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Measurement Methods for Solubility and Diffusivity of Gases and Supercritical

Fluids in Polymers and Its Applications

Article  in  Polymer Reviews · May 2017

DOI: 10.1080/15583724.2017.1329209

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Measurement Methods for Solubility and Diffusivity of Gases and Supercritical Fluids in
Polymers and its Applications

Jason K. Leea,1, Selina X. Yaob,1, Patrick C. Leeb,*, Martin B.G. Juna, Guangming Lic
a
Department of Mechanical Engineering, University of Victoria, Victoria, BC, V8W 3P6, Canada
b
The School of Engineering, University of Vermont, Burlington, VT, 05405, USA
c
The Dow Chemical Company, 2301 N Brazosport Blvd, Freeport, TX, 77541
*
Corresponding author at The school of Engineering, University of Vermont, 33 Colchester Ave,
VT, 05405, USA. E-mail: patrickc.lee@uvm.edu
1
These authors contributed equally to the publication.
The authors declare that this work has not been published elsewhere and not been submitted
simultaneously for publication elsewhere.

Abstract

Over the last century, polymer processes involving a gas or supercritical fluid (SCF) have attracted

significant attention. The attributes of a gas/SCF in polymers benefited many polymer processing

applications. In polymer applications, the solubility and diffusivity of the gas/SCF in polymers

are important parameters. This review discusses experimental and theoretical methods for

determining gas/SCF solubility and diffusivity in polymers. The Henry’s law, Flory-Huggins,

Sanchez-Lacombe, Simha-Somcynsky, and statistical association fluid theories are discussed for

a gas/SCF solubility in polymers. The experimental methods are categorized into five: gravimetric,

piezoelectric, manometric, chromatographic, and spectroscopic methods, and are compared in

terms of the operating temperatures, pressures, and types of a gas/SCF. The solubility from

different methods in literatures are compared in summary plots. In addition, the main advantages

and disadvantages of each measurement methods are tabulated. In the diffusivity section, the

steady and unsteady diffusion including the Crank’s, dual-mode sorption, gas-polymer matrix, free

volume, mass transfer, and empirical models are reviewed. For unsteady diffusion, the pressure

  1
decay and the gravimetric method are discussed. For steady state diffusion, the permeation method

is discussed as the experimental methods. The different methods used for obtaining information

on diffusivity are tabulated for comparisons.

Keywords: Gas; Supercritical fluid (SCF); Polymer; Solubility; Diffusivity; Equation of state

  2
 Contents
1. Introduction and Motivation ................................................................................................ 4
2. Research Approaches for Solubility of SCFs and Gases in Polymers ............................ 10
2.1. Theoretical Approaches for Solubility .....................................................................................10
2.1.1. Henry’s law ..........................................................................................................................11
2.1.2. Flory-Huggins Theory (Cell Model) ....................................................................................12
2.1.3. Sanchez-Lacombe Theory (Lattice Fluid Model) ................................................................13
2.1.4. Simha-Somcynsky Theory (Hole Model) ............................................................................14
2.1.5. Statistical Association Fluid Theory (SAFT) ......................................................................15
2.2. Experimental Approaches for Solubility Study ......................................................................16
2.2.1. Gravimetric Method .............................................................................................................17
2.2.2. Piezoelectric Method ...........................................................................................................25
2.2.3. Manometric Method.............................................................................................................28
2.2.4. Chromatography Method .....................................................................................................31
2.2.5. Spectroscopic Method ..........................................................................................................34
2.2.6. Comparison of Different Solubility Measurement Methods ...............................................36
3. Research Approaches for Diffusivity of Gases/SCFs in Polymers .................................. 45
3.1. Theoretical Approaches for Diffusivity Study ........................................................................46
3.1.1. Steady Diffusion ..................................................................................................................46
3.1.2. Unsteady Diffusion ..............................................................................................................47
3.2. Experimental Approaches for Diffusivity Study .....................................................................54
3.2.1. Pressure Decay Method .......................................................................................................54
3.2.2. Gravimetric Method .............................................................................................................55
3.2.3. Permeation Method for Steady State Diffusion ...................................................................56
4. Outlook for the future ......................................................................................................... 60
5. Conclusions .......................................................................................................................... 60
6. Declaration of Interest......................................................................................................... 63
7. Acknowledgements .............................................................................................................. 63
8. References............................................................................................................................. 63

  3
 1.   Introduction and Motivation

Polymers are widely used in various applications after becoming high-value products by many

processing techniques such as composite manufacturing, blending, and foaming. Depending on

how polymers are processed, the properties of finished products can be significantly different.

Polymer processes may go through chemical reactions and/or mechanical processes to shape raw

polymer materials in pellets, granules, flakes, or powders, into the desired finished products. The

finished product may have different morphologies and properties from the raw materials 1.

Polymer processes involving supercritical fluids (SCFs) and gases can be categorized into two

major groups. The first group is a process where a polymer is dissolved into a gas/SCF solvent.

The fine polymer particles of sizes in a few microns used as pharmaceutical substances are an

example 2. The second group involves the processes where a gas/SCF is dissolved into a polymer.

An example would be polymer blending either by a polymer impregnation or an extrusion process

3, 4
. Moreover, plastic foam products used for heat insulation, food packaging, and light-weight

structural components are another important application of this group as well, which are fabricated

by nano-/micro-cellular foaming processes such as foam extrusion, injection foam molding, or

batch foaming chamber processes 5, 6. In both groups, correct understandings about the interactions

between a gas/SCF and a polymer are critical for the optimum fabrication process. Many
7, 8 9, 10
properties of polymers, such as viscosity , the glass transition temperature , and the

crystallization 11, 12 are affected by the presence of dissolved SCFs and gases at high temperatures

and pressures, and solubility, diffusivity, plasticization behavior, surface tension, and

crystallization are some of critical parameters for polymer processing applications. In particular,

solubility and diffusivity are key parameters to understand and predict these property changes.

  4
SCFs are frequently involved in polymer processes because their unique properties provide

numerous advantages as an alternative to other organic solvents. A SCF is a substance above its

critical temperature and pressure as shown in Figure 1. SCFs behave similarly to gas in terms of

viscosity and diffusivity while they behave like liquid for density and solvating properties. The

properties such as density, diffusivity, or viscosity can be tuned simply by adjusting the operating

pressure and temperature.

Figure 1. Schematic of pressure-temperature phase diagram where the triple and critical points are shown. The phase
regions are labeled in the diagram13 (permission granted by Elsevier)

SCFs are widely used due to their economic advantages. SCFs can be recovered and reused

without any purification processes. In addition, the usage of SCFs can benefit many industrial

processes from low energy consumption and minimum toxicity when compared to the

conventional organic solvents. SCFs are non-carcinogenic, non-flammable, and

thermodynamically stable, which are the health and safety advantages of SCFs 14. Some polymer

processes, such as the micro-particle generation, use SCFs as solvents to dissolve polymers 7, 15-20.

Other polymer processes such the polymer blending involves gas/SCF sorption into polymers 18,
21-23
. The polymer blending can be processed using the gas/SCF sorption in polymers with batch

  5
mixing, single screw and twin screw extrusion, and tandem extrusion processes. The types of

polymers, SCFs, and devices used to fabricate polymer blends are shown in Table 1. Polymer

blend structures can also be fabricated through polymer synthesis, polymer impregnation, and

modification processes, which utilizes a gas/SCF as a solvent 4, 20, 24-39. Similar processes are used

to fabricate the polymer composites 40-51. Using a gas/SCF as a solvent for a polymer and gas/SCF

sorption in a polymer are different mechanisms and should be differentiated. In this review, the

scope specifically covers for the polymer-gas/SCF solubility processes where gases/SCFs are

dissolved into polymers (i.e., gas sorption in a polymer).

Table 1. Polymer blending using CO2

Gas / Supercritical
Polymer Blended Devices Ref Year
Fluid
Polyethylene (PE)/
CO2 Twin screw extruder 7 1998
Polystyrene (PS)
PS/ Poly-(methyl
methacrylate) CO2 Batch mixing 52 1999
(PMMA)
PS/PMMA CO2 Twin screw extruder 53 2000
Single screw extruder
PE/PS Twin screw extruder
CO2 3 2000
Single screw tandem
Twin screw tandem
PS/Rubber Impact
Modifier (SP2207)
PMMA/Rubber CO2 Twin screw extruder 54 2001
Impact Modifier
(SP2007)
PS/Liquid Crystal
CO2 Twin screw extruder 55 2001
Polymer (LCP)
iPP/Grafting Maleic
Anhydride CO2 Twin screw extruder 56 2010
(MAH)
PP/EPDM CO2 Twin screw extruder 57 2010
Poly(D,L-lactic
CO2 Batch mixing 58 2012
acid) (PDLLA)/PEG
PP/PS CO2 Twin screw extruder 59 2012

60
According to the International Union of Pure and Applied Chemistry (IUPAC) definition ,

solubility is the proportional ratio of a solute in a solvent. Diffusion can be described as the process

  6
where a material is transported by the thermal motion of the molecules in a fluid or a matrix.

Solubility and diffusivity act as crucial parameters in many of polymer processing applications,

such as in the study of the fabrication of nano-/micro-cellular foamed plastics. The nano-/micro-

cellular foams are fabricated in different methods, mainly batch processing 21, 55, 61-80, extrusion 5,
18, 19, 81-94 95-100
, and injection molding . Foam aging is a common drawback for many polymer

foam products due to product dimension changes and storage times. Gas/SCF diffusivity and

solubility significantly affects foam aging behaviors. During the fabrication of the nano-/micro-

cellular foams, information on solubility provides the maximum allowable amount of a gas/a SCF

dissolved into a polymer resin at a specific temperature and pressure. Once a foaming process

finishes, blowing agents leave the polymer matrix and replaced by air. This gas exchange rate

strongly depends on diffusivity. Some volatile gases, such as CO2 and N2 leave the structure

quickly, while others long-chain molecule gases, such as fluorocarbons and hydrocarbons escape
101
slowly . Furthermore, gas diffusion is also critical to the initial foam expansion control. The
102
study performed by H. E. Naguib, C. B. Churl, and P. C. Lee demonstrated that an initial

expansion behavior at the die exit determines the final foam volume expansion ratio as the

solubility grows with the sudden pressure drop. Diffusivity plays a key role in this process too.

The higher the temperature is, the greater the gas diffusivity will be and this gives low expansion

ratios. On the other hand, at low temperatures, the polymer matrix is too stiff to expand and thus
102
yields low expansion ratios . Also, solubility and diffusivity significantly affects the cell

nucleation and growth processes and thus, the final foam product morphology 103, 104. In polymer

blending, two or more immiscible polymers are mixed and processed to fabricate polymer blends

with different morphologies. The morphology of polymer blends can be modified by controlling

a viscosity ratio of the polymers. The higher viscosity ratio of minor/predominant components is,

  7
 8, 82, 105
the larger droplets are . The solubility and diffusivity of a gas/SCF are crucial since these

affect the viscosity of the polymers in blending. Since solubility and diffusivity have significant

effects in the many of polymer processes, further knowledge in solubility and diffusivity

measurement methods is essential to allow more flexibility in these polymer processes and the

relevant applications.

Recently, a SCF is found to be useful in many of the new polymer applications, such as the film

annealing, the fabrication of bio-sourced materials, and the interpenetration of networks. Although

compressed fluids generally serve as poor solvents, supercritical CO2 has been lately demonstrated

as an efficient plasticizer for the block copolymer annealing 106-108. The presence of CO2 has been
107, 108
observed to have a surprising effect on the miscibility of two different blocks . As V.S.

RamachandraRao et al. reported, controlled decompression leads to facile desorption of CO2

107
without damaging the ordered copolymer structure . A SCF sorption in polymers is very

important for bio-sourced materials especially for the tissue engineering application. The SCF is

an optimal candidate due to their potential ability to fabricate scaffolds with controlled porosities
109
, medicine 110, DNA 111 for controlled delivery to develop tissues, and the improvement of tissue

samples’ biointegration 112. Moreover, the SCF is also attractive from its potential to preserve the

activity of particular protein molecules which may form an integral component in the tissue
113
regeneration process . Another application of a SCF is the preparation of interpenetrating

networks. In D. Li, Z. Liu, and their coworkers’ study, polypropylene/polystyrene (PP/PS)

interpenetrating networks were first synthesized by using supercritical CO2 as a solvent and

swelling agent. They also claimed that composition of the interpenetrating networks can be

affected by supercritical CO2 pressures 114. Table 2 summarizes related studies on the new SCF

applications and the experimental conditions.

  8
 Table 2. New landscape of Supercritical Fluid application in polymer  
Application Operating Operating
Polymers Gas Ref Year
field Temperature Pressure
PS-Perfluorooctanoic Supercritical
40-65 °C 45 MPa 115 1997
Block polymer acid(PFOA) CO2
Supercritical
PS and PMMA 175 °C 34.6 MPa 107 2001
CO2
Poly (L-lactic acid)
(PLLA), Poly (D,L-lactic
acid) (PDLLA),
Supercritical Room
Polyglycolic acid (PGA) 5.5 MPa 109 1996
Bio-sourced CO2 temperature
and a 50/50 copolymer of
materials
D,L-lactide and glycolide
(PLGA)
Copolymers of lactide and Supercritical 10.34
37 °C 111 2003
glycolide (PLGA) CO2 MPa
Supercritical 10-20 113,
PP/ PS 35 °C 2004/2002
Interpenetrating CO2 MPa 114
network Linear low-density Supercritical
-100~300 °C n/a 116 2012
polyethylene/PMMA CO2

Many literatures related to the solubility of a SCF in various polymers have been reviewed by

numerous researchers. S.P. Nalawalde et al., and D. L Tomasko.’s group have covered CO2

solubility in various polymers and their applications in their review papers 82, 105. Furthermore, S.

G. Kazarian and A.I. Cooper elaborated on the applications of polymer processes using SCFs as

solvents 117, 118. However, these reviews focused only on SCFs and not on gases, such as N2, He,

H2, and CH4, which are also used extensively in various polymer processes. Furthermore,

diffusivity of a gas/SCF is hardly discussed at all. These review studies only emphasized on the

SCF solubility and SCF fluid applications rather than the measurement techniques. Although the

review by Kadam et al. discussed solubility and diffusivity measurement techniques, their focus
119
was only in the food packaging application . The main motivation for this review is to

investigate the available measurement devices and techniques for solubility and diffusivity of

gases and SCFs in various polymers at wide ranges of temperatures and pressures. Lastly, the

  9
limitations in these measurement methods are discussed. A comparison of various measurement

methods along with a summary is also tabulated to help the readers in selecting a suitable method

for the particular study.

2.   Research Approaches for Solubility of SCFs and Gases in Polymers

Solubility data are crucial in many of polymer processes, such as polymer impregnation, blending,

and microcellular foaming. Hence, different techniques for measuring gas/SCF solubility in a

polymer have been investigated by numerous researchers. In this section, various experimental

and theoretical methods used to obtain solubility data are discussed in detail. In addition, the

limitations of each method are described as well. In section 2.1.5., all the methods described in

this section are tabulated based on operating temperature and pressure ranges, the types of

gas/SCFs and polymers. The comparison figures are also plotted to elucidate the differences in

the solubility data obtained from different techniques.

2.1.   Theoretical Approaches for Solubility

Many thermodynamic models are developed to study polymer melts and multi-component polymer

blend systems. These theoretical thermodynamic models have been utilized by researchers to

study the phase equilibrium behaviors between a gas/SCF and a polymer. Theoretical

thermodynamic models can be useful tools to study many fundamental properties such as solubility

and diffusivity of polymer/gas mixture systems. The basic theories and various equations of states

(EOSs) are briefly discussed in this section, and the summary of EOS models are tabulated in .

Table 3 for the comparison.

An EOS is a mathematical relation among volume, pressure, temperature, and the composition of

a closed system. In general, EOSs can be categorized into two types: empirical and theoretical

  10
models. The empirical EOSs are used more in the interpolation of obtained data, and thus result

in poor predictions when extrapolated to high temperature or pressure conditions much beyond the

ranges of experimental data. Furthermore, the empirical EOSs are difficult to use in systems with

strong polar molecules or supercritical components. In contrast, the theoretical methods based on

statistical thermodynamics offer many advantages over the empirical approaches. These models

require less mixture data for the parameter fitting, allowing more reliability in the extrapolation at

high temperatures and pressures, and simplifying the calculations of multi-component mixtures or

systems with supercritical components. The following sections describe the theoretical approaches

based on statistical thermodynamics.

2.1.1.   Henry’s Law

Henry’s law is not considered as an EOS model but it is a relation to estimate gas/SCF solubility

in a polymer. According to Durill et al. Henry’s law is reliable only at low pressures 105, 120. These

researchers tested up to 30 MPa assuming that a Henry’s law constant is independent of pressure
23, 121
. However, at high pressures, a gas sorption isotherm has deviated significantly from the
105
Henry’s law . This deviation has been improved through the Langmuir type isotherm which

accounts for gas solubility in interstitial spaces and micro-voids 122, 123. Michaels et al. correlated

the solubility of He, N2, O2, Ar, CH4, CO2, and ethane in polyethylene terephthalate (PET) and
124
studied the deviations of gas sorption isotherms from the Henry’s law . The Henry’s law

represents reliable data in low pressures below 2 MPa and thus is commonly used in many

solubility studies 125, 126. The relation between a Henry’s law constant and a temperature can be

described as: H1=H0exp(-Es/RT), where H0 and are the Henry’s law constants, Es is the heat of

solution, and T is the temperature 23.

  11
 2.1.2.   Flory-Huggins Theory (Cell Model)

The classical Flory-Huggins theory is based on a lattice model for describing polymer/solvent or

polymer/polymer mixture systems. In a lattice model, all the cells are occupied with segments

(i.e., solvent molecule or segment of a long polymer chain) as shown in Figure 2. The volume

among different segments (segments of a long polymer chain or small solvent molecules) is

assumed to be the same. Moreover, an assumption is made where a polymer segment and a solvent

molecule could replace one another in the liquid lattice. The energy of mixing for a mixture system

is from both enthalpy of mixing and entropy of mixing.

The Flory-Huggins theory is a special model of the general cell model where all the cells are

occupied by either the polymer chain segments or the small solvent molecules. This cell model

demonstrates that the thermodynamic properties of a mixture strongly depend on the

thermodynamic properties (volume, compressibility, etc.) of each pure component.

Figure 2. Schematic of a Flory-Huggins thermodynamic model 127. Black circles and white circles represent polymer
molecule chains and small solvent molecules, respectively.

  12
Y. L. Cheng et al. first used the Flory-Huggins theory to study gas solubility in a polymer 128. The

Flory-Huggins theory is useful to investigate solubility and phase equilibrium within limited

pressure and dissolved gas concentration ranges, but the concern is that this theory fails to predict

isothermal data at high pressure and high dissolved gas concentration ranges as it ignores the

volumetric changes of a polymer/gas mixture system by pressure, temperature, and mixing 129.

2.1.3.   Sanchez-Lacombe Theory (Lattice Fluid Model)

To overcome the limitations of the Flory-Huggins theory, Sanchez and Lacombe proposed a

dimensionless theoretical model based on a fluid-lattice theory (i.e., the SL EOS). Vacant cells

are adopted in Sanchez-Lacombe theory, as shown in Figure 3 and these cells are introduced in

the lattice to illustrate the extra entropy change in the system as a function of volume and

temperature of the polymer/gas mixture system. The changes in volume only occur when new

holes or vacant sites occur on the lattice because the lattice size, or cell volume (i.e., occupied

volume), is fixed. To obtain a pure component, SL EOS requires three EOS parameters such as a

characteristic temperature T*, a characteristic pressure p*, and a characteristic specific volume

v*sp, similar to the Flory-Huggins theory.

  13
Figure 3. Schematic of a Sanchez-Lacombe theory model 127. Empty circles and vacant sites represent new holes and
vacant sites on the lattice, respectively.

The SL EOS is a quantitative theory and it is applicable for both gaseous and liquid states. The

chemical potential of a gas component can be calculated the same way as that of a liquid phase.

Therefore, the SL EOS is not required to define a standard state for a gas (i.e., gas standard state

fugacity) unlike the Flory theory. The SL EOS model is the most widely used EOS model, and C.

Panyaiotou extended this SL EOS further by accounting for the strong interactions (i.e., hydrogen
130
bonding) between the polymer and the solvent . The SL EOS model is simple while being

capable of extrapolating the available experimental data to high temperatures and pressures and

thus is used widely to investigate gas solubility in polymers 131-136.

2.1.4.   Simha-Somcynsky Theory (Hole Model)

To improve the Flory-Huggins thoery for the liquid state (i.e., polymer melts), Simha and his co-
137, 138
workers proposed the SS theory based on the lattice-hole theory . The lattice-hole model

considers a lattice of cells, each of which can accommodate either a small molecule or a chain

segment. Also, similar to the lattice fluid model, the hole model improves the liquid state cell

  14
 137
model by introducing the vacancies in the lattice, which can describe the thermal expansion .

In obtaining the characteristic parameters of SS EOS, it uses the “square well” approximation to

the cell potential and the nearest neighbor contributions to the lattice energy are not included. The

resulting coupled equation of states must be solved simultaneously with an expression minimizing

the partition function with respect to the fraction of occupied sites. Unlike SL EOS, in the SS

theory, the change in a cell volume, or the occupied volume, is also allowed with temperature and

pressure. According to Q. Gao, C.B Park, X. Xu, and J. Wang, SL EOS better fits for the data of

gas while SS EOS better fits for data of polymers 139.

2.1.5.   Statistical Association Fluid Theory (SAFT)

140
Statistical Association Fluid Theory or SAFT, is an EOS based on the lattice theory where it

assumes that real fluids exist in a continuous space rather than in a lattice 105. The SAFT EOS has

been proven to successfully forecast the thermodynamic properties of small molecules over a wide

density range, and has also been applied effectively to polymeric fluids and their mixtures. Instead

of using a hard sphere reference fluid as in many other engineering EOS, the SAFT is developed

from an idea of a reference fluid incorporating both the molecular geometry and molecular

association effects. In the SAFT model, the fluids (molecules) are described as equi-sized

spherical segments interacting according to a square-well potential. Therefore, the component

(molecules) is well described with the following three component parameters: m, υ00, and u0/k,

where m is the number of segments per molecule, υ00 is the segment molar volume in a close-

packed arrangement in milliliters per mole of segments, and u0/k is the segment energy or the well

depth, a temperature-independent energy parameter, in kelvin.

The SAFT EOS can be used for various gas/SCF polymer systems at high pressures 141, 142. S.H.

Huang et al. extended the SAFT EOS theory to study the mixtures of real, molecular, and

  15
macromolecular fluids over a wide density range to investigate gas solubility in a polymer 141, 143.

This model is more complex than the SL EOS but it accounts for the specific interaction such as

hydrogen bonding among the segments of polymer molecules 82.

Table 3. Theories for solubility study  

Temperature Pressure
Theory Gases Polymers Ref Years
(˚C) (MPa)
Henry’s CO2, CH4, Ar, Polycarbonate (PC), 1977/1986
35 0.2-2, 6.2 125, 126
Law N2, He Silicon Rubber
H 2, O 2, N 2,
Henry’s CO2, CH4, polydimethylsiloxan
35 0-2.75 144 2000
Law C 2H 6, C 3H 8, e (PDMS)
CF4, C2F6, C3F8
Henry’s
Law (Low
Poly (ethylene-co-
P) Flory- N2, CH4, CO2 10-40 0-5.06 145 1994
vinyl acetate)
Huggins
(Higher P)
Below
Flory- N2, O2, CO2, Polylactic acid atmospher
10-40 146 2004
Huggins H 2O (PLA) ic
pressure
CO2, N2, Polypropylene (PP), 100-180, 160-
0-20, 0-
Sanchez- Polypylene, Polystyrene (PS), 200, 50-75, 1996,1999,
17, 0-200, 133-136
Lancombe Butane, Semicrystalline 40-300, 75- 2001,2004
0-3
isobutane polypropylene 200
Sanchez- Isotactic
CO2 100-150 1-15 147 2009
Lacombe polypropylene (iPP)
Sanchez-
Polyactide, PP and
Lacombe 103, 148, 2007,
CO2, N2 Ethene/Octene Up to 250 Up to 35
and Simha- 149 2006, 2007
Copolymer
Somcynsky
Sanchez-
Poly (ethylene
Lacombe CO2 25-50 7-25 150 2008
glycol) (PEG)
and SAFT
Propane, CO2,
SAFT PEG 50-120 0.5-30 142 2000
N2

2.2.   Experimental Approaches for Solubility Study

Different methods and techniques are available for gas/SCF solubility measurements in polymers.

In this section, the methods will be grouped into four categories based on the measurement types

and within each category, different measurement techniques are described as shown in Table

4Error! Reference source not found..

  16
 Table 4. Solubility measurement types and techniques
Category Measurement Type
A Gravimetric
B Piezoelectric
C Manometric
D Chromatography
E Spectroscopic
Measurement Techniques
McBain Balance (Quartz spring balance)
Electronic Microbalances (Cahn Instruments,Sartorius,
and Mettler AE 163)
Magnetic Suspension Balance (MSB)
Quartz Crystal Microbalance (QCM)
Equilibrium Desorption
Phase Separation
Pressure Decay (single and multiple sorption cells)
Inverse chromatography
Fourier transform infrared spectroscopy (FTIR)

2.2.1.   Gravimetric Method

The gravimetric method measures solubility of a gas/SCF dissolved in a polymer by acquiring the

changes of the sample weight by a gas/SCF. When a polymer sample is exposed to a gas/SCF, the

sample swells and the volume change occurs which affects the calculation of solubility data.

Therefore, in gravimetric methods, it is critical to compensate for a volume swelling of the sample

since the volume swelling correction can affect up to 40% of the measured weight difference
151
depending on gas/SCF and polymer types, and pressure ranges . There are experimental

techniques such as a photometric method or a thermomechanical analyzer (TMA) method to

measure the sample swelling and buoyancy behaviors 82, 131, 152, 153. Also, the EOS theories such

as Henry’s Law, SL-EOS, Flory-Huggins theory, SS EOS, or SAFT EOS are used to account for

swelling. Y. Zhang and co-investigators studied the swelling and sorption behaviors of various

polymers in the presence of CO2 at 35 ˚C and 10.3 MPa 132.

A quartz spring balance is one of the early gas/SCF solubility measuring techniques based on the

gravimetric method. This apparatus determines solubility by monitoring the extension of a spring

from an increased sample’s weight. Using the Hooke’s Law, the mass of the sample is determined

as a function of a spring elongation. The spring used in this technique is fabricated from quartz or

  17
similar materials such as tungsten. J.W. McBain is one of the early researchers who used a quartz

spring apparatus to study the gas sorption behaviors in rubbers and naturally occurring polymers154.

Thus, this apparatus is commonly referred as a McBain Balance. The schematic of a quartz spring

balance used by McBain can be seen in Figure 4. A McBain balance is suitable for the sorption

study of organic vapors or gases that are highly soluble in polymers. Only a small portion in a

McBain balance is required to be heated and a pressure is held constant for solubility

measurements. Precautions are necessary when operating a McBain balance as this device is

sensitive to vibration. The preliminary volume calculations required for solubility calculations in

other types of gravimetric measurement techniques are not required in a McBain balance. Instead,

the sensitivity of a spring and the extension per unit weight calculations must be done for solubility
151
calculations . The sensitivity of a McBain balance is low and therefore it is hard to measure

solubility of light gases in a polymer 151. However, this limitation can be overcome by using more

modern and sophisticated types of quartz spring for a higher sensitivity. These modifications on

a McBain balance allow the users to operate up to 1.01 MPa 155. Furthermore, precise temperature

and pressure controls can be implemented to improve the experimental accuracy 156, 157. A McBain

balance is compatible with different gases and polymers in the moderate range of temperatures (35

– 178 ˚C) with modifications. G.E. Serad and co-researchers used a McBain balance to study the
158
sorption and diffusion behaviors of n-Butane in PET . S. Lequin and co-investigators used a
159
McBain balance to study water vapor sorption on cork , and Y. Iwai and Y. Arai studied

solubility of m-xylene and nonane vapors in PS, and ethylbenzene and nonane vapors in

polybutadiene (PBD) in the temperature ranges from 130 to 175 ˚C and 80 to 130 ˚C, respectively
160
. A McBain balance is also capable of measuring gas/SCF solubility of a thin film sample. This

can be done by suspending the thin film sample in the cell. However, this technique is impossible

  18
if the sample is in a semi-liquid state or in a molten state (i.e., high temperature experiments). For

a sample in a semi-liquid state or in a molten state, utilizing suspended pans or caps is necessary

but this can cause other experimental challenges such as sample adhesion to the bottom of the pan.

As mentioned above, gravimetric methods must consider for the buoyancy effect and, in case of a

McBain balance, the calibration of the unstrained spring needs to be calculated as well before the

solubility calculation 156, 161, 162. The weight, temperature, and pressure sensitivities of a modified

McBain balance have been known as ± 0.05 mg, ± 0.5 ˚C up to 400 ˚C163, and ±1 Pa 159
,

respectively. The sample of 5 to 20 mg can be loaded on the spring according to Kadam’s group
119
. More information on the types of polymer, gas/SCF, and temperature and pressure ranges are

tabulated in Table 5.

  19
  

Figure 4. Schematic of a McBain Balance in superposed thermostats: (A) heating coil, (B) quartz spring, (C) polymer
specimen 154 (permission granted by American Chemical Society)

Electronic microbalances are also utilized to obtain gas/SCF solubility measurements in polymers.

Electronic microbalances can take a smaller sample sized specimen because of a higher sensitivity.

In addition, these microbalances have a shorter measurement time compared to McBain type
82
balances . Three electronic microbalances are frequently mentioned in literatures: ones

manufactured by Cahn Instruments, Sartorius Stedim Biotech GmbH, and Mettler Toledo. In a

Cahn type microbalance, the sample is positioned in a high pressure chamber and is balanced with

a weight suspended on the other end of a beam. Electronic signals with a variable gain amplifier

and a digital to analog converter are used to observe any imbalances of the device. A Cahn

microbalance was used by Y. Kamiya and the research group to study sorption and dilation of a

  20
polymer with various gases 145, 164-166. In Y. Kamiya’s studies, they measured the weight change

of polymers in both sorption and desorption and found that the sorption and desorption runs
145
coincided . Another research group, B. Wong and investigators used a Cahn microbalance to

determine solubility and diffusivity of CO2 and HFC134a in PS, filled poly(vinylchloride) (FPVC),

and unplasticized poly(vinylchloride) (UPVC)167. The schematic of the sorption apparatus using

a Cahn microbalance is shown in Figure 5. In a Sartorius type microbalance, an electromagnet

coil is connected at the center of a beam within a permanent magnet field. The current in the coil

changes relatively to the change in the sample’s weight. This fluctuation of current is monitored

with a microprocessor to determine the weight of the sample. Y. Kamiya and the group studied

CO2 sorption and dilation of PMMA using a Sartorius microbalance 168. In this study, Y. Kamiya’s

research group have used both measurements in sorption and desorption, in which the two runs

coincided closely. Similarly, L. Phan Thuy and J. Springer studied CO2 sorption in poly(butylene

terephthalate) (PBT) 169. In addition, N. Von Solms and co-authors made a direct measurement of
170
solubility and diffusion of methane and CO2 in high density polyethylene (HDPE) . The

schematic of a sorption apparatus using a Sartorius electronic microbalance is shown in Figure 6.

Several sorption studies in literature used a Mettler AE163 electronic microbalance to study

sorption of CO2 in different polymers, such as poly(chlorotrifluoroethylene) (PCTFE), PDMS,

24, 25, 171, 172
PMMA, and PS . These literatures investigated solubility of gas/SCF in polymers

gravimetrically based on the weight decay method suggested by Berens et al. using the Mettler

AE163 electronic microbalance 171. The gravimetric method by weight decay used by Berens et

al. is similar to the Y. Kamiya’s desorption measurement using Cahn 2000 or Sartorius electronic

microbalances. In the weight decay method, first, the polymer specimen is pressurized by the

gas/SCF at desired temperature and pressure. After the equilibrium has reached, the chamber is

  21
depressurized and the specimen is quickly transferred to the Mettler AE163 electronic

microbalance where the weight loss is observed with a resolution of ±0.0001 g as a function of

time 171. The resultant weight decay plot over time is as seen in the work of K.F. Webb and A. S.
172
Teja in CO2 sorption in PCTFE in Figure 7 . More recently, C. Gutierrez et al. studied the
173
sorption of CO2 in PS using the same technique . A more comprehensive list of gas/SCF and

polymer combinations is available in Table 5.

Figure 5. High pressure sorption apparatus with a Cahn model 2000 electronic microbalance by Kamiya 166: (A)
pressure chamber containing an electronic microbalance, (B) thermostatically controlled air bath, (C) temperature
controller, (D) thermometer, (E) pressure gauge, (F) safety valve, (G) flow meter, (H) columns of active charcoal and
silica gel, (I) pressure regulator, and (J) a gas cylinder166 (permission granted by American Chemical Society)

  22
Figure 6. Sorption apparatus with a Sartorius S3D-P electro microbalance by Kamiya 168: (A) Sartorius microbalance,
(B) constant temperature water bath, (C) auxiliary furnaces, (D) constant temperature air-bath, (E) pressure chambers,
(F) thermocouple, (G) water inlet, (G) gas inlet, (I) polymer sample plus buoyancy corrective (gold wire), (J) counter
balance (aluminum rod)168 (permission granted by American Chemical Society )

 
Figure 7. The weight decay plot from the work of Web et al. on solubility of CO2 in PCTFE 172. (permission
granted by Elsevier)

A magnetic suspension balance (MSB) is another instrument allowing gravimetric measurements

of gas/SCF solubility in polymers. A MSB is differentiated from other gravimetric techniques

described earlier due to contactless weight measurements. A microbalance in a MSB is isolated

  23
from a high pressure and temperature sample chamber and is positioned in an ambient environment.

A MSB is capable of measuring gas/SCF solubility in high pressures and temperatures unlike other

gravimetric techniques such as a McBain balance and shares similar advantages such as a high

sensitivity with other electronic microbalances mentioned earlier. A polymer sample is positioned

in a sample holder and it is isolated from the balance as shown in Figure 8. The sample holder is

hung on to a suspension magnet (i.e., permanent magnet), which is kept free in the sorption

chamber to allow the transmission of a magnetic attraction force to the external electronic balance.

Therefore, the weight measured in the sorption chamber can be precisely transmitted to the isolated

microbalance through this suspension magnet. A MSB is used by numerous researchers to

measure gas/SCF solubility in polymers. For example, Li, G., Gunkel, F., Wang, J., Park, C.B.,

and Altstädt, V. measured solubility of N2 and CO2 in PP and Ethylene Octene copolymers from

180˚C to 220˚C and 160˚C to 200˚C, respectively, up to pressures of 27.6 MPa 149. Y. Sato and

co-workers found solubility of CO2 in Polyphenylene Oxide (PPO) and PPO/PS blends using a

MSB 174. A MSB can detect mass changes of 3×10-5g. A sample mass for measurements is from

0.01 to 30 g with a pressure control of ±10 Pa between 0.1 ×105 and 1.33 ×105 Pa, and a
119
temperature control of ±0.05 ˚C from 20 and 150 ˚C . Many literatures mention a MSB

manufactured by Rubotherm GmbH (Rubotherm) to study solubility and diffusivity of a gas/SCF

in various polymers. B.I. Chaudhary and A.I. Johns studied the sorption of N2, Isobutane, and
175
CO2 in PE in the temperature range of 110 to 200 ˚C up to 20 MPa . Von Schnitzler et al.

measured the sorption of CO2 in PBT with a MSB in the temperature range of 40 to 120 ˚C and

the pressures up to 30 MPa. Y. Sato and the group studied CO2 solubility in various polymers and
174, 176, 177
polymer blends using a MSB . Furthermore, S. Areerat and the research group also

studied solubility of CO2 in molten polymers such as HDPE, Low Density Polyethylene (LDPE),

  24
PP, Ethylene-Ethylacrylate copolymer (EEA) and PS 178, 179. In more recent work, Z. Lei and co-

authors studied CO2 sorption in PP. Similarly, E. Aionicesei et al. studied CO2 solubility in PEG,

poly(l-lactide) (PLLA) and poly(d,l-lactide-co-glycolide) (PLGA). In 2015, N. Trupej and co-

investigators measured the solubility and diffusion coefficient of a Ar gas in PEG using a MSB 150,
180-182
. A comprehensive list of types of polymers and gases/SCFs, and ranges of temperatures and

pressures for solubility measurement using a MSB is tabulated in Table 5.

Figure 8. The schematic of a solubility measurement apparatus with a MSB by Sato176. (permission granted by
American Chemical Society)

2.2.2.   Piezoelectric Method

Piezoelectric crystals can be used to investigate gas sorption behaviors in polymers using the

principle of piezoelectric crystal frequencies. The vibration frequency of a piezoelectric crystal

changes with respect to its mass, and this frequency change can be measured using a control system

  25
151
. The oscillation frequency of a polymer sample coated atop a piezoelectric crystal is used for

the solubility measurement. Prior to the experiment, it is necessary to know the frequencies of

uncoated and coated crystals at an ambient environment. Then, the weight of the sample is

determined as a function of gas pressures, and through the mass balance, the weight of a gas

dissolved in the sample can be calculated. D.C. Bonner and Y.L. Cheng used a piezoelectric

crystal sorption device to study N2 sorption in LDPE 183. Moreover, this method is well elaborated

in the studies of B.J. Brisco and the research group where they measured gas solubility and gas

induced dilation in poly(urethane) elastomers using a vibrating beam technique, which involves

the measurement of the first harmonic resonant frequency of the beam that can vary with the mass

of gas absorbed in a polymer 184-186. More recently, the work by K. Miura and co-authors with a

quartz crystal microbalance (QCM) attracted people’s attention, where quartz crystals are used as

mass ‘sensors’ to obtain CO2 solubility and adsorption data at high pressures 187. The schematic

of a solubility measurement setup using a QCM are shown in Figure 9. K. Miura et al. used a

platinum resistance thermometer to measure a temperature inside the cell and a strain gauge to

measure the pressure of the cell. The solubility was obtained by calculating the frequency

difference between the initial frequency and the measured frequency at a certain pressure and

temperature. G. Wibawa and co-investigators used a QCM to measure solubility of seven nonpolar

organic solvents such as octane, cyclopentane, cyclohexane, benzene, toluene, ethylbenzene and

p-xylene in cis-1,4-polyisoprene, poly (isobutylene) PIB, poly(n-butyl methacrylate), and

188
poly(vinyl acetate) (PVA) . The advantages of a piezoelectric method are; first, this method

does not require a volume change correction as other measurement methods due to its vibration

frequency based measurement; second, a QCM has a short experiment time; third, a very small

change in weights can be measured; and lastly, it is relatively easy to add an automated

  26
measurement system 187, 188. However, the hysteresis error from the adhesion of polymer films to
151, 189
the crystals should be taken into account . Moreover, since a QCM is a fast measurement

device, it cannot detect the slow changes during sorption caused by the polymer relaxation which
119, 190
is independent of the film thickness . Preparing a thin polymer film on the crystal is a

fundamental challenge, limiting the types of polymers used with a QCM. CO2 solubility in poly

4-methyld-1-pentene (TPX), PMMA, polyimide, PC, PS, chlorinated polyethylene, poly(xylylene),

poly(2-chloroxylylene), poly(2,3-dichloroxylylene), and teflon were investigated by James Aubert

using a QCM up to 40 ˚C and 9.65 MPa 191. D. Boudouris and co-researchers studied the sorption

behaviors of HCFC-22 and HFC-152a in PMMA, PS, and PC, and M. Pantoula and C. Panayiotou
192
studied CO2 sorption in PMMA and PS . In their work, M. Pantoula and C. Panayiotou

compared the obtained solubility data with a QCM with other literature data to elucidate the

accuracy of their results 193. N.S. Oliveira et al. found solubility of N2, O2, CO2 and water in PLA

with an overall average absolute deviation of 6% when compared with the theoretical values
146
obtained with the Flory-Huggins theory . More recently, F. Herran and the research group
194
studied the sorption of H2O vapor in PC using a QCM . A.L. Smith and H.M. Shirazi have

obtained the temperature control of 0.0001 ˚C up to 45 ˚C and 0.005 ˚C up to 110 ˚C in their QCM
195
experimental setup . More comprehensive information regarding the types of polymers and

gases/SCFs, and the measurement ranges of temperatures and pressures is tabulated in Table 5.

  27
Figure 9. Schematic of a sorption apparatus with a QCM used by Miura et al.187. (permission granted by Elsevier)

2.2.3.   Manometric Method

A manometric method determines the solubility of gases/SCFs in polymers by measuring the

pressures or volumes of the gases sorbed in or desorbed from the sample in equilibrium 151. Early
196, 197
studies were performed in sub-atmospheric pressures (0.101 MPa) . C.S. Venable and T.

Fuwa acquired solubility data of different gases in rubber using a direct experimental procedure,

which is to calculate solubility data from volume differences between before and after a gas
198
exposure at 100 ˚C in a sub-atmospheric pressure . By monitoring the pressure or volume

changes of a gas in a chamber, the solubility of gases in polymers are determined. The chamber

volume calibration must be done prior to an experiment in this configuration. In these early direct

experimental techniques, one of the challenges is the process of removing all ambient gas phases

as soon as possible once the equilibrium is reached, while preventing the dissolved gas from being

pumped out of the sample. The usage of a high power pump for evacuating the chamber removes

a gas phase effectively 199, 200.

A phase separation technique is one type of manometric methods used to obtain solubility data. In

a phase separation method, the molten polymer sample is exposed to a gas under a certain pressure

  28
in an autoclave. Once equilibrium is attained, the solubility can be determined by calculating the

amount of gas present in the polymer-rich phase of a sample. This method is mainly applicable to

low viscosity polymers as mixings between a low viscosity polymer and a gas/SCF are easier 105.

M. Daneshvar, S. Kim, and E. Gulari used the phase separation method to obtain sorption of CO2

in PEG up to 100 ˚C and 35 MPa, while Garg et al. obtained CO2 and 1,1-difluroroethane sorption
105, 201, 202
in PDMS and PS in the range of 50 to 160 ˚C and up to 26 MPa . The solubility of

propane, N2, and CO2 in PEG was also investigated by Wiesmet and the research group using a

phase separation method 142, 203.

A pressure decay method is a prevalently used manometric based solubility measurement

technique. This technique was developed by Newitt and Weale in 1948 to measure solubility of

H2 and N2 in PS 204. In a pressure decay method, a polymer sample is placed in a closed pressure

vessel with a known volume and a temperature. As a preheated gas is introduced to the chamber,

pressures are measured as a function of time until gas sorption to the sample completes. The

solubility is determined by calculating the pressure difference between an initial gas amount and

a gas amount at equilibrium. It is important to consider for the polymer sample swelling during

gas sorption because this changes the total sample volume. Theoretical EOSs can be used to

compensate for the swelling volume of a sample due to gas sorption. The solubility measurement

at a high temperature is particularly difficult with a pressure decay method due to the lack of

suitable pressure sensors 82, 177. Moreover, at a high pressure experiment, small gas leakage from

the chamber can lead in underestimating the solubility data. Therefore, solubility measurements

at high pressures require accurate EOSs, and should take account of Pressure-Volume-

Temperature (PVT) behaviors of the polymers at high pressure and temperature conditions.

Furthermore, polymer degradation problems could also occur at high temperature experiments 82.

  29
For a pressure decay method, a large amount of samples is required. Hence, a long measurement

time is required to obtain solubility data because reaching equilibrium takes a long period of time.

The measurement errors can arise when accounting for an initial gas pressure introduced to the

cell because a stabilization period is required for a pressure measuring device. During this

stabilization period, a substantial amount of gas sorption can occur and this can cause solubility

measurement errors. The extrapolation of a pressure decay curve to a zero time was conducted in

attempt to correct for this error 205-208. Moreover, a reference reservoir was used to correct for this

type of error 209. An attempt to use dual sorption cells was made by W.J. Koros, A.H. Chan, and

D.R. Paul and they were able to measure solubility of multiple gases in PC without a stabilization

related error 126. Multi-sorption cells were also used to eliminate the errors as in the experiments
133-136, 210
by Y. Sato’s research group and V.I. Bondar’s research group . Using these multi-

sorption cells allowed the researchers to perform solubility measurements at high pressures. The

schematic of a dual cell pressure decay sorption apparatus is depicted in Figure 10. Not only gas

sorption behaviors, but also the diffusivity and permeability of different gases in PEO at 35 ˚C and

pressures up to 4 MPa were obtained using a dual sorption pressure decay method by H. Lin and

B.D. Freeman 211. Moreover, J.E. Groiler and the research group used a vibrating wire sensor with

a pressure decay method to obtain solubility of CO2 in medium density polyethylene (MDPE) and

poly (vinylidene fluoride) (PVDF) 212, 213. Recently, D. Li and investigators studied CO2 sorption

in solid-state isotactic polypropylene (iPP) in the temperature and pressure ranges of 100 to 150

˚C and up to 15 MPa, respectively. S. Kim and co-authors studied the gas sorption of H2, N2, O2,

CH4, and CO2 in different thermally rearranged polymers, and C.G.F. Rezende et al. studied the

sorption of propylene and propane in polyurethane containing silver nanoparticles 147, 214, 215. More

  30
types of polymers, gases/SCFs, and ranges of temperatures and pressures in this method are

tabulated in Table 5.

Figure 10. Schematic of a sorption apparatus with dual sorption pressure decay used by Stern208: (A) Auxiliary glass
system for volume calibrations, (A1) reference volume, (A2) thermocouple gauge, (A3) mercurial manometer, (B, C,
D, E) calibrated volumes of apparatus, (D) gas reservoir, (E) gas absorption cell with polymer sample, (F) differential
pressure null indicator, (G) null indicator control, (H) dead-weight gauge, (1-7) needle valves208 (permission granted
by John Wiley and Sons)

2.2.4.   Chromatography Method

A gas chromatography method is the only dynamic method of determining gas solubility in

polymers while other methods mentioned earlier are static methods. In static methods, the sorption

is continued until equilibrium is reached at a certain pressure and temperature. In dynamic

methods, sorption is studied in a flow of gas, which depends on the factors such as temperatures

  31
 216
and/or velocities of carrier gases, to measure a retention volume of a solute molecule . In

chromatography, a very thin polymer film in a micrometer range is fixed in the column (i.e.,

stationary phase or solid phase) and the gas is inserted to the column (i.e., mobile phase or

gas/vapour phase). Because gas sorption is related with the retention time and retention volume

of the solute in the chromatographic column, a chromatography technique measures retention time

and retention volume to acquire sorption data 151. The advantages of a gas chromatography method

are that it is more simple, and fast than the gravimetric or manometric measurement methods 217.

Moreover, this method provides other thermodynamic properties other than solubility such as
217-221
dispersion surface energy or acid/base interaction data . One disadvantage of

chromatography method is that this technique is limited to volatile substances because a finite

fraction of the polymer sample has to be distributed into the gaseous phase. Another crucial

problem with the gas chromatography occurs from diffusion limitations. O. Smidsrod and J.E.

Guillet plotted the retention volume against the flow rate for glassy polymers and demonstrated

that they are frequently Z-shaped near the glass transition temperature of the polymer. According

to the authors, this retention diagram shape is closely related with diffusion limitations 220. As a

result, specific retention volumes are hard to determine for glassy polymers with low diffusion

coefficients near the glass transition temperatures. N.F. Brockmeier et al. used a gas

chromatographic method to study PS with benzene and etylbenzene at 120 ˚C and 185 ˚C

respectively, PE with n-decane at 185 ˚C, atactic PP with hexane at 80 ˚C, HDPE with n-hexane

and hexane-isopropyl alcohol azeotrope at 80 ˚C, and stereo-regular PP with hexane at 80 ˚C at

0.304 MPa 222, 223. R.N. Lichtenthaler and the research group used a chromatographic method to

study gas sorption behaviors in PIB, PVA, PDMS, and PE 224, 225. The inverse chromatography,

another chromatographic technique where stationary and mobile phases are inverted from a regular

  32
gas chromatography technique, is used by Y. Yampolski and the research group to study sorption

of n-alkanes in poly(vinyltrimethyisilane) 226. I.C. Sanchez and P.A. Rodgers studied the sorption
221, 226
behaviors of 40 different gases in various polymers using the inverse chromatography .

Sorption of CO2 in PMMA was studied using a mass spectrometric tracer pulse chromatography

(MSTPC) by Edwards et al. in a temperature range of -19 to 190 ˚C at pressures up to 9.12 MPa
227
. The schematic of a MSTPC sorption apparatus is shown in Figure 11. Recently, solubility

coefficients and sorption isotherms of gases in polymers were determined by Y.A. Nizhegorodova

et al. using a novel static-dynamic chromatography method 228. This method is novel in how the

advantages of static (i.e., the sorption until equilibrium) and dynamic (i.e., the sorption in a flow

of carrier gases) approaches for sorption measurements are combined in determining the solubility

coefficients. They were able to obtain equilibrium state solubility data like the static method while

still acquiring data of polymer quantity in a gas using the chromatographic detector like the

dynamic method. More information on the types of gases/SCFs, polymers, and ranges of

temperatures and pressures using this method can be seen in Table 5.

Figure 11. Schematic of a MSTPC sorption apparatus used by Edwards227: (1) carrier gas (He), (2) carrier gas (CO2),
(3) sample gas, (4) high-pressure pump, (5) flow regulator, (6) pressure sensor, (7) isolation valve, (8) multi position
valve, (9) valve oven, (10) vacuum pump, (11) analytical column, (12) gas chromatography oven, (13) capillary

  33
 227
restrictor, (14) capillary column injector, (15) uncoated capillary tubing, (16) mass-specific detector, (17) vent .
(permission granted by American Chemical Society)

2.2.5.   Spectroscopic Method

A spectroscopic method gives a characteristic pattern of absorption bands for the sample and a

change in the characteristic pattern can clearly indicate the change in the composition of the

material. Gas/SCF solubility and volume swelling behavior can be measured from this method by

analyzing the characteristic pattern. In 1995, S. G. Kazarian’s team studied the interaction of CO2
229
and polymers by Fourier Transform Infrared Spectroscopy (FTIR) . High pressure CO2 was

used to pressurize PS, PE, PMMA, PEMA, Poly(vinyl acetate) (PVA) and Poly(vinyl methyl

ketone) (PVMK) films. In-situ spectra patterns were collected by FTIR for the CO2 pressurized

systems. By comparing the characterized CO2, IR spectra patterns in these six films, they observed

a steady increase in CO2 sorption in copolymers with increasing a vinyl acetate content and also

proposed that specific interactions might be responsible for this effect. Thus, they considered that

the changes in spectra of CO2 incorporated into polymers may serve as a basis for prediction of

the solubility of CO2 in polymers. Developed from the FTIR, Attenuated Total Reflection-FTIR

(ATR-FTIR) uses diamond and germanium crystals to seal the pressure cell and transfer IR with

less optical distortion due to its higher reflective index. This experimental setup enables accurate

measurements at different pressures and temperatures, providing quantitative information on the

physical changes occurring to the polymers. Therefore, it is possible to determine the degree of

swelling of the polymer, the concentration of CO2 absorbed into the polymer, and interactions

between the functional groups in polymers and CO2 230. N. M. B. Flichy, S. G. Kazarian, and their

colleagues used the ATR-FTIR to obtain CO2 absorption and Poly(Dimethylsiloxane) (PDMS)

swelling in the supercritical CO2/PDMS system in 2001 231. The schematic view of the polymer

on the ATR-FTIR crystal during CO2 exposure is shown in Figure 12. A specially designed

  34
“covering-cap” high-pressure cell, which was compatible with the single-reflection ATR

accessories, was used. All ATR FTIR spectra were recorded with a FTIR spectrometer. The

absorbance of the 2335 cm-1 band of CO2 dissolved in PDMS was used to determine the

concentrations of CO2 in PDMS by applying the Beer-Lambert Law. Polymer swelling was also

calculated by the absorbance of the 1259 cm-1 band. The CO2 absorption and swelling were found

to be very consistent with the values estimated by J. D. Wind et al. by a spectroscopic ellipsometer
232
.

Figure 12. Schematic view of the polymer on the ATR-FTIR crystal during exposure to CO2

Many researchers used the spectroscopic reflectometer to monitor thickness of the polymer in
233, 234
SCF/polymer systems . The sample was placed in a pressure chamber with high pressure

CO2 and it was observed through a sapphire window. Although the sapphire window affects the

light transmission more than the ATR crystal, which influences the accuracy, the error were

  35
corrected in the study of T. Shinkai, K. Ito and H. Yokoyama 234. The swelling behaviors of four

polymers, PDMS, PMMA, Poly(n-butyl methacrylate) (PBMA), and PS were measured in T.

Shinkai et al.’s paper and their results were consistent with former studies 235-237.

2.2.6.   Comparison of Different Solubility Measurement Methods

Four solubility measurement methods: gravimetric, piezoelectric, manometric, and

chromatographic methods have been discussed. The gravimetric measurement methods provide a

high sensitivity and a capability to measure solubility of many different gases in polymers.

However, the buoyancy and swelling effects must be corrected, and the methods require a long

experimental time. The piezoelectric methods, in comparison to the gravimetric methods are faster

processes, although the sample preparations are more complex. The manometric methods offer

wide ranges of operating temperatures and pressures but require a long experimental time.

Moreover, PVT relations along with swelling and buoyancy effects must be taken into an account.

In a chromatographic method, the simplicity and time efficiency of the experiments are the main

advantages. However, there is a limitation on the types of polymers and gases/SCFs that can be

used with this method (i.e., unable to measure for the glassy polymers with low diffusion

coefficients near the glass transition temperature). To compare the solubility data of gases/SCFs

in various polymers using different measurement methods the data on the polymers and

gases/SCFs used are tabulated in Table 5. Moreover, to outline the main advantages and

disadvantages of several measurement techniques, a summary table has been constructed in Table

6. In order to validate the reliability of different solubility measurement methods, solubility data

from different methods are compared from literature and plotted in Figure 13 and 14. Since PS

and PMMA are the most frequently investigated polymers, they are chosen as reference polymers
28, 132, 167, 168, 171, 193, 227
for the comparison . According to Figure 13a, the solubility data for all

  36
gravimetric, piezoelectric, and manometric methods are comparable for PS at 35 ˚C. There are

slight differences in the data obtained by gravimetric methods (i.e., McBain balance and Cahn

microbalance experiments), but these variances should be from the differences in compensation

for the buoyancy effect. The CO2 solubility data for PMMA at 35 ˚C also verifies that the solubility

data from the gravimetric and the piezoelectric methods are comparable as shown in Figure 13b.

Between the chromatographic and gravimetric methods, the solubility data seem to deviate as the

pressure becomes higher as seen from Figure 13c. The solubility at higher temperatures (50 ˚C to

200 ˚C) was also investigated from literatures as shown in Figure 14. The gas solubility at lower

temperatures is higher for both PS and PMMA than those at higher temperatures. The literature

data confirmed that all methods are comparable in terms of solubility data. However, at extreme

temperatures and pressures (above 10 MPa and 80 ˚C), many researchers used a MSB and pressure

decay methods.

Table 5. Comparison table of solubility experiments: (A) Gravimetric, (B) Piezoelectric, (C) Manometric, (D)
Chromatographic, and (E) Spectroscopic methods
Temperat Pressure
Cate ure working
Technique Gas Polymer Ref Year
gory working range
range
Quartz Spring 1971/
160 – 178 atmospheri 157,
Balance Ethylbenzene PS 1973
˚C c 238
(McBain)
PS, PMMA, Poly(vinyl
pyridine) , Polyisoprene,
Quartz Spring
and of styrene-methyl
Balance CO2 35 ˚C ~10.3 MPa 132 1977
methacrylate, styrene-vinyl
(McBain)
Pyridine and styrene-
isoprene block copolymers
A CO2,N2,
1986,
Methane, Poly(vinyl benzoate), 145,
1986,
Electronic Ethane, LDPE, PC, Polysulfone, 164-
1989,
microbalance ethylene, Poly(ethyl methacrylate), 25-85 ˚C ~5.07 MPa 166,
1992,
(Cahn) ethane, PMMA, Poly(ethylene-co- 168,
1994,
propane, vinyl acetate) 239
1998
Argon
Electronic
100-200
microbalance CO2 PMMA ~7.09MPa 168 1998
˚C
(Sartorius)

  37
 Quartz Spring m-xylene,
130-175 atmospheri
Balance nonane, PS, Polybutadiene 160 1989
˚C c
(McBain) ethylbenzene
Electronic
PS, PVC, Filled PVC, ~12.16
microbalance CO2 35 ˚C 167 1998
unplasticized PVC MPa
(Cahn)
Electronic 24, 1994.
Poly(chlorotrifluoroethylen
microbalnace 25, 1995.
CO2 e), Poly(dimethylsiloxane), 40 ˚C ~10.5 MPa
(Mettler 171, 1992.
PMMA, PS
AE163) 172 1999
Electronic
Poly(butylene
microbalance CO2 25-65 ˚C ~3 MPa 169 1988
terephthalate)
(Sartorius)
MSB N2, Isobutane, 110-200
PE ~20 MPa 175 1998
(Rubotherm) CO2 ˚C
MSB
CO2 PET 150 ˚C ~35 MPa 240 1999
(Rubotherm)
Poly(butylene succinate),
174, 2000,
Poly(butylene succinate-
MSB 176, 2001,
CO2 co-adipate), PVA, PS, 50-200 ˚C ~20 MPa
(Rubotherm) 177, 2002,
PPO, PPO/PS blends,
241 2005
PMMA
MSB PE/titanium dioxide
(Rubotherm composite, LDPE, HDPE, 178, 2004,
CO2 ~250 ˚C ~35 MPa
and BEL PP, ethylene-ethylacrylate 179 2002
Japan, Inc.) copolymer, and PS
Electronic
2004
microbalance methane, CO2 HDPE ~150 ˚C ~15 MPa 170
(Sartorius)
103, 2006,
MSB Polyactide, PP,
CO2, N2 ~250 ˚C ~35 MPa 148, 2007,
(Rubotherm) ethane/octane copolymer
149 2007
MSB
CO2 PP ~250 ˚C ~35 MPa 180 2007
(Rubotherm)
PEG, Poly(l-lactide) and
MSB 150, 2008,
CO2 Poly(d,l-lactide-co- 25-80 ˚C 7-25 MPa
(Rubotherm) 181 2008
glycolide)
Electronic
Microbalance
CO2 PS 30-100 ˚C 1-20 MPa 173 2015
(Mettler
AE163)
MSB 100-160
Argon PEG 0-33 MPa 182 2015
(Rubotherm) ˚C
Piezoelectric
crystal
0-11.72
sorption N2 LDPE 125 ˚C 183 1975
MPa
device
(Bonner)
Polydimethyl siloxane,
B Vibrating
nitrile rubber, PTFE, 1991,
beam 184-
CO2 diphenylmethyl-4,4- 80 ˚C ~30 MPa 1996,
technique 186
diisocyanate Polyester, 1998
(Briscoe)
Poly(Vinylidene Fluoride)
QCM Poly 4-methyl-1-pentene
CO2 40 ˚C ~9.65 MPa 191
(TPX), PMMA, Polymide

  38
 (PI) Ultern 1000, PC, PS,
Chlorinated Polyethylene 1998
(CPE-725), Parlene-N
(Par-N); Poly(xylylene),
Parylene-C (Par-C);
Poly(2-chloroxylylene),
Parylene-D (Par-D);
Poly(2,3-
dichloroxylylene), Teflon
AF-1600
QCM CO2 PS 40 ˚C ~17 MPa 187 1998
Octane,
cyclopentane,
cyclohexane, Cis-1,4-polyisoprene, PIB,
QCM bezene, Poly(n-butyl methacrylate), 20-80 ˚C n/a 188 2002
toluene, and PVA
ethylbenzene,
and p-xylene
HCFC-22 and
QCM PMMA, PS, PC 35-85 ˚C n/a 192 2001
HFC-152a
QCM CO2 PMMA, PS 35-81 ˚C 6 MPa 193 2006
Atmospher
QCM H 2O PC 15-35 ˚C 194 2015
ic
CO2,CO,CH4,
Direct Sub
O2,H2,N2,SO2,
experimental Rubber 100 ˚C atmospheri 198 1922
C2H4,H2S,NH3
procedure c
,He
Pressure Hydrogen,
PS 20-190 ˚C 8-30 MPa 204 1948
Decay Nitrogen,
Direct Sub
experimental He, Ne, H2 PVA 8-40 ˚C atmospheri 242 1958
procedure c
Pressure 206, 1960,
N2, Methane PE, PS 25-250 ˚C 33 MPa
decay 243 1963
Phase Poly(ethylene glycol)
CO2 ~100 ˚C ~35 MPa 201 1990
separation (PEG)
CO2,
Phase
1,1- PDMS, PS ~160 ˚C 0-26 MPa 202 1994
separation
difluoroethane
C
Phase Propane, N2, 142, 1997,
PEG ~150 ˚C ~50 MPa
separation CO2 203 2000
Pressure
Decay (2 CO2, CH4, Ar,
PC 35 ˚C 0.2-2 MPa 126 1977
sorption N2, He
Cells)
Pressure
Decay (2 CO2 Cellulose 2.4-acetate ~70 ˚C 0-4.56 MPa 208 1978
sorption cells)
Pressure
133,
Decay 1996,
CO2, N2 PS, PP ~200 ˚C 0-20 MPa 135
(3 sorption 1999
cells)
Polypylene,
Pressure Semicrystalline PP, Molten 134, 2001,
Butane, ~300 ˚C 17.5 MPa
Decay (2 PP, and PS 136 2004
isobutane

  39
 Sorption
cells)
Polyether-polyamide
He, H2, N2, O2, copolymers containing
Pressure
CO2, CH4, PEO or PTMEO as rubbery
Decay (2 35 ˚C 0-27 MPa 210 1999
C2H6, C3H8, n- Polyether phase and PA6
sorption cells)
C4H10 or PA12 as hard Polyamide
phase
He, H2, N2, O2,
Pressure
CO2, CH4,
Decay (2 PEO 35 ˚C 0-3.4 MPa 211 2004
C2H6, and
sorption cells)
C 3H 8
Pressure Isotactic Polypropylene 100-150
CO2 1-15 MPa 147 2009
Decay (iPP) ˚C
Vibrating
Wire- 212,
MDPE, Polyvinylidene
Pressure CO2,N2 ~ 200 ˚C ~70 MPa 213, 2005
fluoride (PVDF), PS
Decay (VW- 244
PVT)
Pressure
decay H2, CO2, N2,
TR-beta-polymers (PHAs) 20-65 ˚C 2.03 MPa 214 2015
(2 sorption O2, CH4
cell)
Pressure
Propylene and Polyurethane containing
decay (1 40-50 ˚C 0.7 MPa 215 2015
propane silver nanoparticles
sorption cell)
Benzene and
ethylbenzene,
n-decane, and
hexane, n-
Gas
hexane, PS, PE, atactic PP, HEPE, 222, 1972,
Chromatogra 80-185 ˚C 0.304 MPa
hexane- stereo-regular PP 223 1973
phic
isopropyl
alcohol
azeotrope,
cyclohexane
Cyclohexane,
Gas-Liquid benzene, n-
PIB,PVA, and
Chromatogra haxane, 50-175 ˚C n/a 224 1974
Poly(dimethylsiloxane)
phy toluene,
D chloroform
Ethyl ketone,
acetone,
isopropyl
alcohol, vinyl
Gas-Liquid acetate, sulfur
PE, and copolymers of 125-225
chromatograp dioxide, n/a 225 1976
ethylene and vinyl aceate ˚C
hy methyl
chloride,
ethane,
ethylene, and
CO2
Inverse gas
C2-C10 n- Poly(vinyl trimethylsilane)
chromatograp 25-250 ˚C n/a 226 1984
alkanes (PVTMS)
hy

  40
 Inverse gas
PS, PVA, PMMA, PP 20-200 221,
chromatograp 40 gases 35-280 ˚C 1990
(iso),Poly(1-gutene) MPa 226
hy
Polyether-polyamide
He, H2, N2, O2, copolymers containing
Inverse Gas
CO2, CH4, PEO or PTMEO as rubbery
Chromatogra 35 ˚C 0-27 MPa 210 1999
C 2H 6, C 3H 8, Polyether phase and PA6
phy
and n-C4H10 or PA12 as hard Polyamide
phase
Mass
spectrometric
-19-190
tracer pulse CO2 PMMA ~9.12 MPa 227 1998
˚C
chromatograp
hy (MSTPC)
Polyvinyltrimethylsilane,
Polyp3,4-
Nitrogen,
Chromatogra bis(trimethylsiyl)- Room
Oxygen, CO2,
phic Dynamic tricyclononene-7)], temperatu 0.253 MPa 228 2015
CH4, Ethane,
and static Polyhexafluoropropylene, re
and propane
and OH-containing
Polyimide
PS, PE, PMMA, PEMA,
1.4-8.97
FTIR CO2 Poly(vinyl acetate) and 25-40 ˚C 229 1996
MPa
Poly(vinyl methyl ketone)
25 ˚C and
ATR-FTIR CO2 PDMS ~12 MPa 231 2002
E 50 ˚C
Spectroscopic PDMS, PS, PMMA and 45 ˚C, 60
CO2 ~30 MPa 234 2014
Reflectometer PBMA ˚C, 75 ˚C
0.17~0.28 245
ATR CO2 HDPE 33 ˚C 1998
MPa

  41
Table 6. Comparison table of solubility measurements’ advantages and disadvantages: (A) Gravimetric, (B)
Piezoelectric, (C) Manometric, (D) Chromatographic, and (E) Spectroscopic methods
Category Technique Main Advantages
•   Relatively simple gravimetric
technique
•   Only small portion of the
balance required to be heated
and pressurized
•   Operates in moderate ranges
of temperature and pressure
•   Capable of measuring thin
McBain Balance film sample
•   Capable with small samples
of polymers due to high
sensitivity of the balances
Electronic •   Operates in wide ranges of
Balance (Cahn pressures and temperatures
and Sartorius) •   High sensitivity
A balance
•   Simpler to use compared to
the electronic balance and
MSB
•   Do not require embedded
pressurizing system
Weight Decay •   High sensitivity
•   Operates in high pressures
•   Contactless weight
measurement
•   Capable of operating in high
temperatures and pressures
and is not limited by the
MSB
balance because a sample is
isolated from the balance
•   High sensitivity
•   Compatible with corrosive
samples
 
Main Disadvantages
•   Not suitable for light
gases/SCFs that are not
highly soluble in polymers
•   Sensitive to external
vibration
•   The sensitivity of a spring
and extension per unit
weight calculations are
required
•   Must account for swelling
and buoyancy of polymers
•   Difficult with molten
polymers (i.e. polymers in a
liquid state)
•   Long experiment time
•   Limitation on corrosive
samples
•   Must account for swelling
and buoyancy of polymers
•   Complex to use
•   Long experiment time
•   Operating temperatures and
pressures limited by the
•   Limitation on corrosive
samples
•   Lose data during the
transportation of the sample
from a chamber to the
balance
•   Must account for swelling
and buoyancy of polymers
•   Operating temperatures and
pressures limited by the
balance
•   Limitation on corrosive
samples
•   Must account for swelling
and buoyancy of polymers
•   Long experiment time
•   Complex to use
•   Relatively expensive in cost
compared to other methods
42
 •   Does not require a volume
change correction
•   Fast experiment time
•   Sensitive enough to measure
small changes in weights
B QCM
•   Easy to add modifications to
system
•   Relatively simple and cost
efficient method to measure
solubility compared to the
gravimetric method
C Pressure Decay •   Compatible with numerous
gases and polymers
•   Wide ranges of temperatures
and pressures
•   Relatively simple and quick
compared to gravimetric and
manometric methods
D Chromatographic •   Provides other
thermodynamic properties
other than solubility
•   Unique dynamic method
•   Works for in-situ analysis
•   Useful for individual
diffusion analysis
•   Gives both polymer swelling
and gas absorption
E Spectroscopic
•   Provides valuable molecular-
level insights into the various
interactions between the
polymer and the solute
 
•   Hysteresis error from the
adhesion of polymer films
to crystals
•   Cannot detect slow changes
during sorption caused by
the polymer relaxation
•   Difficulty in preparation of
a thin polymer film on the
crystal – may be a limiting
factor
•   Require long experiment
time
•   Large amount of a polymer
sample required
•   Need to consider pressure-
volume-temperature
behaviors of the polymers
•   Must account for swelling
of polymers
•   Limited to volatile
substances
•   Difficult to determine for
glassy polymers with low
diffusion coefficients near
the glass transition
temperature
•   Cannot measure thick
samples
•   Only work for short time
gas diffusion cases
•   Background spectra could
not be recorded
43

 

 

       

Figure 13. Solubility plots of (a) CO2 in PS at 35 ˚C, (b) CO2 in PMMA at 35 ˚C, and (c) CO2 in PMMA at 25 ˚C
using various methods

  44
Figure 14. Solubility plots of (a) CO2 in PS at higher temperature, (b) CO2 in PS at extreme temperatures, 180 ~ 200
˚C , (c) CO2 in PMMA at higher temperatures, (d) CO2 in PMMA near 80 ˚C, and (e) CO2 in PMMA at 100 ˚C

3.   Research Approaches for Diffusivity of Gases/SCFs in Polymers

Diffusion describes the movement of one component from a high concentration region to a low

concentration region, resulting in a uniform distribution of a substance in a matrix. Diffusivity

  45
describes the rate of this diffusion process. The diffusivity is an important and critical property in

many polymer processes such as nano-/micro-cellular foaming, protective coating, separation-

membrane designing, and food and beverages packaging. Thus, clear understandings on the

gas/SCF diffusion mechanisms in a polymer and the relevant measurement methods are highly

desirable for many applications. There are two stages in diffusion: as the diffusion process

progresses, a permeant concentration continuously changes (i.e., unsteady diffusion) until it

reaches an equilibrium (i.e., steady diffusion) where a permeant concentration does not change

with time.

3.1.  Theoretical Approaches for Diffusivity Study

Two kinds of diffusion, steady and unsteady diffusion, are discussed here. The diffusivity values

of these two types of diffusion are always obtained by applying mathematic models with the

corresponding experimental data. Common equations and models are described below.

3.1.1.   Steady Diffusion

For steady diffusion, a flux does not change with time but with space. It is expressed as:

𝐽 = −𝐷∇𝐶 (1)

where J is the fluxes of atoms in atoms/(m2 × s), D is a diffusion coefficient in m2/s, and ÑC is a

concentration gradient in atoms/m4. It is called a Fick’s first law. Considering a unidirectional

case, this equation can be simplified as:

()
𝐽' = −𝐷
('
(2)

This simplification is valid in a membrane diffusion case when the thickness of a membrane is

much smaller than the other dimensions. The mean diffusion coefficient over the entire range of

  46
concentrations can be obtained by the “time lag” method developed by R. M. Barrer and E. K.

Rideal in 1939 246. In a steady state, the mean diffusion coefficient is directly proportional to time:

*+
𝐷= (3)
,-

where D is the diffusion coefficient, 𝑙 is the length of a polymer sample which a gas travels

through, and 𝜃 is the time lag which is the intercept of the time axis with the extrapolated linear

steady state portion of the pressure-time curve.

3.1.2.   Unsteady Diffusion

This is the case where a gas flux changes with respect to time before a diffusion process reaches

equilibrium. Many different models are used to describe this type of diffusion: Crank’s model,

Dual mode model, Gas-Polymer Matrix Model, Free Volume Model, Mass Transfer Model, and

some Empirical Models. Some of these models have very limited applications. For example, a

Dual mode model and a Gas-Polymer Matrix Model are only used for glassy polymers. The

detailed descriptions on each of these models are described below, and the comparison table for

diffusivity studies is tabulated in Table 7.

1)   Crank’s model

Crank’s model developed by J. Crank and G. S. Park is most used, since this model is easy to

understand, and suitable for various experimental geometries, accommodating different boundary

conditions. A sample shape has a great effect on gas transport behaviors. In 1968, Crank and Park

derived several equations based on the sample geometries. The following equation was used to

describe unsteady gas diffusion through a polymer film 247:

8
01 45 +
=2 (4)
02 67+

  47
where Mt and M∞ represent the mass uptakes of a penetrant at time t and at a long time, respectively.

L is a diffusion length. This model is mostly used in pressure decay experiments. This equation

can also be applied to diffusion cases along a cylindrical rod or tube with a length of L, where one

end of its surface is sealed and the other end is maintained at a constant concentration 247.

01 45
Although the simplified model is widely used, the original model ( = 2( + );/= 𝜋 ?;/= +
02 *

H B B*
2 BI;(−1) ierfc (45) ) gives more comprehensive descriptions of solubility and diffusivity

calculations 248.

2)   Dual-mode Sorption Model

This model divides diffusing molecules into two different populations: (i) the molecules dissolved

by an ordinary dissolution process whose concentration is CD, and (ii) the molecules trapped in

micro-voids which do not diffuse whose concentration is CH.

The dissolved gas molecules obey The Henry’s law:

𝐶4 = 𝑘4 𝑝 (5)

The concentration of the trapped gas molecules in micro-voids is given by the equation of

Langmuir 249:

)MN OP
𝐶L = (6)
;QOP

where C’H is a Langmuir saturation constant, which is directly related to the global volume of a

specific site (i.e., micro-voids), and b is an affinity constant for these sites, p is the pressure.

  48
These two populations have their own constant diffusion coefficients (𝐷4 ,𝐷L ) 250 and J is the total

flux.

R)S R)N
𝐽 = 𝐽4 + 𝐽L = −𝐷4
R'
− 𝐷L
R'
(7)

3)   Gas-Polymer Matrix Model

Different from the dual mode model described in the previous section, this gas-polymer matrix

model is based on the assumption that there is only one population of a penetrant but with an

interaction between a solute and a polymer matrix. The basic concept involves an activation

energy which represents the necessary energy for the separation of macromolecular chains by

cooperative motions of sufficient amplitudes to allow a penetrant to execute its diffusional jump.

This model assumes that the presence of a penetrant reduces the intermolecular forces between the

polymer chains, resulting in a smaller necessary activation energy for the separation of chains.

The increase in a penetrant concentration leads to a higher diffusion coefficient due to an enhanced

segmental mobility of the chains. From a mathematical viewpoint, this theory proposes the

following relation to express the interaction between a penetrant and a polymer 250:

𝐷 = 𝐷T (1 + 𝛽𝐶)exp  (𝛽𝐶) (8)

where 𝐷T is a diffusion coefficient in a zero-concentration limit, 𝛽 is a constant relating the excess

activation energy of chain separation to the depression of the glass-transition temperature of the

polymer by a gas, and 𝐶 is a gas concentration. As for the concentration, it can be expressed as:

𝐶 = 𝜎T 𝑝exp(−𝛼𝐶) (9)

where σT is a solubility coefficient at infinite dilution, 𝑝 is pressure, and α is a constant describing

the effect of gas-polymer interactions on solubility changes. The smaller α is, the less effect a

  49
penetrant has on solubility 251. This model gives a better understanding of molecular interactions,

gas perturbation, and thermodynamics than the dual-mode sorption model.

4)   Free Volume Model

The basic idea of this theory is that a gas molecule can move from an original position to another

when a local free volume exceeds a certain free volume fraction limit. This model explains the

relationship among a diffusion coefficient and parameters such as a glass transition temperature, a

penetrant shape and size, a temperature, and a concentration.

A free volume fraction,  𝑓, is one of the most important parameters for solubility and diffusivity

definitions. It is defined as:

^_ ^`a1 ?^abb
𝑓= = (10)
^`a1 ^`a1

where 𝑉de5 is a total volume, 𝑉eff is an occupied molecules volume and 𝑉g is a free volume.

A thermodynamic diffusion coefficient, 𝐷d , is given by H. Fujita and K. Kishimoto 252 as:

?kl
𝐷d = 𝑅𝑇𝐴( exp = 𝑅𝑇𝑚( (11)  
g

where 𝑅 is a gas constant, T is a temperature, 𝐴( is a parameter related to a penetrant size and

shape, 𝐵( is a characteristic parameter of an available free volume fraction, and 𝑚( is a mobility

of diffusing molecules relative to a polymer. The combined free volume fraction, 𝑓  is defined as:

𝑓 = 𝜙; 𝑓; + 𝜙= 𝑓= (12)

where 𝜙p  𝑎𝑛𝑑  𝑓p are corresponding volume fraction and the free volume fraction for a

component 𝑖. The index 1 refers to the diffusing molecule and the index 2 to the polymer.

Defined by J. Comyn 253, 𝐷d can also be expressed as:

  50
 R*B)
𝐷d = 𝐴exp( ) (13)
R*Bu

where C is a penetrant concentration, and 𝑎 is a penetrant activity parameter.

Based on the J. Comyn’s research, A. Peterlin modified the equation (11) and proposed the
following equation 254:

𝐷 = 𝐷 0 exp  (𝛼( 𝐶) (14)

where,

kl g8
 𝛼( = (15)
(w+  g+ )+
?kl
𝐷 0 = 𝑅𝑇𝐴( exp  ( ) (16)
w+ g+

Here, index 1 refers to the diffusing molecule and index 2 to the polymer. However, this model is

considered inappropriate for diffusion of small molecules. Therefore, correction for a free volume

fraction was applied to the model. The free volume fraction depends on three thermodynamic

variables as shown below 254-256:

𝑓 T, p, C =𝑓{|g 𝑇{|g , 𝑝{|g , 0 + 𝛼 𝑇 − 𝑇{|g − 𝛽 𝑝 − 𝑝{|g + γC (17)  

where the first term describes a standard fractional free volume in a reference state; the second

term shows the increase of a free volume with thermal dilation where a is a thermal expansion

coefficient of the free volume; the third term indicates free volume shrinking during a hydrostatic

compression (b is compressibility); and the forth term weighs the influence of a gas concentration

on a free volume.

5)   Mass Tratnsfer Model  

This theory is based on the Fick’s second law. This model can determine a diffusion coefficient

by measure a gas concentration in the polymer phase. The basic procedure of this model is to fit

  51
experimental gas concentration data with a predicted function.

In a transient state, a penetrant concentration could be expressed by functions of gas location in

the sample and time. A diffusion coefficient is an optimization parameter in this function.

The fundamental equation for this model is:

Rf R+ f
R5
=𝐷
R~ +
(18)

where 𝑐 is a penetrant concentration, 𝑡 is time, and 𝑧 is a gas travel direction in the sample, and 𝐷
257-259
is a diffusion coefficient. This equation was modified by many researchers . An initial

condition is given as below, describing no gas concentration in a polymer sample at time t = 0 247:

𝑐 𝑧, 0 = 0                0 < 𝑧 ≤ 𝐿 (19)

For gravimetric experiments with the samples with one sealed end, the boundary conditions

for  𝑧 = 0 are as below with no gas concentration change at the sealed end:

𝑐 0, 𝑡 = 𝑐 𝑡              0 ≤ 𝑡 ≤ 𝑇 (20)
Rf
R~ ~I7
= 0                  0 ≤ 𝑡 ≤ 𝑇 (21)

This model can also be approached with an iterative algorithm with an initial guess value for a

diffusivity coefficient. The value for a diffusivity coefficient keeps changing until the difference

between calculated and experimental data are within the tolerance limit.

6)   Empirical Model

For gas/polymer systems in which gas solubility essentially obeys The Henry’s law (e.g.,

hydrocarbons in elastomers), the dependence of a diffusion coefficient on the absorbed penetrant

concentration has been empirically represented at a given temperature by the equations shown

below 260:

  52
 Linear model 261:
 𝐷 𝐶 = 𝐷T (1 + 𝛽𝐶)                                                                                                                                                        (22)
Exponent model 255, 262:
𝐷 𝐶 = 𝐷T 𝑒 †) (23)
Concentration and pressure dependent model 263:
𝐷 𝐶, 𝑝 = 𝐷(0,0)𝑒 (†PQ‡)) (24)

Where 𝐷 is a diffusion coefficient, 𝐶 is a penetrant concentration, 𝑝 is a pressure,  𝐷T is a diffusion

coefficient when 𝐶 is zero, 𝛽 is a temperature dependent constant, and 𝛼 is a constant related to

plasticization.

The equations (21) and (22) obey the Henry’s law. In equation (22), the diffusion coefficient

shows a stronger dependence on the concentration. Equation (23) takes hydrostatic constraint and

plasticization into account 260.

Table 7. Comparison table for various diffusivity measurement methods

Experimental Temperature Pressure Diffusivity

Theories Polymers Gas 2 Ref Year
Methods (°C) (MPa) Range (m /s)
Fick's 2nd Pressure 3.53×10-9 -
PP N2 170,180,190 0.99-6.75 -9 257, 259 1998
law decay 10.32×10
highly -10
Fick's 2nd Pressure CO2, CH4, 2.5 × 10
viscous 75 and 90 3.96-4.08 -10 264 1999
law decay and N2 - 7.8 × 10
bitumen
Fick's 2nd Pressure 4.3×10-7
PS CH4 100-180 32 206 2000
law decay - 5.6×10-7
Fick's 2nd -12
2.19×10 -
law & free MSB PVA ; PS CO2 100, 150, 200 0.199-6.876 -12 265 2000
volume 554×10
Poly(butylen
e succinate /
0.68×10-9 -
Free volume MSB Poly(butylen CO2 120,150,180 2-9 176 2001
2.68×10-9
e succinate-
co-adipate)
-10
Empirical Pressure Heavy oils 1.12×10 - 266, 267
CH4 75 7.5-23.5 -10 2001
theory decay and bitumen 147.58×10
Polyethylene
Manome , polyamide He, Ar,
0.98×10-7
Time lag tric 11 and N2, CH4 41-132 0.14-30 268 2010
- 95×10-7
method poly(vinylide and CO2
ne fluoride)
high-
Polysulfone ,
pressure 1.03×10-7 -
Time lag Poly(vinylide CO2 40-80 5 269 2010
permeati 9.37×10-7
nefluoride
on cell

  53
 hexafluoropr
opylene) ,
and
Poly(tetraflu
oroethylene)
0.1×10-12
Time lag Pressure decay PVDF CO2 40-130 0.5-100 260 2012
- 2.5×10-12

3.2.  Experimental Approaches for Diffusivity Study

In this section, two main experimental methods for measuring gas/SCF diffusivity in a polymer

under unsteady states are introduced. The advantages and disadvantages of each method are also

discussed. Furthermore, a diffusivity measurement method for a steady state is also briefly

described.

3.2.1.   Pressure Decay Method

Figure 15. Schematic of common pressure-decay apparatus 258

Among all experimental methods for measuring gas diffusivity in a polymer, a pressure-decay

method, as shown in Figure 15, is attractive because of its convenience, simplicity, and accuracy
270
. In 1963, J. L. Lundberg and his team members used this method to measure diffusivity and

solubility of methane in PS at 33 MPa in the temperature range between 100 and 188 °C 206. In

  54
1969, his group repeated similar experiments using PIB 271. In a pressure decay method, a molten

polymer is molded to form a sheet where the sides of the samples are sealed to satisfy a single-

sided diffusion process. The sample is placed in the center of a high-pressure cell and the both

ends of the pressure cell are sealed to ensure a gas can only diffuse in a vertical direction. Prior to

a measurement, a vacuum is applied to desorb the sample of any impurities. Then, a testing gas is

injected and absorbed in the polymer sample. Gas diffusivity is indirectly calculated by measuring
272
the rate of gas volume or gas pressure changes after gas injection . There are many different

kinds of sensors such as laser and nuclear magnetic resonance sensors 258, 272 used in this method

to get the graphs of gas volume vs. pressure. Diffusion parameters could be obtain by using the

graph information with the models described in section 3.1.2.

3.2.2.   Gravimetric Method

A magnetic suspension balance (MSB) 257, 265 is one of the most popular and precise devices based

on the gravimetric method for diffusivity measurements. This technique gathers sample mass

change data with respect to measurement time and then fits the data with a diffusivity equation to

get a gas diffusivity coefficient.

An electronically controlled magnetic suspension coupling is used to transmit the measured force

from the sample enclosed in a pressure vessel to a microbalance located at an ambient temperature

and pressure as discussed in an earlier section 2.1.1. When a gas dissolves in a polymeric sample,

the weight of the sample grows due to the dissolved gas weight. A mutual diffusion coefficient is

then determined by measuring the weight change of the sample with respect to time as shown in

Figure 16.

  55
Figure 16. (a) CO2 Sorption profiles in LDPE and PS samples obtained by the step change in pressure from 11 to 12
MPa at 200 °C. The solid fitting lines are calculated by Fick’s second law178; (b) a typical diagram of
sorption/desorption experimental measurements 273 (Permission granted by Elsevier)

Many diffusion experiments generate permeate flux data with respect to time to fit modified Fick’s

second law functions to estimate diffusion coefficients. For example, Figure 16a shows the Fick’s

second law fit on the experimental data.

3.2.3.   Permeation Method for Steady State Diffusion

Numerous publications regarding measuring transport parameters, such as diffusion coefficients,

mass fluxes, equilibrium sorption data are readily available, but studies about steady state diffusion

in sorption and permeation are not easy to find in open literatures 274.

In the gas permeation experiments, after a certain period of a diffusion process, the gas

concentration for all points in the polymer does not change with time. This is called a steady state.

The permeation experiments create a desired gas concentration difference between two sides of

polymer membrane to reach steady state. If there are no gas concentration difference between

these two sides, the membrane will reach equilibrium which means every points of the polymer

has same constant gas concentration.

It is reported that, in the toluene/linear low density polyethylene (LLDPE) system, the ratio of

  56
steady state and equilibrium absorbed amounts is 0.5 275. It is improper to represent a steady state

property with an equilibrium state data. The permeant absorption difference between a steady

state and an equilibrium state can also provide valuable information about material swelling and

gas concentration profiles across the membranes 275. In this case, it is necessary to obtain steady

state diffusion data.

As demonstrated in section 3.1, the simplest technique to calculate a diffusion coefficient at a

steady state is based on the Fick’s first law:

Rf
𝐽 = −𝐷 (25)
R'

Figure 17 shows a vapor permeation device for a steady state measurement. A sweeping gas (e.g.,

N2) flows on one side of the membrane in a chamber and the opposite side of the membrane is

contacted with vapor. Both the upstream and downstream gas flows to maintain a certain pressure

on the surfaces of the membrane. A Flame Ionization Detector (FID) is widely used to detect a

vapor concentration in the upstream side of the chamber. The FID signal displays a maximum

value when a steady state is reached. A steady state flux then can be calculated from the FID

maximum signal 274.

  57
 Figure 17. Permeation device for steady state measurements

Unlike the pressure decay equipment shown in Figure 15, the pressures on both sides of the

membrane in Figure 17 are fixed due to continuous gas supplies and this makes it easier to obtain

steady state data.

For gas transport experiments, a membrane is always moved from a sorption/permeation cell to a

desorption cell to determine the amount of absorbed permeants, but the loss of absorbed permeant

during the transfer is unavoidable. To reduce this loss and error, a new apparatus, as shown in

Figure 18, based on a permeation device was designed by U. Petr , P. Roman and S. Katerina

which requires no transfer of a membrane from a permeation cell to a separate desorption cell 259,
266, 275
.

  58
 Figure 18. New apparatus for steady state diffusion study 275. (Permission granted by Elsevier)

By using the apparatus shown in Figure 18, permeants absorbed in a steady state can be determined.

As shown in Figure 18, the system is cleansed and purged with a sweeping gas, N2, in steps 1 and

2. In Step 3, N2 is substituted by feed vapor (i.e., the gas for the diffusivity experiments) as the

membrane is separated from the feed by piston 1. After that, a vapor permeation process starts

which allows a steady feed flow over a membrane and permeates on the other side (Step 4). The

vapor permeate from the feed is detected by a FID sensor which gives a vapor concentration in N2.

  59
Lastly, the cell is purged in step 5 and the feed gas absorbed in the membrane was desorbed in step

6 274.

4.   Outlook for the Future

Many different techniques for measuring gas/SCF solubility and diffusivity including the

limitations of each method have been discussed in this review. Some of the limitations are

inevitable due to its operating principles such as the long measurement time of a pressure decay

method. These types of limitations can be overcome by using a different measurement method

such as a QCM or inverse gas chromatography. The high cost of equipment such as the MSB can

be avoided by conducting experiment using the pressure decay method. Most of the problems

encountered in measuring solubility and diffusivity could be resolved with collaborations among

the researchers from various laboratories. Nevertheless, there still exists an outlook for the future

work in solubility and diffusivity measurement techniques and devices. The accessibility of the

measurement devices is a major factor. The measurement devices that are simple, durable, easily

accessible, and cost efficient encourage the researchers to investigate further in this field. Another

interesting aspect to study in the gas/SCF solubility and diffusivity measurement devices is the in-

situ measurements in the processes. If solubility and diffusivity measurement can be conducted

in-situ to the experiments or processes, it would allow more opportunities to investigate interesting

phenomenon such as static versus shear induced solubility and diffusivity in many applications.

5.   Conclusions

Final plastic products result in different morphologies depending on how they are processed, and

whether gases or SCFs are utilized in the process or not. Understanding solubility and diffusivity

of gases/SCFs in polymers is very significant for many application areas such as polymer

  60
impregnation, polymer blending, and plastic foaming. In this review, solubility and diffusivity

measurement principles and techniques are discussed in details along with the practical

applications requiring solubility and diffusivity data.

The measurements of gas/SCF solubility in polymers can be categorized into four methods:

gravimetric, piezoelectric, manometric, and chromatographic techniques. A gravimetric method

measures gas/SCF solubility in polymers by monitoring sample weight changes due to gas/SCF

sorption over time. Earlier devices used a quartz spring balance (McBain balance) based on the

Hooke’s Law to derive sample weight changes but later on, more sensitive balances such as

electronic balances or magnetic suspension balances (MSBs) are favored. A piezoelectric method

uses piezoelectric crystals to investigate the gas sorption behaviors. The vibration frequency of a

piezoelectric crystal depends on the weight change and can be measured accurately. The weight

of the sample is expressed as a function of gas pressures and using a mass balance equation, the

weight of a gas dissolved in a polymer can be calculated. A QCM is used widely by many

researchers to obtain solubility data and it is favoured because of its short operation time. A

manometric method measures solubility by measuring the pressure or volume of a gas absorbed in

or desorbed from a sample at an equilibrium state. In early studies, the experiments were

conducted in a sub-atmospheric pressure but eventually techniques such as a pressure decay

method with dual sorption cells allowed solubility measurements at higher temperatures and

pressures. A pressure decay method is also favoured due to cost efficiency. However, this method

is time consuming. The last method mentioned in this review is a chromatographic method. In

chromatography, gas sorption is dependent on the retention time and volume of a polymer, thus a

gas chromatography technique measures the retention time and volume to acquire the sorption data
151
. Gas chromatography is more reliable and simpler with a short measurement time than other

  61
measurement methods such as gravimetric and manometric techniques 217. Moreover, this method

can measure solubility with respect to temperatures while providing other thermodynamic

parameters such as dispersion surface energy or acid/base interaction data. However, due to

diffusion limitations, solubility data cannot be measured for glassy polymers at temperatures below

their glass transition temperatures. The solubility data obtained from various methods are

compared in this review. A theoretical model should be integrated with the experimentally

obtained solubility data to improve data accuracy. For gravimetric and manometric methods, a

theoretical model must be used to compensate for the buoyancy effect and volumetric expansion

due to gas sorption. A Sanchez-Lacombe (SL) theory is widely used in many studies.

Different diffusivity measurement methods are also described in this review paper. Diffusivity

data can be acquired in two methods: gravimetric and pressure decay methods. Similar to the

solubility measurements, a MSB can be utilized in diffusivity measurements. As for a pressure

decay method, a pressure decay cell is widely used in literature to measure diffusivity. A new

apparatus obtaining diffusivity in one step, and thus, simplifying the measurement process greatly,

was also developed and is introduced in this review. Diffusion theories are relatively more

complicated than solubility theories. Various diffusion theories are described in this paper, and

each one could build a different model. PVT data are always used to fit the theoretical models and

optimize the model parameters.

Solubility and diffusivity are key parameters in many polymer application areas such as polymer

impregnation, polymer blending, and nano-/micro-cellular foaming. In a polymer impregnation

process, particles are implanted into the selective regions inside a polymer matrix by a gas or a

SCF and thus, the solubility and diffusivity of a gas/SCF can affect the polymer modification

process greatly. Moreover, for the fabrication of polymer blends and composites, the solubility of

  62
supercritical CO2 in a polymer determines the viscosity of the polymer resins, and thus the final

morphologies of the polymer blends. In a similar manner, the solubility of supercritical CO2 in a

polymer controls the finished foam product morphologies and qualities in a nano-/micro-cellular

foaming process.

The importance of solubility and diffusivity data in many applications implies great needs for

deeper understanding of the current measurement principles and methods and the future

improvements on the measurement techniques.

6.   Declaration of Interest

The authors declare that there are no conflicts of interest.

7.   Acknowledgements

Funding supports from Natural Sciences and Engineering Research Council (NSERC) Discovery

Grants and NASA Vermont EPSCoR are acknowledged. The authors would also like to

acknowledge critical manuscript review performed by Joseph Dooley, J. Dooley Consulting LLC.

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