier membranes: AF and MF design.
Table 1
Comparison of thermal bridges due to MF and AF membranes for a 1 m 1 m VIP.
Type
memb (mW/(m K))
MF
min
max
AF
min
max
1.3
24
41
105
memb (mW/(m K))

0.1
2.1
3.3
8.4
memb /cop (%)

2.5
38
66
210
Data from [1214,1820].
and metalized polymer membranes, polyurethane layers are used

to glue the layers [15,16].
Aluminum has a thermal conductivity alu 200 W/(m K) ve
orders of magnitude higher than the evacuated core material
conductivity cop 0.004 W/(m K). The conventional polymer conductivity (PE, PET, PP, etc.) poly 0.10.5 W/(m K) is only two
orders of magnitude above cop . This difference explains why MF
membranes have a better thermal performance: the aluminum
layer thickness is much lower than for AF membranes. The comparison of thermal performance for several AF and MF membranes
is reported in Table 1. These values have been obtained by numerical simulations [13,18] and measurements [12,14,19,20]. memb is
the thermal bridge linear coefcient, memb the elementary thermal
conductivity due to the membrane thermal bridge, calculated as
the difference of apparent thermal conductivity between a square
meter VIP with its gas barrier envelope and a without this envelope.
2. Mass transfer modeling: the linear sorptiondiffusion
model
2.1. Introduction to the theory of gas permeation through
membranes
Laminated aluminum foils (AFs) and multilayer membranes
with metalized lms (MFs) are the main gas barrier membranes
able to satisfy the thermal and gas barrier requirements [1]. MF
membranes have better thermal properties, but the dispersion of
their gas barrier performances is much higher, between low and
high quality membranes [21]. The usual way to evaluate the gas
barrier performance is to use the permeability or permeance of the
membrane [21]. It is based on the sorptiondiffusion model, a linear mass transfer model established for polymer membranes, in
particular rubbery polymers [11,22].
This model is applied to non-porous and homogeneous polymer
membranes, at a given temperature. The transport mechanism is
divided in three main steps (see Fig. 5): condensation and sorption at one surface of the membrane (Sorption 1), diffusion of the
dissolved permeant, driven by a concentration gradient, and then
evaporation at the other surface (Sorption 2).
It is common to use volumetric units for gases: amount of gas
in cm3 (STP), concentrations in cm3 (STP)/cm3 , GTR (gas transmission rate, i.e. mass ow rate) in cm3 (STP)/(m2 s). 1 cm3 (STP) is the
amount of gas that has a volume of 1 cm3 in standard conditions of
temperature and pressure (IUPAC denition of STP: 273.15 K and
1 bar [23]). For water vapor, however, mass units are often used
(respectively kg, kg/cm3 , and kg/(m2 s)). This units change is a
source of complexity and the use of STP volumes is only arbitrary.
Moreover, about fteen denitions of Standard conditions can be
found in several publishing or establishing entities [24].
In order to increase the consistency of mass transfer theory and
experimental data, it might be smart to use the same unit for all
gases, as it has already been pointed out in the literature [25]. Mass
units are somehow more objective units. Equations in this section
are all written with mass units, nevertheless properties found in the
literature may be written in volume units as it is the most convenient way to rewrite them here. In Table 2, some conversions are
907
Table 2
Conversion between volume and mass units for dry gases.
N2
O2
Dry air
Volume
Mass
cm3 (STP)
kg
1
1.23 106
1
1.41 106
1
1.28 106
Flow rate (GTR)
cm3 (STP)/(cm2 d)
cm3 (STP)/(m2 s)
g/(cm2 d)
kg/(m2 s)
1
0.116
1.23 103
1.43 107
1
0.116
1.41 103
1.68 107
1
0.116
1.28 103
1.48 107
Permeability
cm3 (STP)/(cm2 d bar)

cm3 (STP)/(m2 s Pa)
g/(cm2 d bar)
kg/(m2 s Pa)
1
1.16 106
1.23 103
1.43 1012
1
1.16 106
1.41 103
1.68 1012
1
1.16 106
1.28 103
1.48 1012
proposed between the most commonly used technical units and

SI units. The amount of experimental data expressed in technical
units prevents to get rid of them in the technical literature.
in the x-direction (orthogonal to the membrane plane), the equation is simplied:

gi = Di
2.2. Linear sorptiondiffusion model

2.2.1. Ficks law of diffusion
The mass ow rate gi is dened as the amount of permeant dmi
that crosses a surface of area dA during one unit of time dt:
gi =
dmi
dA dt
(4)
(6)
This unidirectional equation is valid for membranes where the

thickness is much smaller than the other dimensions. That is the
case for thin VIP barrier membranes. For transient state, Ficks second law of diffusion is applicable, where the mass uxes and the
concentrations are function of time and position (written here in
unidirectional case):
2
It is dened at a microscopic scale. At a macroscopic scale, the

surface gas transmission rate (GTRsurf,i ) is dened as the mass ow
rate that is transferred through the whole membrane, from one side
to the other one, per surface and time unit (see Fig. 5). It is equal
to the mass ow rate gi in steady state, when gi is constant and
homogeneous through the membrane thickness.
The Ficks rst law sets the linear relation between the mass
ow rate of a molecule diffusing through a membrane and the
concentration gradient of this molecule in the membrane [26]:
gi = Di ci
ci
x
(5)
Di is called the diffusion coefcient, ci is the molecule concentration in the membrane, in kg/m3 . This is a steady state equation,
applicable for a constant concentration distribution and mass ow
rate. For a unidirectional case, when the diffusion is only important
ci (x, t)
g (x, t) (Di ci ) Di ci
ci
= i
=
=
+ Di (ci )
t
x
x
x x
x2
(7)
For several polymerpermeant systems, Di can be considered as

a constant in the whole membrane, so that the equation is simplied:
2
ci
ci
= Di
t
x2
(8)
This equation is formally equivalent to Fourier heat equation

and thus has the same kind of solutions based on Fourier series and
Fourier transform [27].
2.2.2. Henrys law of sorption
The boundary conditions of the diffusion problem depend on the
sorption at the polymer/gas interface. The sorption is a general term
for the dissolution of the transported molecule in the polymer. It
includes absorption, adsorption, and trapping in micro-voids [22].
The simplest law is Henrys law, which considers a linear relation
at xed temperature between the dissolved molecule concentration at the interface and the partial pressure of the molecule in the
gaseous phase:
ci = Si pi
(9)
Si is called the solubility coefcient and is a constant at given

temperature if Henrys law is respected. Henrys law is more likely
to be respected for ideal gases and low pressure [22].
2.2.3. Spatial integration and permeability
For an homogeneous and non-porous membrane at given
temperature, with the assumption of an homogeneous diffusion
coefcient and at steady state, the steady state Ficks law (Eq. (6))
can be integrated on the whole membrane thickness l, between the
interfaces 1 and 2. One gets an homogeneous mass ow rate which
is thus the gas transmission rate:
Fig. 5. Sorptiondiffusion mechanism for mass transfer through a polymer membrane.
GTRsurf ,i = gi = Di
ci,2 ci,1
l
(10)
908
From Henrys law (Eq. (9)), the permeant concentration at the

interfaces is a function of the partial pressure. Assuming that the
solubility coefcient is the same on both sides:
Si (pi,2 pi,1 )
= Di
l
GTRsurf ,i
Pesurf ,i = Di Si
(12)
So that the GTR is only a function of the permeability and the

partial pressure gradient over the membrane:
Pesurf ,i
l
pi
(13)
For an heterogeneous material, the permeability has no meaning. It is however possible to dene the surface permeance surf,i ,
a global membrane property, so that the GTR is a function of the
permeance and the partial pressure difference over the membrane:
GTRsurf ,i = surf ,i pi
(14)
For an homogeneous membrane, the relation between permeance, permeability, diffusion and solubility coefcients is written:
surf ,i =
Pesurf ,i
l
2.3.1. Chemical potential as a driving force

The demonstration starts with the proposition that the driving
forces (pressure, temperature, concentration, electromotive forces)
are interrelated and that the overall driving force can be expressed
as a function of the chemical potential i of the permeant species.
Hypothesis 1. The mass ow rate gi is proportional to the chemical
potential gradient.
(16)
For pressure and concentration gradients only, it is possible to

write:
di = RT d ln(i Xi ) + Vm dp
(17)
Xi is the molar fraction (mol/mol), i the activity coefcient so that

the chemical activity ai is written ai = i Xi , p is the total pressure
and Vm the molar volume.
For a compressible gas, the saturation pressure pi,sat can be taken
for the reference potential. In the liquid phase, the potential can be
written:
i =
+ RT ln(i Xi ) + Vm (p pi,sat )
p
pi,sat
(18)
(19)
Hypothesis 2. The pressure in the membrane is homogeneous,

equal to the high pressure side.
RT Ki d(i Xi )
i Xi
dx
memb /M )
i ci (Vm
i
memb /M ))
d((i ci )(Vm
i
dx
(22)
memb from Hypothesis 3,

Mi is independent of x, so are i and Vm
they vanish in Eq. (22).
gi =
RT Ki dci
ci dx
(23)
It should be noted that this equation is formally identical to

Ficks law (Eq. (6)), the diffusion coefcient is:
RT Ki
ci
(24)
The membrane is isothermal, the concentrations
It is possible to integrate Eq. (23) and to get the expression of

the GTR as a function of the permeant concentrations ci,1 and ci,2 at
interfaces 1 and 2:
gi = Di
ci,1 ci,2
l
(25)
2.3.2. Interface gas/membrane and sorption

The thermodynamics equilibrium at the liquid/gas interface is
written:
0i + RT ln(i,memb Xi,memb ) + Vm (p pi,sat )
= 0i + RT ln(i,g Xi,g ) + RT ln
p
pi,sat
(26)
It is possible to rewrite this equation:

Xi,memb =
i,g
i,memb pi,sat
Xi,g exp
Vm (p pi,sat )
RT

(27)
The expression of molar fractions is:

Xi,memb =
Xi,g =
ci memb
V
Mi m
(28)
pi
p
(29)
We get:
ci =
Mi
i,g
pi
memb
Vm
i,memb pi,sat

exp
Vm (p pi,sat )
RT

(30)
It is reasonable to assume that exp(( Vm (p pi,sat ))/RT) 1 in

most cases. Indeed, the deviation from this assumption is below 1%
for p < 10 bar and below 10% for p < 100 bar.
Hypothesis 5.
p is small, so that exp(( Vm (p pi,sat ))/RT) = 1.
The equilibrium is then written:
Then Eqs. (16) and (18) can be combined:

gi =
RT Ki
Hypothesis 3. The activity coefcient and molar volume are

homogeneous in the membrane
and in the gaseous phase:

i = 0i + RT ln(i Xi ) + RT ln
(21)
Hypothesis 4.
vary slightly.
In this section, the sorptiondiffusion model is obtained thanks

to thermodynamics equations, from the review by Wijmans and
Baker [11]. At each step, the hypotheses used to progress are put in
emphasis.
0i
gi =
(15)
di
dx
ci memb
V
Mi m
memb
where Vm
is the average molar volume of the
membranepermeant system and Mi the molar mass of the
permeant i. Then:
Di =
DS
= i i
l
2.3. Thermodynamics justication of the sorptiondiffusion

model
gi = Ki
Xi =
(11)
It is then possible to introduce the surface permeability Pesurf,i :
GTRsurf ,i =
The molar fraction Xi and the concentration ci (kg/m3 ) are

related thanks to the following equation:
(20)
ci =
Mi
memb
Vm
i,g
pi
i,memb pi,sat
(31)
where pi = p Xi,g is the partial pressure in the gaseous phase. It

is formally equivalent to Henrys law for sorption, the solubility
coefcient is written:
i,g
Mi
Si =
(32)
memb

Vm
i,memb pi,sat
2.3.3. Total mass transfer
From Hypothesis 3, activity coefcients and membrane molar
volume are homogeneous. The solubility coefcients on both sides
are equal as soon as the activity coefcients in both gaseous phases
are equal.
Hypothesis 6.
i,g is equal on both sides of the membrane.
Combining Eqs. (25) and (31), one gets:

GTRsurf ,i = gi =
Di Si
pi
l
(33)
which is the global sorptiondiffusion transport model, identical to

Eq. (13), where:
Di =
RT Ki
ci
(34)
Si =
i,g
Mi
memb
Vm
i,memb pi,sat
(35)
2.4.1. Diffusion and solubility coefcients

The value of Di can be measured by the time lag method. It
is based on the transient state, at the beginning of a permeation
experiment. The quantity of permeants that has crossed the membrane has to be plotted as a function of time. The interception of the
extrapolated linear steady state line (asymptotic curve) with the
time axis is the time lag
. If Di is independent of the concentration,
time lag and diffusion are linked through [22]:
l2
6
is the product of a solubility coefcient, governing the equilibrium

between the gas phase and the sorbed phase inside the membrane, and a diffusion coefcient, governing the transport from
the high concentration area toward the low concentration area.
The simplicity of the set of equations is one of its great advantage and the consistency with experimental measurements as well
[11]. However, the demonstration from thermodynamics needs
a lot of hypotheses, which may not be true in all cases, especially hypotheses concerning the properties homogeneity in the
membrane. Measurements of the solubility coefcient, diffusion
coefcient and permeability on the same sample with independent
methods should be a good way to separate diffusion and sorption
phenomena and to test the validity of the sorptiondiffusion theory
for a determined couple polymer/permeant.
3. Alternative mass transfer modeling
The sorptiondiffusion was developed for rubbery polymers, but
mechanisms of transport in glassy polymers differ totally because
of the difference in polymer structure [22]. Other analytical models
are thus available, for glassy polymers and rubbery polymers as
well.
3.1. Dual mode model in glassy polymers
2.4. Measurements
Di =
909
(36)
Volumetric or gravimetric methods are available for measuring the sorption isotherm and thus the solubility coefcients
of polymers. These methods are independent of permeation measurements. The principle of the gravimetric method, for instance,
is to measure the mass variation of a sample when the surrounding
gas atmosphere is modied.
2.4.2. Permeation measurements
Several methods are available to measure the permeation rate
through a sample, for gases or water vapor: the manometric
method (any gas), the cup method or gravimetric method (water
vapor), the electrolytic process (water vapor), the calcium test
(water vapor), and the tritiated water method (water vapor) [1,28].
The principle is to put a membrane sample between two gaseous
phases at different pressures, the upstream side at high pressure
and the downstream side at low pressure, and to measure the
amount of permeant that crosses the sample as a function of time.
High pressure and low pressure are assumed to remain constant
during measurements, until the steady state is reached. The gas
transmission rate is calculated from the denition, Eq. (4), and the
permeability from Eq. (13).
2.5. Synthesis
The sorptiondiffusion model has been widely used for gas permeation through polymer membranes [11]. It assumes that the
transmission rate of a species is proportional to its partial pressure gradient over the membrane. The proportionality coefcient
3.1.1. Dual mode sorption

In semi-crystalline polymers with a glassy part and a crystalline
part, the molecular conguration is different from the rubbery
state. To explain the deviation from the linear sorption, the dual
mode sorption model was developed [29].
Let us introduce the Langmuir-mode sorption. Contrary to the
linear Henrys law of sorption (Eq. (9)), this mode is based on
the assumption that the permeant molecules occupy specic sites
(micro-voids, etc.) and that a saturation may occur while all the
Langmuir sorption sites are occupied [22]. The Langmuir concentration cH is expressed as:
cH =
bp
cH
i
(37)
1 + bpi
is the Langmuir capacity (or hole saturation constant) and b

cH
is the Langmuir afnity coefcient (or hole afnity constant). At
low pressure (bpi 1) the behavior is linear and at high pressure
(bpi 1) the saturation is reached and the concentration of this
.
population is very close to the constant value cH
In a semi-crystalline polymer below the glass transition temperature, the dual mode sorption model postulates that two
populations of sorbed molecules coexist in the polymer matrix. In
the dense area, ordinary dissolution occurs and linear Henrys law
is respected. In this area, Henrys sorption population has a concentration written cD . The idea that micro-voids are present because
of the glassy phase was suggested by Barrer et al. [30] and these
micro-voids are responsible for a Langmuir sorption population, at
a concentration cH . The total concentration is thus the sum of Henry
and Langmuir populations:
ci = cD + cH = kD pi +
bp
cH
i
1 + bpi
(38)
kD is equal to the solubility coefcient Si in the case of pure

Henrys mode sorption. Otherwise, the solubility coefcient dened
by Eq. (9) is equal to:
Si = kD +
b
cH
1 + bpi
(39)
The solubility coefcient is thus a function of the gas pressure.
910
Fig. 6. Typical sorption isotherm curves [22].
A typical Langmuir and dual mode sorption isotherm is plotted

in Fig. 6, together with a Henry sorption isotherm to illustrate the
difference.
One analysis of the dual-mode sorption model was conducted by
Kanehashi and Nagai [31], based on 250 types of glassy polymers.
They tried to nd correlation parameters for dual mode parameters
and b) on various factors (glass transition temperature, frac(kD , cH
tional free volume, etc.). Good correlations were observed when
several analyses were conducted with the focus on one polymer
family at a time. However, a wide variation appears when looking
at the whole polymer panel.
3.1.2. Diffusion coefcient and permeability
The rst mass transfer models based on the dual mode sorption
model postulate that the adsorbed molecules population of Langmuirs mode is immobilized and that it doesnt participate to the
total transfer [29]. Ficks law is thus respected only for the Henrys
mode population. For a unidirectional ux:
gi = Di
cD
x
(40)
The second Ficks law in the case of homogeneous diffusion coefcient (Eq. (8)) is then written:
2
(cD + cH )
cD
= Di
t
x2
(41)
This unsteady state equation has analytical solution for the

limiting cases bpi 1 and bpi 1, but not for the general case
[29]. And for steady state, it is equivalent to the sorptiondiffusion
model, since Langmuirs mode population vanishes from the
equation, once in equilibrium with the gas partial pressure and
immobilized.
Other authors developed a model of partial immobilization,
where Langmuirs mode population is not totally immobilized but
has a diffusion coefcient different from the one of Henrys mode
population [3234]. Ficks rst law is thus written for a unidirectional ux:
gi = DD
cD
cH
DH
x
x
(42)
For a steady state and homogeneous membrane, considering a

pressure that vanishes at the downstream side (pi,2 = 0), the mass
ow rate becomes after integration:
GTRsurf ,i = gi =
1
l
DD kD pi,1 +
bp
DH cH
i,1
1 + bpi,1
(43)
Diffusion, solubility and permeability coefcients are thus written for this case:
Si =
b
cH
ci
= kD +
pi
1 + bpi,1
Pesurf ,i =
Di =
GTRi l
1
=
pi,1
l
lPesurf ,i
Si
DD kD +
(44)
b
DH cH
1 + bpi,1
b)/(1 + bp ))
DD kD + ((DH cH
i,1
b)/(1 + bp ))
kD + ((cH
i,1
(45)
(46)
All three parameters are thus dependent on the pressure. Evolutions of S, D and Pe as a function of the pressure have been observed
experimentally. This model would be able to explain these behaviors [22]. However, there is no clear evidence of the existence of
both populations of Henrys mode and Langmuirs mode sorption,
which would have different solubility and diffusion coefcients.
The nature and distribution of the micro-voids responsible for Langmuirs mode sorption remain unknown.
Islam and Buschatz [35] have developed a theoretical explanation of the Dual Mode formalism, based on a ux equation
expressed in term of chemical potential gradient. In this model,
the formalism is identical but the meaning is different, since the
Langmuirs mode population is assumed to be fully immobilized.
3.2. Brief review on other modeling concepts for mass transfer in
polymers
3.2.1. FloryHuggins mode sorption
This sorption mode was presented by Flory [36]:
ln(ai ) = ln
pi
= ln i + (1 i ) + (1 i )2
pi,sat
(47)
where i is the volume fraction of the permeant in the polymer

and the enthalpic interaction parameter between the polymer
and the solute. This model is supposed to be adapted when the

interactions between diffusing molecules are stronger than the
permeantpolymer interaction [22]. This may be due to plasticization by sorbed molecules, or the association of clusters
for hydrophobic polymer/water systems. A typical FloryHuggins
sorption isotherm is plotted in Fig. 6.
3.2.2. BET mode sorption
A BET mode sorption corresponds to the combination of the
Langmuir and FloryHuggins modes [22]. In practice, it can be representative of the sorption of water in highly hydrophilic polymers.
A typical isotherm sorption is plotted in Fig. 6.
3.2.3. Gaspolymer matrix model in glassy polymers
This model is presented as an alternative to the dual mode model
for glassy polymers able to explain the dependence of solubility and
diffusion coefcients to the permeant concentration [22]. In this
model, it is assumed that there is only one population of permeant, but that an interaction between the permeant and the polymer
matrix exists. The effect of a concentration increase in the polymer
is an increase of the diffusion process (through an increase of the
polymer mobility) and a decrease of the sorption rate. The proposed
equations are:
Tglass (0) Tglass (ci )
=
Si = Si,0 exp(KS )
Di =
Di,0 (1 + KD ) exp(KD )
4.1. Inuence of the temperature
(51)
Di = Di,0 (1 + KD ci ) exp(KD ci )
(52)
If KD ci is small, one gets for the permeability:
3.2.6. Free Volume theory

Free volume models are based on the assumption that molecular transport is due to free volume redistribution and not thermal
activation [22]. The free volume fraction f is dened as:
=
Vf
Vtot
Di =
Di0
exp
(54)
EaD
RT
(55)
H
S
RT
(53)
3.2.5. Molecular models of transport in rubbery polymers

These models are based on the assumption that a certain amount
of energy is necessary for a molecule to jump from one position to
another [22]. It is consistent with the observations of an energyactivated behavior. The estimation of the energy level differs from
one model to another, it is basically related to polymer chain displacements and interaction forces which are involved in molecular
displacement.
Vf
4.1.1. Arrhenius law

The diffusion in polymers is a thermally activated process.
Experimental data suggest that Arrhenius law is an appropriate
equation for the thermo-activation, at a given pressure and on a
narrow range of temperature [22]:
Si = Si0 exp
3.2.4. Site distribution model for sorption in glassy polymers

An other model is based on the assumption that all sorption sites
have different energy levels [37,38]. The distribution of site energies can be chosen, the linear Henrys law and dual mode sorption
model are two particular cases for this model. The variation of the
solubility coefcient as a function of pressure is well tted thanks
to this model, with a lower amount of tting parameters than for
the dual mode model.
Vtot
Several alternative models have been developed, especially for

sorption, in order to explain experimental behaviors different from
what is predicted by the linear sorptiondiffusion model. These
models mainly apply for glassy and semi-crystalline polymers,
where it is assumed that the crystalline part and the amorphous
one have different properties. For these non-linear behaviors, several physical explanations coexist, which may be relevant or not
depending on the polymer and permeant species that are studied.
This section is just a brief review on these alternative models, the
literature about theory and experimental results is too extensive to
be exhaustively presented here.
(49)
Si = Si,0 exp(KS ci )
f =
3.3. Synthesis
4. Parameters inuence on transport coefcients for

polymers
Tglass (0) and Tglass (ci ) are respectively the glass transition temperature of the pure polymer and of the polymergas system
at concentration ci . With the additional assumption of a linear
dependence of Tglass (ci ) on ci , one gets:
Pei = Si,0 Di,0 exp((KD KS )ci )
Correlations between f and S or D, able to explain the dependence of D to some parameters like concentration, permeant shape
and size, temperature and glass transition temperature, are proposed. This theory seems to be well tted to rubbery polymers/large
organic vapors systems, but not for small molecules (the dependence on concentration is much lower). It is however not predicting
an Arrhenius temperature dependence, which is a source of controversy [22].
(48)
(50)
911
Pei = Pe0i exp

i = i0 exp
EaP
RT
EaP
RT
(56)

(57)

(58)
From Eq. (15), it comes:

EaP = EaD + HS
(59)
For diffusion, the activation energy EaD
corresponds to the energy

level necessary to jump from one position to another, it is thus
always positive [22]. The heat of sorption HS may be positive or
negative. It is generally positive for gases far from their critical temperature (H2 , N2 , O2 , etc.) and negative for condensable gases and
vapors (CO2 , SO2 , H2 O, etc.). Diffusion has a greater dependence to
temperature than sorption, the permeability energy activation EaD
is thus positive.
4.1.2. Experimental results
Flaconnche et al. [39] measured the diffusion coefcient, solubility coefcient and permeability to He, Ar, N2 , CH4 and CO2
of various polyethylenes (LDPE, MDPE, HDPE, HPDE-RI). Measurements were made from 40 C to 80 C, at a pressure between 4 and
10 MPa for He and CH4 , and at constant pressure of 10 MPa for other
gases. Energy activations are positive for permeabilities, between
29 and 51 kJ/mol, for diffusion as well, between 17 and 46 kJ/mol,
912
and for sorption between 3 and 20 kJ/mol, except CO2 that has an
activation energy between 2 and 1 kJ/mol.
Gajdos et al. [40] also measured the diffusion coefcient, solubility coefcient and permeability to O2 and N2 of PE and PP (normal
and co-extruded) for three temperatures: 20 C, 40 C and 60 C. For
PE, on both thicknesses (0.03 mm and 0.1 mm), a very good correlation for Arrhenius thermo-activation is observed, for all coefcients
(correlation coefcient between 0.90 and 0.99). For PP, Arrhenius
law is respected in some cases, but not for all coefcients and
both gases. The diffusion coefcient, in particular, has a temperature dependence that deviates from Arrhenius thermo-activation.
In these measurements, all activation energies for permeability
are positive (between 57 and 187 kJ/mol), the permeability is an
increasing function of the temperature. But all enthalpies of sorption are positive (between 57 and 197 kJ/mol) and all activation
energies for diffusion are negative except one (27 kJ/mol for the
positive value of O2 in PP, between 4 and 44 kJ/mol for others).
It is in contradiction with the theoretical inuence of the temperature on the diffusion coefcient. An inversion between D and S is
possible, or a bias in the estimation of D, which is based on the time
lag method.
Other measurements on a polyimide membrane (6FDA-durene)
were made by Lin et al. [41], Lin and Chung [42]: the diffusion coefcient, solubility coefcient and permeability to He, H2 , O2 , N2 ,
CH4 and CO2 , from 30 C to 49 C and at 1 MPa. Activation energies are positive for the permeability of O2 , N2 and CH4 (from 2.4
to 7.25 kJ/mol), and for the diffusion coefcient of O2 , N2 , CH4 and
CO2 (from 17.55 to 24.29 kJ/mol). The heats of sorption are negative for O2 , N2 , CH4 and CO2 (from 19.84 to 15.14 kJ/mol). The
permeability energy activation of CO2 is almost null (0.24 kJ/mol).
4.2. Inuence of the pressure and the concentration
4.2.1. Diffusion coefcient
The effect of high pressure at the upstream side may lead to two
opposite effects [22]:
An increase of the polymer density, that may result in a free
volume reduction and then a transfer velocity decrease.
An increase of the permeant concentration, that may result in
plasticizing of macromolecular chains and thus an increase of free
volume and transfer velocity.
Below 10 MPa, Naito et al. [4345] proposed the following equation for rubbery polymers (PE, PP, poly(ethylene-co-vinyl-acetate)
and polybutadienes):
D(c, p) = D(0, 0) exp(1 p + 2 c)
(60)
D(0, 0) is the diffusion coefcient at c = 0 and p = 0, exp(1 p) is the

term for pressure effect (1 is a negative term) and exp(2 c) is the
term for concentration effect.
4.2.2. Solubility coefcient
At pressure lower than 10 MPa, the solubility coefcient appears
to be independent on gas pressure and concentration for slightly
condensable gases [22].
4.3. Inuence of the crystallinity

Most attempts to take into account the crystallinity are based
on the two-phase model [22,48]. The assumption is that in a semicrystalline polymer, sorption and diffusion only happen in the
amorphous part. Crystalline areas are impermeable barriers for
diffusion and excluded volumes for sorption. The following expressions are proposed:
Si = S amor
(61)
D
Di =

(62)
where S* and D* are the coefcients in an amorphous completely

relaxed state (degree of crystallinity = 0%), amor the amorphous
phase volume fraction, the chain immobilization factor (the crystalline zones might decrease the mobility of polymer chains in the
amorphous phase) and the tortuosity factor. It is assumed that
the nature of the amorphous phase remains the same despite the
existence of crystalline areas. Thus:
S = Samor
D = Damor
(63)
(64)
From Eq. (61) it appears that a high crystallinity rate has a positive impact on the barrier properties, as it has a linear and direct
impact on the solubility coefcient and thus the permeability.
4.4. Inuence of the orientation
The inuence of the amorphous chains morphology was
observed, showing that oriented polymers may have different
properties [22]. The interpretation is based on a free volume fraction modication due to the polymer chains reorganization, leading
to an increase or a decrease of transport properties.
4.5. Synthesis
Temperature appears to be the main parameter which inuences the transport properties of polymer membranes. The
dependence is close to an Arrhenius activation in most cases. The
inuence of the pressure and concentration has not been observed
on experimental measurements below 1 MPa, which includes in
theory the atmospheric pressure (outside VIPs) as well as any vacuum level (inside VIPs). The crystallinity rate and orientation are
also playing a role in the permeation properties, since they have a
great inuence on the microstructure thus on the sorption sites
shape and density and on the diffusion properties. In the literature, the inuence of the total pressure is almost never reported,
the permeant partial pressure on both sides of the polymer membrane is the only physical input. The variation of total pressure and
thus on the permeant concentration in the gas phases, from one
measurement to another, should be taken into account in order to
ensure that this total pressure does not play a role in the permeation
properties.
5. From polymer permeability to multilayer gas barrier
membrane permeability
5.1. Multilayer gas barrier membrane morphology
4.2.3. Experimental results

On the measurements of Flaconnche et al. [39], between 4 and
10 MPa, no inuence of total pressure was observed for the permeability of PE to He and CH4 . Other measurements lead to the
conclusion that CH4 and CO2 solubilities in PE are independent of
pressure below 4 MPa [46], as well as CH4 and N2 solubilities in PE
below 15 MPa [47].
When a moderate gas barrier performance is needed, i.e. the

requirements for air or water vapor tightness are not too high and
the service life is not longer than few months, simple polymers can
be used as gas barrier membranes. One of the main applications
for barrier polymers is food and beverage packaging [49,50]. The
permeability of cheap polymers are listed in Table 3.
913
Table 3
Transfer properties of food packaging polymers.
Ref.
Sample
PET 20% cryst.
[48]
[39]
PET amorphous
LDPE 30% cryst.
HDPE 63% cryst.
PE 0.1 mm
[40]
PP 0.03 mm
Temperature (K)
Gas
S (cm3 (STP)/(cm3 Pa))
D (cm2 /s)
Pe (cm3 (STP)/(cm s Pa))
4 10
5 107
9 107
4 10
2 109
5 109
1.6 1011
1 1015
4.5 1015
298
298
298
H2 O
N2
O2
343
342
N2
N2
2.6 107
9.0 108
2.0 106
1.2 106
5.1 1013
1.0 1013
333
333
333
333
N2
O2
N2
O2
1 104
1 102
8 105
7 105
6 108
5 108
6 109
9 109
5 107
5 105
1 107
1 107
Simple polymers are really too permeable for VIP. The mass
transfer has to be as low as possible to get a service life of several
decades and it is only reachable if the barrier properties of the envelope are increased. Multilayer membranes are designed to improve
the gas barrier properties of simple polymer lms. The idea is to
combine several material properties to get a membrane that has
better properties than each individual lm alone.
As presented in Section 1, two types of multilayer membranes
can be used for VIP envelopes (see Fig. 4): laminated aluminum
membranes (AF type) and metalized polymer membranes (MF
type) [1]. Unfortunately, even if laminated aluminum membranes
have good gas barrier properties, they are responsible for a thermal bridge that drastically decreases the thermal performance of
the whole panel (see Section 1 and Ref. [6]). That is why multilayer
membranes with metalized polymer lms are developed for VIP
envelopes. They are based on polymer lms coated with a thin layer
of metal, often aluminum. The low amount of metal in the membrane decreases the heat transfer through the membrane thermal
bridge. An example of such a gas barrier membrane is represented
in Fig. 7.
Coating polymer lms with a thin metallic or inorganic layer
is a very efcient way to improve the barrier properties of the
lm, without losing the good mechanical properties of the polymer. Barrier properties can be improve by a factor of 100, for a
coating thickness less than 1% of the polymer thickness [5053]. For
example, oxygen and water vapor permeabilities were decreased
by respectively 99% and 98.5% on a metalized PET lm compared
to a non-metalized PET lm [50] and oxygen permeability was
decreased by 99.2% on a SiOx -coated PET [53]. This kind of coated
polymers was extensively developed as oxygen and water vapor
barrier envelope for food and medical packaging [51] and more
recently for electronic devices like solar cells or at panel displays [54]. Mass transfer modeling is thus focused on multilayer
membranes with metalized polymer lms, as they have better performances for vacuum insulation panels.
5.2. Analytical modeling for mass transfer through the barrier

membrane
5.2.1. Permeation properties of the whole barrier membrane
Most laboratories working on gas barrier membranes of VIPs
use the model of sorptiondiffusion detailed in Section 2 for water
vapor and dry air transport [1,8,9,17,21,28,5558]. It is indeed a
very easy model for property identication and for mass transfer
simulation.
The assumptions commonly used are listed below:
1. The outer and inner gaseous phases are binary mixtures of water
vapor and dry air, considered as a mixture of ideal gases.
2. For each of these gases, the total transmission rate GTRtot is the
sum of a faces contribution GTRsurf (on the whole surface A) and
an edges contribution GTRlin (on the whole perimeter P):
GTRtot = A GTRsurf + P GTRlin
(65)
3. The mass ow rates from outside to inside follow the linear sorption/diffusion model, i.e. each gas transmission rate proportional
to the partial pressure difference (pg is the positive difference,
i.e. pg = pout pin which is different from the convention used
in Section 2):
GTRsurf = surf pg
(66)
GTRlin = lin pg
(67)
4. Permeances are independent of the gas composition.

5. Permeances are only dependent on the temperature, following
an Arrhenius law.
0
exp
surf (T ) = surf
EaP
R
Fig. 7. Example of a multilayer membrane with metalized polymer lms [8].
1
T
1
T0

(68)
914

0
lin (T ) = lin
exp
EaP
R
1
T
1
T0

(69)
The heat-sealed joint and the envelope are supposed to obey the
sorptiondiffusion model for both dry air and water vapor, with different transfer coefcients for each case. As stated previously, this
paper does not address the issue of gas permeation through the
heat-sealed joint of the envelope, or gas permeation at the scale
of a whole VIP. Following paragraphs are thus focused on the surface permeation through barrier membranes, excluding the edge
effects.
5.2.2. Ideal laminate theory for a multilayer membrane
As an heterogeneous material, a multilayer coated polymer
membrane has no intrinsic permeability. It is possible to dene the
apparent permeability, from Eq. (13), as a function of the surface
gas transmission rate and the pressure gradient:
Pei,app (T ) =
GTRi
l
pi
(70)
It is possible to get the total permeability of a multilayer barrier

membrane thanks to the law of superposition of the ideal laminate theory, as soon as the property of each layer is known. This
law can be written as [25,59]:

l
elem
=
Peapp
Peelem
(71)
where elem and l are respectively the thickness

of each elementary
layer and the whole multilayer membrane ( elem = l), Peelem and
Peapp are respectively the apparent permeabilities of each elementary layer and of the whole multilayer membrane. It is possible to
use permeances, dened by Eq. (59), to rewrite the law [17]:
1
1
=
app
elem
Fig. 8. Mechanism of gas permeation through a defect free substrate coated with
barrier layers containing defects [54].
the permeation rate through the micro-defects free areas is negligible (molecules are blocked) [51,62,67]. Nano-defects may still
be present, they would result for the micro-defects free area in an
apparent permeability greater than the bulk material permeability
[62,67].
The improvement of the elementary coated lms properties
leads to the improvement of the multilayer barrier membrane
made from these coated lms, as explained above (see Eq. (71)). To
compare the coated lm permeability Peapp,coated to the uncoated
lm permeability Peapp,uncoated and thus the barrier improvement,
the barrier improvement factor BIF can be used [51]. It is dened
as:
BIF =
Peapp,uncoated
Peapp,coated
Pepoly
Peapp,coated
(73)
Since the coating thickness is much smaller than the polymer

substrate thickness in most cases (coat poly ), the coated polymer
thickness is equal to the uncoated one. It is thus possible to write:
(72)
It is actually the same law as for an electric system that contains

resistances in series. The resistance to gas is dened as Rg = 1/ g
and the total resistance is the sum of the individual resistances.
5.3. Apparent permeability of a coated polymer lm
5.3.1. Transport mechanisms in a coated polymer lm
An elementary coated layer is made from a polymer substrate
and a thin coating barrier layer. The mass transfer through a coated
polymer lm is assumed to follow two separate mechanisms [51]:
1. In non-damaged bulk materials (the polymer substrate and nondamaged area of the coating layer), mass transfer follows the
Fickian diffusion model, with the bulk material properties.
2. In damaged areas (the thin coating layer containing defects), gas
transport can occur through the layers defects: pinholes, grain
boundaries, micro-cracks, etc.
These mechanisms of mass transfer are different, so that the
permeation properties of many coating layers are different from
the permeation properties of their bulk counterparts [51]. This
assumption of double transport mechanism was mainly studied
for oxygen and water vapor transport, it can be used for any
gas [17,25,28,51,52,54,6066]. These mechanisms of transport in
defect free and imperfect layers are illustrated in Fig. 8.
It should be noted that two kinds of defects may be identied: nano-defects (between 0.3 and 1 nm) and micro-defects
(>1 nm, generally about 1 m) [62,67]. Most studies consider that
micro-defects like pinholes or microcracks are much more effective paths through the coating layer for gas permeation and that
BIF =
poly
coated
GTRpoly
GTRcoated
(74)
5.3.2. Inuence of the coating layer and polymer substrate

thicknesses
The permeability of a coated lm is experimentally a function of
the polymer substrate material, coated layer material and coated
layer geometry: thickness and distribution of defects (size and density) [51]. It has been observed that for many polymer/coating
associations, the apparent permeability decreases when the coating thickness increases, until a minimum value Pemin obtained for a
coating thickness greater than a critical value coat,crit [51,54,6769]
(see Figs. 9, 10 and 11a). It should be noted that for the association
PET/aluminum used in most VIP barrier membrane, coat,crit is fairly
low, approximately 15 nm [51,68].
Numerical simulations from Hanika [63] showed that a critical
thickness also exists for the polymer substrate. For a coating layer
with a constant defect size and density, the apparent permeance of
a coated polymer decreases when the substrate thickness increases,
until a value which remains constant while the thickness is above
a critical thickness poly,crit (see Fig. 12)
If the coating layer and polymer substrate both have a thickness above the critical one (respectively coat,crit and poly,crit ), the
apparent permeance of the coated polymer is independent of the
thicknesses. It is then possible to normalize the barrier improvement factor, if the reference lm thickness (uncoated polymer) is
set to 100 m [25]:
BIF 100 =
app,uncoated,100
app,coated
(75)
915
Fig. 9. OTR of coated PET as a function of coating thickness [51].
Fig. 10. WVTR of coated PET as a function of coating thickness (T = 28 C and RH=90%)
[54].
5.3.3. Roberts model for the permeability of a coated lm

The intrinsic permeability of a coated lm has no meaning, but
the apparent permeability can be measured, following the same
principle as presented above for multilayer barriers (see Eq. (70)).
From the hypothesis of the coexistence of a bulk diffusive transfer and a micro defect dominated transfer, a model is proposed by
Roberts et al. [62] for the total apparent permeability as a function
of the ideal laminate theory permeability PeILT (see Section 5.2.2)
and the defect driven permeability Pedef :

Peapp,coated = Pedef +
Pedef
Pepoly

PeILT
(76)
Fig. 12. Oxygen permeance of a coated PET lm as a function of the polymer substrate thickness (defect density n0 = 104 cm2 , AD is the individual defect area) [63].
Pedef is the effective permeability of the coating layer with

defects in the case where this layer is totally impermeable to the
permeant in the non-damaged area. From Eq. (71), the ideal laminate theory permeance is equal to:

PeILT = tot
poly
Pepoly
coat
Pecoat
1
(77)
where poly and coat are respectively the thicknesses of the polymer substrate and the coating layer (poly + coat = tot ), Pepoly and
Pecoat are respectively the permeabilities of the coating layer and
the polymer substrate. The most favorable case is when the coating
layer is practically impermeable to the permeant gas, then PeILT 0
Fig. 11. Water vapor permeance of aluminum-coated PET as a function of (a) aluminum thickness and (b) surface fraction of pinholes (defects). The value close to each point
is the aluminum thickness (T = 25 C, RH=90%) [17].
916
and the permeation is only due to the defects driven transport:

Peapp = Pedef . Otherwise, the apparent permeability is written:

Pedef
Pepoly
poly /tot
Pepoly
coat /tot
Pecoat
1
(78)
For sufciently good coating layer

Pedef /Pepoly < 0.05, so that Eq. (78) becomes:
poly /tot
Pepoly
coat /tot
+
Pecoat
barrier
properties,
1
(79)
If nano-defects are present in the coating layer and increase the

gas transport, then the value of Pecoat is different from the bulk coating material permeability. It would be the sum of a Fickian diffusion
value (non-damaged bulk material) Pecoat,bulk and a nano-defect
diffusion value Pecoat,nanodef :
Pecoat = Pecoat,bulk + Pecoat,nanodef
(80)
5.3.4. Analytical modeling of the micro-defects permeability

Prins and Hermans [60] found approximate solutions for the
diffusion problem in a polymer substrate with a coating layer containing only cylindrical defects (defects density n0 , defects radius
r0 , substrate thickness poly ). The rst limiting case is for large
defects, when the defects size is greater than the substrate thickness (poly /r0 < 1):
Peapp,coated = Pedef = n0 r02 Pepoly
(81)
It means that the coated layer permeability is proportional to

the non-covered area: only the total defects area n0 r02 participate
to the mass ux.
On the contrary, the second limiting case is for small defects,
when the defects size is much smaller than the substrate thickness and the total defects area much smaller than the total area
(poly /r0 1 and n0 r02 1). The defect driven permeability can
then be estimated by:
Pedef = 3.71n0 r0 tot Pepoly
(82)
In this case, the permeance def = Pedef /tot is independent of

the substrate thickness, which means that the substrate thickness
is above the critical thickness poly,crit according to Section 5.3.2 (see
Fig. 12).
An intermediate case, providing poly /r0 > 1 and n0 r02 1, gives
the following equation:
Pedef = n0 r02 1 + 1.18
poly
r0
Pepoly
(83)
Pedef is from these three equations independent of the coating

thickness, if the total thickness is assimilated to the substrate thickness (coat /poly 1). This result is consistent with the experimental
observations reported in Section 5.3.2 concerning the coating thickness (see Figs. 9, 10 and 11a), as soon as the coating thickness is
above the critical thickness coat,crit . Nevertheless, the permeability
is indirectly dependent on the coating thickness since the defects
size distribution (size and density) is dependent on the coating
thickness among other things. Garnier et al. [69] measured this
inuence (see Fig. 13).
The critical value of the coating thickness coat,crit is probably the
minimal thickness that allows the complete or maximal coverage of
the polymer, so that the pinhole number as well as size decreases to
a minimum situation for coat,crit and stays constant for thicknesses
greater than coat,crit [51]. For a determined couple polymer/coating,
the critical thickness coat,crit appears to be the same for oxygen and
water vapor [51].
Rossi and Nulman [70] and Yanaka et al. [71] came to the conclusion that the defects permeability is directly proportional to the
bulk polymer permeability, following a proportionality constant
Kdef that is function of the defects size distribution:
Pedef = Kdef Pepoly
(84)
This result is consistent with Eq. (81). An expression of Kdef is

proposed for circular holes by Rossi and Nulman [70] and rectangular holes by Yanaka et al. [71]. Kdef is only dependent on the
geometry, but is independent of both temperature and permeant
species.
From the results of different numerical simulations, Hanika [63]
proposed the following heuristic equation for evenly distributed
defects of equal area Adef and density n0 :
Pedef =
n0 Adef
1 exp(0.507(
Adef /poly )) + 0.01n0 Adef
Pepoly
(85)
If the defects size is not uniform, the defects size distribution

is split in different classes. For each class, one elementary defect
permeability is computed from the average defects density and size.
The total permeability is the sum of all elementary permeabilities.
Garnier et al. [69] have measured that the water vapor permeability linearly increases with the surface fraction of micro-defects
(see Fig. 11b). It is consistent with Eq. (81) (and thus Eq. (84))
without restriction, with Eqs. (82) and (83) only if poly /r0 remains
constant, and with Eq. (85) only if

Adef poly remains constant
and above 1 (equivalent to poly /r0 < 1 for circular micro-defects).
Garnier et al. [17] have also measured that the water vapor permeability is an exponentially decreasing function of the coating
thickness for an aluminized PET (see Fig. 14)
5.3.5. Musgrave model for the permeability of a coated lm
Musgrave [72] proposed to use nite element method simulations to estimate the oxygen permeation rate through a polymer
layer between two coating layers containing defects. The geometry is reduced to a rectangular PET box (2.5 mm 2.5 mm area and
12 m thick) with two quarters of pinholes in opposite corners.
Fig. 13. Micro-defects (pinholes) surface fraction of aluminum-coated PET as a function of aluminum coating thickness (T = 25 C, RH=90%) [69].
917
5.3.7. Garnier model for the permeability of a coated lm

Garnier et al. [17] proposed an other model based on the analogy
with an electric system, with resistances in parallel and in series.
The principle is analog to what is presented in Section 5.2.2. The
polymer layers and the coating layers are considered as resistances
in series (see Fig. 16a) and the coating layer permeance is calculated
considering that the defect-free aluminum coating area and the
glue lled holes act as resistances in parallel (see Fig. 16b).
For an aluminum-coated polymer lm, where the total surface
fraction of pinholes in the aluminum coating layer is equal to r02 n0 ,
and providing that n0 r02 1, the apparent permeability Peapp,coated
is from this model:
Peapp,coated = tot
Fig. 14. WVTR of aluminum-coated PET with one PET protective layer as a function
of aluminum coating thickness (T = 25 C, RH=90%) [17].
Ficks law of diffusion is solved for oxygen transport thanks to

the formal analogy with Fouriers law. The simulation parameters
are tted with experimental results of one and two aluminumcoated layers membrane, permeances used are respectively 0.055
and 0.0005 cm3 (STP)/(m2 d bar). Permeance for 3 and 4 layers are
computed, but no experimental data are used to validate the results
since these ultra high oxygen barrier membranes had permeance
below the limit of measurement for oxygen permeance in 2005,
0.0005 cm3 (STP)/(m2 d bar). It is still the case in 2011 [66].
5.3.6. Thorsell model for the permeability of a coated lm

Thorsell [65,73] proposed a hybrid model for a polymer lm
between two coating layers containing defects. Based on the
assumption that the defect free coating is impermeable and that
the size and distribution of circular defects are known, the double coated lm is assimilated to a partial resistance network (see
Fig. 15). Each defect (considered as an input or an output depending on the side) has a so-called cylinder resistance, calculated from
axisymmetric FEM simulations (COMSOL Multiphysics ). Close
cylinders defects are linked through so called eld resistances, calculated from a 2D analytical resolution of the dipole problem in
eld theory.
Oxygen permeability estimated with this model is coherent with
results from other models and measured data, even though the
defect distribution used for simulation and the experimental value
of permeability are not taken on the same sample, which prevents
to estimate the accuracy of this model.
poly
Pepoly
coat
n0 r02 Peglue + Pealu
1
(86)
Comparison of model and experimental results shows an agreement described as surprisingly good by the authors (see Fig. 17).
The surface fraction of pinholes n0 r02 was measured by scanning
electron microscopy. The good agreement is surprising since it was
observed by many authors that the permeability is a function of
defects density and not a function of the total defect surface fraction
[53,74].
5.3.8. Inuence of temperature and transport mechanisms
Henry et al. [52] have measured the activation energies of permeability to oxygen and water vapor for normal PET, AlOx coated
PET and indium tin oxide (ITO) coated PET. The activation energy of
the oxygen permeability is found identical for all lms. The interpretation is that the transport is diffusive and occurs only on the
polymer, and that the coating layer is an absolute barrier, only
crossed by the permeant molecules through the micro-defects.
Oxygen transport is thus a micro-defect dominated permeation.
The activation energy of the water vapor permeability is dependent
on the coating, which suggests that diffusive transport might occur
through the non-damaged part of the coating layer, or at least that
an interaction between water vapor and the coating layer exists.
Fahlteich et al. [54] have observed the same behavior for oxygen and water vapor permeation through silicon oxide (SiOx )
coated PET and zinc tin oxide (ZTO) coated PET. Oxygen permeation through those lms is a micro-defect dominated permeation
with constant activation energy, whereas water vapor permeation
is also driven by chemical interaction between water vapor and the
coating layer, with a varying activation energy.
The difference of value of the permeability activation energy, for
uncoated and coated polymer, appears to be a good way to detect
the transport mechanism of gas in coated polymer lms. Beyond
these two particular examples, other experiments in the literature
Fig. 15. Hybrid model from Thorsell for gas permeation through a double coated polymer lm [65,73]. (a) Three resistances in series between two defects. (b) Resistance
network between defects in the upper coating (black solid circles) and defects in the lower coating (gray dashed circles).
918
Fig. 16. Electric resistances analogy for the permeance modeling of an aluminum-coated polymer lm [17]. (a) Aluminum-coated polymer lm as a bilayer. (b) Aluminum
coating with micro-defects (pinholes).
tend to prove that the oxygen and nitrogen permeation through

non organic coated polymer lms is a micro-defect driven process,
whereas for water vapor an additional transport mechanism exists,
probably involving capillarity condensation [51,67,25].
5.4. Synthesis
Barrier properties of simple polymer membranes are not sufcient for several applications where the atmospheric gases
transmission rates should be extremely low, including vacuum
insulation panels. With a coating layer of inorganic material on the
polymer substrate, typically 10100 nm of silica, metal oxide or
pure metal, the permeation properties can be improved by one or
two orders of magnitude. The superposition of several coated layers
leads to even better barrier properties, the multilayer membrane
acting like several barriers in series. The apparent permeability
can be calculated thanks to physical laws analog to those used for
electric circuits.
The transport mechanism through the coated polymer layers is
considered as a micro-defect driven process. Indeed, the very low
thickness of the coating layers leads to the presence of a microdefects distribution, depending among other things on the polymer
and coating materials and on the coating layer thickness. Materials used for coating layers have bulk permeabilities several orders
of magnitude below the permeabilities of polymers or glues (in
multilayer membranes) that are directly adjacent to them, so that
Fig. 17. Comparison of model and experimental results for the permeability of a
coated polymer lm (T = 25 C, RH=90%) [17].
the micro-defects represent a much more efcient path through a

coating layer than the defect free area.
In order to increase the barrier properties, the number and
size of the micro-defects should be minimized. The apparent permeability of a coated polymer lm, or a multilayer membrane
containing coated polymer lms, appears to have the same temperature dependence as the polymer alone for oxygen and nitrogen
permeation: the gas ux is totally blocked by the defect free
areas of the coating layers, dry air only diffuses through the
polymer and the empty or glue-lled micro-defects. For water
vapor, however, it seems that an interaction between water
molecules and coating layer exists, as the activation energy difference between uncoated and coated polymers permeabilities could
indicate.
6. Conclusion
Mass transfer in VIPs is a crucial issue when looking at the durability of vacuum super insulation materials. A decent service life
for building applications is only insured if the ability to maintain a
low pressure and a low humidity during several decades is proved.
The gas barrier envelope thus plays a key role in the durability of
vacuum insulation panels, it is supposed to decrease at a minimum
level the permeation rates of atmospheric gases. The understanding of gas permeation mechanisms through multilayer membranes
with metalized polymer lms is needed in the scope of aging modeling, especially the dependence of barrier properties to materials,
manufacturing, and climatic conditions (temperature and relative
humidity).
Mass transfer theory for the permeation of atmospheric gases
through a VIP envelope is based on the sorptiondiffusion model,
initially designed for permeation through homogeneous polymer membranes. This model, very easy to use, has shown a
certain consistency with experimental observations on several
polymers. However, the thermodynamics demonstration of this
model is not straightforward, a lot of hypotheses is needed. Many
alternative models are also proposed, mainly for glassy and semicrystalline polymers. They are often based on the assumption that
the crystalline volume fraction of the polymer and the amorphous one have different behaviors. Sorption is not linear in
these alternative models, but follows other isotherm curves, like
Langmuir of FloryHuggins modes for instance. Concerning the
inuence of external parameters on the permeation properties of

polymers, the thermo-activation, following an Arrhenius law for
the temperature dependence, has been repeatedly observed. The
inuence of a low pressure (below atmospheric pressure), however, has not been observed. For high pressures, the permeation
properties may vary, and some alternative models have been developed in order to explain this pressure dependence of transport
coefcients.
For VIPs, the requirements concerning the atmospheric gases
permeation rates are very constraining, and simple polymer
envelopes would not be able to maintain the vacuum over a sufciently long period. However, polymer membranes have very
good mechanical properties, particularly in term of exibility and
strength. In order to benet from these polymer properties, a very
efcient strategy to increase the barrier properties is to coat polymer lms with a thin inorganic layer, made of a material having
very good barrier properties to the gases considered. Polymer lms
coated for instance with aluminum can increase by two orders of
magnitude or more their barrier properties. The superposition of
several coated lms is also a way to increase the barrier properties
of the membrane.
The sorptiondiffusion model has been extended to this kind of
multilayer membranes containing aluminum-coated lms. It has
been shown that the transport mechanism of permeant molecules
in a coated layer is a micro-defects driven process. The transport
through the polymer layer substrate is a Fickian diffusion, whereas
gas molecules can only cross the coating layer through microdefects. Indeed, the coating layer material is often chosen for its
very good barrier properties, but the low thickness prevents the
manufacturing of a homogeneous and perfect layer. In the coating
layer, the defect free area is totally blocking the gas molecules, they
have to diffuse through the polymer layer to nd a micro-defect and
to cross the coating layer. The apparent permeance of the coated
polymer lm is thus a function of the micro-defects distribution.
The total permeance of a multilayer membrane can be calculated
thanks to the ideal laminate theory, based on the electric analogy
of resistances in series.
Concerning the temperature inuence on the instantaneous
gas permeation rates through an aluminum-coated polymer lm,
experimental results and numerical results based on Arrhenius law
are consistent. For dry air permeation, the energy activation is only
dependent on the polymer properties: the energy activation is the
same for coated or uncoated lms. For water vapor permeation, it
seems that a metal/water interaction exists in the mass transfer
phenomenon. Because of this interaction, the energy activation of
the water vapor permeation rates is different for coated or uncoated
lms. For the humidity inuence, no explicit model is proposed to
explain the inuence of the humidity level on the air and water
vapor instantaneous permeation rates that has been observed on
experimental results.
An advanced research work on permeation experiments and
modeling is needed to improve the knowledge about mass transfer through the multilayer gas barrier membranes, in particular the
combined effect of humidity and temperature on the permeation
rates. Considering the permeation of dry air and water vapor as a
coupled mass transfer of several atmospheric gases through these
membranes, instead of independent mass transfers as it has always
been considered so far, might be a rst step toward a more realistic
permeation model.
Acknowledgments
This work was partially supported by the French National
Agency for Technological Research [ANRT] under the grant-in-aid
CIFRE 2009/1012.
919
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Mass Transfer Modeling in Gas Barrier Envelopes For Vacuum Insulation Panels - A Review

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Energy and Buildings 55 (2012) 903920

Contents lists available at SciVerse ScienceDirect

Energy and Buildings

Corresponding author. Tel.: +33 1 60 73 69 57; fax: +33 1 60 73 65 39.

M. Bouquerel et al. / Energy and Buildings 55 (2012) 903920

Brief review on other modeling concepts for mass transfer in polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Naito equation parameter

M. Bouquerel et al. / Energy and Buildings 55 (2012) 903920

free volume fraction

Fig. 1. Constitution of a vacuum insulation panel [3].

1.1. Vacuum insulation panels

sol (u) = sol,dry + Bu

Fig. 3. Gas transfer in a VIP.

M. Bouquerel et al. / Energy and Buildings 55 (2012) 903920

Fig. 4. Ultra gas barrier membranes: AF and MF design.

 memb (mW/(m K))

memb (mW/(m K))

memb /cop (%)

Data from [1214,1820].

and metalized polymer membranes, polyurethane layers are used

M. Bouquerel et al. / Energy and Buildings 55 (2012) 903920

Flow rate (GTR)

cm3 (STP)/(cm2 d bar)

proposed between the most commonly used technical units and

in the x-direction (orthogonal to the membrane plane), the equation is simplied:

2.2. Linear sorptiondiffusion model

This unidirectional equation is valid for membranes where the

It is dened at a microscopic scale. At a macroscopic scale, the

For several polymerpermeant systems, Di can be considered as

This equation is formally equivalent to Fourier heat equation

Si is called the solubility coefcient and is a constant at given

M. Bouquerel et al. / Energy and Buildings 55 (2012) 903920

From Henrys law (Eq. (9)), the permeant concentration at the

So that the GTR is only a function of the permeability and the

2.3.1. Chemical potential as a driving force

For pressure and concentration gradients only, it is possible to

Xi is the molar fraction (mol/mol), i the activity coefcient so that

Hypothesis 2. The pressure in the membrane is homogeneous,

memb from Hypothesis 3,

It should be noted that this equation is formally identical to

It is possible to integrate Eq. (23) and to get the expression of

2.3.2. Interface gas/membrane and sorption

It is possible to rewrite this equation:

The expression of molar fractions is:

It is reasonable to assume that exp(( Vm (p pi,sat ))/RT) 1 in

p is small, so that exp(( Vm (p pi,sat ))/RT) = 1.

The equilibrium is then written:

Then Eqs. (16) and (18) can be combined:

Hypothesis 3. The activity coefcient and molar volume are

and in the gaseous phase:

In this section, the sorptiondiffusion model is obtained thanks

2.3. Thermodynamics justication of the sorptiondiffusion

It is then possible to introduce the surface permeability Pesurf,i :

The molar fraction Xi and the concentration ci (kg/m3 ) are

M. Bouquerel et al. / Energy and Buildings 55 (2012) 903920

where pi = p Xi,g is the partial pressure in the gaseous phase. It

i,g is equal on both sides of the membrane.

Combining Eqs. (25) and (31), one gets:

which is the global sorptiondiffusion transport model, identical to

2.4.1. Diffusion and solubility coefcients

is the product of a solubility coefcient, governing the equilibrium

3.1.1. Dual mode sorption

 is the Langmuir capacity (or hole saturation constant) and b

sol (u) = sol,dry + Bu

memb (mW/(m K))

memb (mW/(m K))

memb /cop (%)

p is small, so that exp(( Vm (p pi,sat ))/RT) = 1.

is the Langmuir capacity (or hole saturation constant) and b

GTRlin = lin pg

Pedef = n0 r02 1 + 1.18