Untitled
Untitled
Untitled
by
VIDYA MAHANKALI BURRA, B.Tech., M.Tech.
A DISSERTATION
IN
CHEMICAL ENGINEERING
Submitted to the Graduate Faculty
of Texas Tech University in
Partial Fulfillment of
the Requirements for
the Degree of
DOCTOR OF PHILOSOPHY
Approved
May, 1993
r'
ACKNOWLEDGEMENTS 7/. - •'
complete freedom in defining and directing my research. I also appreciate his insightful
and constnictive critique and his emphasis on writing with clarity and precision. I would
like to thank Dr. Richard Wm. Tock, Dr. Raymond E. Desrosiers and Dr. Harry W.
Parker for their valuable advice and suggestions during the course of this research. I also
I also owe thanks to Mr. Robert Spruill for helping me in the fabrication of the
apparatus required for the experimental work, and to the Department of Chemical
this would have been possible, and to my family back home in India. My grandmother,
parents, brothers and sister have encouraged me in aU my endeavors, and will always be
11
TABLE OF CONTENTS
ACKNOWLEDGEMENTS ii
LIST OF TABLES v
LIST OF FIGURES vi
CHAPTER
1 INTRODUCTION 1
2 LITERATURE SURVEY 11
3 DEVELOPMENT OF MODEL 29
3.1 Theory 29
111
4 EXPERIMENTS 37
4.3 Materials 40
rates of membranes 42
5 COMPUTATIONS 46
7 CONCLUSIONS 79
8 RECOMMENDATIONS 81
REFERENCES 83
APPENDICES
VI
LIST OF SYMBOLS
a^ activity of species i
d^ combinatorial component of a^
Gjj^ excess molar Gibbs free energy for binary solution of species i and j
AGjj molar Gibbs free energy change of mixing for binary solution of species
i and j
^Q_^M4d molar ideal Gibbs firee energy change of mixing for binary solution of
species i and j
T temperature
|Xj® chemical potential of pure species i in standard state (25 °C, 1 atm)
vii
CHAPTER 1
INTRODUCTION
A membrane is defined as a thin barrier or film that separates two fluid streams
and restricts or permits the selective transport of a chemical species across it.
the absolute rate at which the permeant is transported across the membrane. The rate at
which two different species permeate through a membrane relative to one another is
used to design separation processes if adequate differences between the transport rates of
There are several naturally occurring membrane processes, such as the uptake of
water and nutrients from soil by plant cells, the transfer of oxygen into blood cells inside
the lung, the removal of solutes such as urea from the blood stream by the kidney, etc.
The barriers or films that are encountered in these processes are caUed biological
synthetic membranes. Conceptually, these processes are similar to the naturally occurring
processes mentioned above. The transport properties of these synthetic membranes can
Membrane processes are normally classified according to the driving force for the
membrane, while in a gas separation process, the driving force is the gradient of the
partial pressures of the gases involved. The driving force in a reverse osmosis process is
the pressure gradient across the membrane, and in dialysis applications, is the concentra-
polymers, metals and ceramics. However, the vast majority of the membranes in
commercial use are based on polymeric material. The permeability and selectivity
influenced not only by the molecular structure of the polymer, but also by the physical
The molecular structure of the polymer includes factors such as the physical state
amorphous polymer are constantly in motion. However, below a certain temperature Tg,
the segments of the polymer chains do not possess sufficient energy to move past one
another, and are trapped in a chaotic, disordered state. A polymer in such a state is called
a glass, and the temperature Tg below which molecular motion is restricted is referred to
temperature above its Tg is called a rubbery polymer. The glassy or rubbery state of the
polymer, the nature of the chemical group comprising the polymer chains, the size and
nature of side groups attached to the main polymer chains, etc, determine the size of the
spaces between the polymer chains and the chemical affinity of the polymer to a chemical
species. These affect the inherent permeability and selectivity properties of the polymer.
shown in Figures 1.1 and 1.2. The morphology of a polymer membrane, determines the
mode of transport of a chemical species across the membrane, and therefore the eflective
The transport of a chemical species across a dense polymer film, for example,
The chemical species dissolves in the polymer membrane matrix and diffuses across it.
phenomenologicaUy the product of its diffusivity and solubility in the membrane polymer.
Dense films of polymers exhibit the inherent permeability and selectivity characteristics
of the polymer material. Dense films of rubbery polymers generally exhibit high
permeabilities but low selectivities for real gases, whereas glassy polymers exhibit high
selectivities at lower transport rates. For example, the pure gas permeabilities of CO^ and
approximately 5700 barrers* and 1800 barrers respectively, which results in an intrinsic
(CO2/CH4) selectivity of 3.16 for this polymer. The large diffusivities, and therefore the
large permeabilities, and low selectivities of rubbery polymers are consistent with the
large scale segmental motion in rubbery material relative to the sizes of the penetrant
identical conditions, on the other hand, are 4.6 and 0.18 barrers respectively [79]. The
intrinsic selectivity in this case would be approximately 25.6. For glassy materials, the
range of segmental motions, and hence the size of the gaps, are much smaller and more
narrowly distributed, thereby providing a much more restrictive environment for different
penetrants. Films of glassy polymers are therefore used in barrier applications, such as
protective coatings and packaging material where low permeabilities are desirable, but are
Porous polymer membranes with pore sizes in the range of 5-10 nm use the
"sieving" mechanism to separate large molecules from smaller ones and find use in
with pore sizes in the range of 0.1-10 |im are employed in microfiltration applications,
Completely dense or porous membranes with a uniform pore size are referred to
as symmetric or isotropic, since membrane structure does not vary across the thickness
of the membrane. Prior to 1960, the only known polymer membranes were isotropic or
Loeb and Sourirajan in 1960 [1,2]. Skinning in a polymer membrane refers to the
formation of a thin dense layer called the "skin" (typically 0.1-1.0 ^im in thickness) which
is bonded to a thick, porous substructure (100-200 |im in thickness). The skin and the
substructure are composed of the same material and are formed at the same time during
s
S
9
•.JLW
7
the membrane preparation process - hence the term integrally-skinned. The thickness and
integrity of the skin determine the transport characteristics of the membrane. The porous
sublayer functions primarily as a physical support for the thin and fragile skin and has
attracted considerable commercial interest [3] since the late 1960s. Asymmetric polymer
membranes are used on a large scale in reverse osmosis [4], ultrafiltration [5,6] and, more
scale by the phase inversion technique [11]. Phase inversion refers to the process in which
single phase into a two-phase system. The two-phase system consists of a solid (polymer-
rich) phase which forms the membrane structure and a liquid (polymer-poor) phase which
forms the pores in the final membrane. Phase inversion membranes can be prepared from
any polymer-solvent mixture which forms a homogenous solution under certain conditions
of temperature and composition, but separates into two phases when these conditions are
changed. For example, phase inversion can be induced by the evaporation of a volatUe
homogenous only at elevated temperatures. Phase separation can also be brought about
8
solution. This particular variation is referred to as the wet phase inversion technique. The
general procedure for the preparation of a wet phase inversion membrane is as foUows.
(b) The homogenous polymer solution is cast into a thin film. The fihn is typically 100
(c) The film is then quenched in a coagulation bath to precipitate the polymer membrane
out of the solution. The coagulation medium is typicaUy water, which acts as a strong
nonsolvent for most of the polymers used in the preparation of these membranes.
properties of these membranes occur in the quenching step, during which nonsolvent-
solvent exchange takes place foUowed by various phase transformations in the polymer
During the phase inversion process, the combination of steps leading to a given
by simUar thermodynamic and kinetic parameters, such as the chemical potentials and
diffusivities of the individual components and the Gibbs free energy of mixing of the
of the phase inversion process have led to several studies of the process conditions and
factors that influence the transport properties of these membranes is far from complete.
thermodynamic factors that can correlate the process variables used in the membrane
10
CHAPTER2
LITERATURE SURVEY
The foUowing sections wiU discuss some of the empirical studies, kinetic and
The earUest studies of membrane formation by the phase inversion technique were
largely empirical in nature. The emphasis of most of these studies was on detaUed recipe-
acetone and formamide solvents. These studies attempted to obtain the "optimum"
conditions for the formation of ceUulose acetate (CA) reverse osmosis membranes.
evaporation time, gelation bath composition and temperature, and relative humidity of the
al. [14,15] examined the effects of these variables on the water content and, therefore, the
porosity of the swoUen membranes obtained at the end of the coagulation step. SimUar
studies were performed by Leymone et al. [16,17]. They also examined the effect of the
11
addition of inorganic salts to the casting solution of CA-acetone mixtures in order to
membranes. These studies revealed that low precipitation rates of the polymer from the
casting solution produced membranes with sponge-like structures, whUe high precipitation
rates yielded membranes with large finger-Uke macrovoids. The authors proposed a
mechanism based on the differences in the precipitation rates of the polymer to explain
the asymmetric nature of the membranes. Studies by Uragami et al. [20] concluded that
it is important to substitute the solvent in the polymer film with the nonsolvent in the
coagulation bath at high velocities in order to make structures with finger-like voids.
SimUarly Bottino et al. [21] performed experiments to estabUsh the relationship between
macrovoid formation and the ratio of solvent to nonsolvent flow between the casting
Strathmann et al. [22] also attempted to correlate the water content of the water-
swoUen membranes at the end of the coagulation step, and therefore the porosity, of
parameters of the solvents used in the preparation of these membranes. Studies simUar
to these were also performed by Chawla and Chang [23], Cabasso et al. [24], and
Uragami et al. [25]. The studies by Chawla and Chang also examined the effect of
solution containing CA and acetone. The solubiUty parameters of the casting solution,
12
plotted on a two-dimensional solubiUty map, were correlated to the porosity and
permeabUity of the resulting membranes. Uragami and Cabasso observed that there were
simUar characteristics in certain solvent groups, which can l^e classified by their solubUity
parameters.
Kesting and Menefee [26] attempted to correlate the effect of increasing the
concentration of formamide in the casting solution and the viscosity of the casting
inversion membranes. Cabasso and KUen [27] also showed tiiat high viscosities for the
spinning dope and relatively moderate quenching conditions in the bore fluid should be
used to get macrovoid-free polysulfone (PSf) hoUow fiber membranes. Empirical studies
ultrafiltration membranes were also performed by Doi and Hamanaka [28]. They found
that a "mixabiUty" parameter, which was obtained from titration experiments, and the
was also noted that finger-Uke void layers appeared under conditions where the coagulant
has both a low mixabiUty parameter and low viscosity. These results were appUed to
solution formulations to control pore formation in polysulfone (PSf) and polyamide (PA)
phase inversion membranes. More recently, Miyano et al. [30] studied the effect of
polymer molecular weight and solvent and casting solution composition on the pore sizes
13
correlate the effective hydrodynamic radius of the polymer in the casting solution and the
average pore size on the membrane surface and proposed a mechanism for pore formation
namic concepts have attempted to provide a more definitive quantitative analysis of the
Kinetic models of the phase inversion process have examined the mass transfer
dynamics of the process. The focus of these models is the analysis of the mass transfer
paths of the solvent and nonsolvent inside the polymer film and their effects on
binodal curves and tie-lines, and examined their relevance to the membrane formation
process.
discussed in this section, foUowed by a review of some of the kinetic and thermodynamic
models.
a temary phase diagram as shown in Figure 2.1, where the comers of the triangle are the
14
Solvent
2
Nonsolvent
15
pure nonsolvent (1), solvent (2) and polymer (3). The polymer is assumed to be mono-
disperse, i.e., even though the polymer is a mixture of molecules of different sizes, aU the
The binodal curve, or cloud point curve, represents the limit of the miscibiUty of
the system. The area inside the binodal curve is caUed the miscibiUty gap. Any system
whose composition Ues inside this gap separates spontaneously into two phases which are
in equiUbrium with each other. The miscibiUty gap is again separated into metastable and
highly unstable regions by the spinodal curve. The area inside the spinodal curve is highly
unstable whUe that between the spinodal and binodal curves is metastable. A line which
connects two points representing two phases which are in equiUbrium with each other is
caUed a tie-line. For example, in Figure 2.1, if the points A and A' represent two phases
in equiUbrium with each other, the line AA' represents a tie-Une across these two points.
Any system whose composition corresponds to a point on the tie-Une AA' demixes
Early models [31,32,33] of the mass transfer processes occurring during the
membrane formation process focused mostly on the optional evaporation step. These
models assumed tíiat skin formation and, therefore, tiie determination of the membrane
characteristics occur during the evaporation step. The basic stmcture of aU the evaporation
models is simUar. The solvent volume fraction in the film was determined by the solution
16
boundary conditions in tíie film. Ray [34] presented a model which claimed to t>e an
improvement on the earUer approaches due to the incorporation of volume changes in the
are strongly affected by changes in the quench batíi conditions, such as bath composition
and temperature. Most of the subsequent efforts, therefore, used the evaporation models
simply in the form of an initial condition for the modelUng of the quenching step.
Cohen et al. [40] developed one of the earUest models for the diffusion-controUed
formation of porous membranes obtained by the phase inversion process. Their theory was
based on the diffusion-induced phase separation at the spinodal of the temary nonsolvent-
at the limit of metastabiUty, i.e., at the spinodal, and by treating the flow of the solvent
and nonsolvent in the film as a one-dimensional diffusion process, they formulated criteria
for the formation of the membrane stmctures. These criteria are expressed in terms of the
chemical potentials of the components in the stable and metastable regions of the temary
phase diagrams.
The above model of Cohen et al. neglects mass transfer in the coagulation bath
and assumes that surface concentrations of the nonsolvent in the bath is constant
17
of Cabasso [41]. In addition, other studies [14,15,18,42] have concludedtíiatmass transfer
on the bath side can have a strong influence on the stmcture of the membranes.
Studies by Yilmaz and McHugh [43,44] were based on the premise that the
principal stmcture-forming processes for both the skin and the sublayer occur during the
movement of the polymer molecules. Their model accounted for the effects of the surface
boundary conditions, they were able to plot the concentration profiles of the solvent and
nonsolvent in the film on the temary phase diagram to determine the conditions under
which the profile enters the unstable region of the miscibiUty gap. These temary
concentration plots were used to differentiate formation conditions for completely dense
morphologies from those of asymmetric and porous stmctures. However, since this model
treats the flux ratio of the nonsolvent to solvent as a parameter that must be determined
Tsay and McHugh [45,46] developed a simUar model to study the mass transfer
processes associated with the quench bath period of the phase inversion process. In
addition to the diffusion equations formulated by Yilmaz and McHugh, the model of Tsay
and McHugh included separate diffusion equations to account for the dynamics of the
bath side mass transfer process. In this model, it was considered that phase separation
occurs whenever the mass transfer path crosses the binodal curve and reaches the
metastable region. DetaUed calculations were carried out for the water-acetone-cellulose
18
acetate system. By imposing the mass transfer path on the temary phase diagram, the
model calculated the precipitation time required for these membranes and attempted to
Tsay and McHugh [47] also analyzed the effects of the combined evaporation and
quench steps of the phase inversion technique. The primary focus of this study was the
effects associated with the evaporation step variables such as evaporation time, initial
Young and Chen [48] investigated the mass transfer mechanism for the diffusion-
controUed formation of ethylene vinyl alcohol (EVAL) phase inversion membranes. They
proposed a two-step mechanism model to describe the mass transfer processes occurring
during the formation of these membranes. The authors hypothesized that the ratio of the
nonsolvent inflow to solvent outflow is important in determining the stmcture of the top
layer or skin of the membrane. More specificaUy, the compactness of the skin depends
on the local composition at the time of phase transition. The solvent and nonsolvent flow
across the lower layers of the membrane and, therefore, the stmcture of the lower layers,
depend on the compactness of the skin. The morphology of various EVAL membranes,
obtained by changing the solvent content of the coagulation bath, was explained on the
inversion process was conducted by Koenhen et al. [49]. They proposed a general
19
two-step mechanism for the formation of these membranes based on the phase equiUbria
of the polymer solutions. According to their hypothesis, the membrane skin is formed by
the direct desolvation of the top layer of the polymer solution, foUowed by gelation of
the polymer chains. The stmcture of the porous sublayer below the skin layer is
dependent on the liquid-Uquid separation in the polymer casting solution. In most cases,
the porous substructure is formed by the nucleation and growth of the dUute polymer
phase. The concentrated polymer phase forms the continuous matrix that constitutes the
fmal membrane after complete desolvation. The authors also noted that when the
difference in chemical potential for the solvent between the polymer solution and the
concentrated polymer phase, are responsible for the buUdup of the dense skin layer and
the supporting porous sublayer in asymmetric membranes. From the temary phase
concluded that the factors which favor tíie formation of a dense skin, i.e., tíie formation
of a reverse osmosis type of membrane are: (a) a higher initial polymer concentration in
the casting solution, which increases supersaturation of the polymer in the top layer of
the membrane during the coagulation step; (b) a lower tendency of the nonsolvent to
20
penetrate the top layer of the cast fUm; and (c) a lower coagulation bath temperature
which, once again, increases the supersaturation of the polymer in the top layer. On the
other hand, factors favoring the formation of ultrafUtration type of membranes are lower
polymer concentrations in the initial casting solution and addition of nonsolvent to the
The authors also observed that membrane-forming systems which require large
ultrafiltration membranes.
Other studies by Altena and Smolders [51], Wijmans et al. [52], and Gaides and
concentrations, on the other hand, suggested that gelation in these systems is amorphous.
Altena and Smolders also discussed the characteristic properties of some of the PSf-DMac
stmcture of the membrane skin obtained in these two cases was explained as foUows in
21
terms of the "composition path" foUowed by these systems during the coagulation step.
The different composition changes for the top layer (skin) and the sublayer as visuaUzed
in the temary phase diagram are referred to as tíie composition path foUowed by the
system. The autíiors hypotíiesized tíiat tíie 35 weight% polymer solution yields a
membrane with a dense skin because the composition path foUowed by the system during
the coagulation step does not crosstíiebinodal curve. Lowering the polymer concentration
in the casting solution to 15 weight % increases the possibiUty of the coagulation path
crossing the binodal curve and, therefore, of liquid-Uquid demixing occurring in the skin
layer. From this analysis, it was concluded that the location of the binodal curve in the
temary phase diagram is important in determining the nature of the membrane skin.
Burghardt et al. [54] also examined the glass transition, crystaUization and
presence of ethanol, methanol and octanol nonsolvents was examined. The effect of the
was studied using DSC. CrystaUization and gelation behavior was examined by DSC and
the falling baU method [55]. Gelation in these systems was found to be entirely
amorphous. The authors hypothesized that knowledge of the glass transition behavior of
in these membranes. Using theoretical equations for the glass transition temperature, they
generated glass transition curves in the temary phase diagrams of these systems. For the
systems under consideration in this study, it was observed that the branch of the binodal
22
curve corresponding to the concentrated polymer phase Ues in the glassy region of the
temary phase diagram in aU cases. Based on these results, it was concluded that as the
solvent diffuses out of the polymer film during the quenching step, the concentrated
polymer phase eventuaUy becomes a glass. The authors thus provided a simple
Reuvers et al. [56] examined the demixing and gelation behavior of temary CA-
acetone and tetrahydrofuran solvents. They measured cloud points as a function of the
rates at which the solutions were cooled and attempted to distinguish the process of
polymer aggregate formation from the more rapid process of Uquid-Uquid demixing using
scanning electron microscopy (SEM). It was observed that the appearance of polymer
aggregates depended strongly on the type of solvent used in the casting solution. The
gelation behavior of these systems was characterized by the falling baU method in order
to determine the position of the sol-gel transition curve in the temary phase diagrams.
reflects different time regimes required for composition changes to occur at different
positions in the coagulating film. They hypotíiesized that for the formation of the skin,
there are two possibiUties: (a) tíie coagulation path crosses the gel region before
intersecting the binodal demixing gap or (b) the coagulation path intersects the binodal
curve prior to entering the gel region. The location of the binodal curve is therefore
important in the formation of the dense top layer. It was observed that as the proximity
of the binodal curve to the polymer-nonsolvent axis increased, the greater was the
23
lUceUhood that the gel region is reached before the binodal curve is crossed by the
Altena and Smolders [58] attempted to predict tíie tíieoretical binodal curves for
Flory-Huggins binary interaction parameters on tiie location of tíie miscibUity gaps in tíie
temary phase diagrams of these systems was examined. Once again, it was observed that
systems which require only smaU amounts of nonsolvent for Uquid-Uquid phase separation
to occur resulted in membranes with ultrafiltration properties, whUe those requiring large
the behavior of the spinodal as weU as the binodal curves, tie-Une slopes and critical
the miscibiUty gap. Two different values of water-acetone interaction parameters obtained
from Uterature sources [40,58] were used to calculate the binodal and spinodal curves and
the tie-Unes for this system. It was observed that by use of varied values of the
24
the locatíon of the curves, but also in the slopes of the tie-lines. Based on these results,
the autíiors hypothesized that during the quenching step, the point of entry of the
coagulation path into the region of immiscibUity wUl have a strong influence on the
porosity of tíie precipitated layers. Therefore, tíie calculation of the sequential buUdup of
porosity in the membrane would require knowledge of the positions and slopes oftiietie-
in this study were obtained from experimentaUy determined excess Gibbs free energy data
interaction parameters were obtained from tabulated values in Uterature for the acetone-
CA system [60].
A simUar study was performed by Shuguang et al. [61] who investigated solution
thermodynamics for the water-DMAc-PSf system. This study assumed constant values for
the water-PSf and DMAc-PSf interaction parameters, whUe the water-DMAc interaction
cloud point curve calculated from these parameters was in reasonably good agreement
water-NMP interaction parameter was obtained from the excess Gibbs free energy data
25
The water-polymer interaction parameter was obtained from polymer swelUng data. The
experimental values of the cloud point curves agree very weU with the theoreticaUy
were water, methanol, ethanol, 1-propanol, acetone and carbon tetrachloride. The authors
determined the cloud point curves for these systems and attempted to correlate the amount
of nonsolvent required for the polymer to precipitate out of the solution to the binary
and water-solvent-PES systems. The solvents used in this study were NMP, DMAc,
The authors obtained tie-Une data and cloud point curve data for these systems, and
correlated the size of the miscibiUty gap in each case to the solvating power of the
solvent for the polymer and the degree of tolerance of the polymer to the nonsolvent,
membrane preparation parameters. Also, the results of some of these studies were too
26
specific to be appUed to other systems in general. For example, Kesting et al. [15]
explained on the basis of the gelation rate of the casting solution in the batíi. SimUarly,
formamide in the CA-acetone casing solutions [26] was attributed to the abUity of
example, Chawla and Chang [23] developed a two-dimensional solubiUty map for CA
using nearly tíiirty solvents and swelUng agents and obtained a "solubiUty envelope".
They hypothesized that any solvent lying inside the envelope was a "good" solvent and
therefore yielded dense membranes, whUe the others were either sweUing agents or
nonsolvents and yielded porous membranes. WhUe this concept is useful in the selection
of a solvent for a particular polymer, it did not in any way account for the coagulation
bath conditions or any of the other membrane preparation parameters. But this approach
was used very often in the membrane manufacture industry and solubiUty maps were
developed for various polymers. Such a process can therefore be time-consuming and
cumbersome.
molecular level, they too have some drawbacks. In most cases, these models are highly
complex and cannot be easUy simpUfied. For example, in model developed by Tsay and
27
McHugh [45,46], the system and model parameters that had to be specified in order to
perform calculations for the quench step are: (a) temperature and pressure; (b) molecular
weights and partial specific volumes of the components; (c) thermodynamic interaction
parameters and their composition dependence; (d) scaling factors for tíie thickness of the
membrane and for the component diffusivities; and (e)frictioncoefficients describing the
The biggest drawback of aU the above models is that for a given set of membrane
formation conditions, none of them can actuaUy make any predictions about membrane
The aim of this study, therefore, was to develop a general model based on
particular membrane-forming system; (b) require data that can be easUy obtained
experimentaUy or from Uterature sources; and (c) most importantíy, be able to predict
conditions.
28
CHAPTER3
DEVELOPMENT OF MODEL
3.1 Theorv
The theoretical basis of the model that was developed as part of this study is
miscibiUty, such as the one represented by Figure 2.1, can be described in terms of the
Gibbs free energy change of mixing. For a stable state to exist, the Gibbs free energy of
composition, at a given temperature T and pressure P. The criterion for the equiUbrium
When a homogenous single phase system separates spontaneously into two phases, the
29
According to the extended Flory-Huggins theory for polymer solutions [59,65], the
given by
kí.
—^^=/iiln<t)i+/i2ln<|)2+n3ln<|)3+Xi2ni<t)2-HXi3ni<|)3+X23/i2<|)3 , ^^'^^
where n^ and <t)i are the number of moles and volume fraction of component i, and n is
the total number of moles in the system. X^j is the concentration-dependent binary interac-
tion parameter for a solution of species i and j . The nonsolvent, solvent and polymer are
ological dimensionless quantity characterizing the nonideaUty of the Gibbs free energy
miscibiUty of i and j within each other. A larger value of X^j indicates a smaUer decrease
in the free energy of mixing, so that when X^j b)ecomes sufficientíy large, a homogeneous
solutíon of species i and j separates into two phases, which are in equiUbrium with each
other. Xij is dependent on state variables such as composition, temperature and pressure.
A more rigorous thermodynamic definition of X^j can be found in other sources [60,66].
The binodal curve or cloud point curve, as shown in Figure 2.1, represents the
30
can be experimentally obtained by a simpletitrationmethod [67]. Binary solutions of the
polymer in the solvent (polymer dopes) at various concentrations are titrated with the
nonsolvent (water, m tfiis study) untU phase separation occurs in the polymer solution.
observed in the solution. The solution is held at a constant temperature. The curve formed
by joining these turbidity points is referred to as the binodal curve or cloud point curve.
The area inside this curve, as explained in Chapter 2, is the miscibiUty gap. Any system
whose composition Ues within the miscibiUty gap is unstable and separates spontaneously
[67] as the amount of nonsolvent required to cause phase separation and yield the first
Therefore, when a polymer dope has a large coagulation value, it indicates that the
each other; a smaU coagulation value impUes that phase separation or demixing is favored
by the system.
separation in a dope at any polymer concentration. But at very high polymer concentra-
locaUy as the nonsolvent is added to the polymer dope. For this reason, it is desirable to
31
polymer dope is therefore defined arbitrarUy as the weight of nonsolvent required to cause
By definition, the coagulation pomt Ues on the cloud point curve of a system at 25 °C.
polymer binary inleraction parameters Xj^, X^^ and X13 on tíie location of the miscibiUty
First, consider the effect of X12, assuming that the other two binary interaction
parameters remain unchanged. As can be observed from Figure 3.2, increasing Xj^
decreases the miscibiUty gap. QuaUtatively, this impUes that a lower tendency of mixing
between the nonsolvent and solvent favors the mixing of the system.
Next, consider the effect of increasing solvating power of the solvent for the
polymer, or decreasing X23, assuming that the other two binary interaction parameters
remain the same. As can be observed from Figure 3.2, this too decreases the miscibiUty
gap. Therefore, greater solvent-polymer affinity favors increased miscibiUty of the system.
that the other two parameters remain constant, decreases the miscibiUty gap. This impUes
can be observed from Figure 3.1 that the effect of increasing X^^ is opposite to that of
32
Increasing X
Decreasing X
Decreasing X
Nonsolvent
33
increasing X23 and Xj^. The miscibiUty gap decreases as (a) Xj^ increases and (b) X23 and
Xi3 decrease. AII three parameters can therefore be combined to quantify the miscibiUty
AX=-Xi2+X23+Xi3 . (3.4)
The negative sign on X,^ takes into account its opposing effect on the miscibiUty
gap, as compared to the effects of X23 and Xj^, as discussed above. AIso, the additive
form of the expression on the right-hand side of the equation can be explained on the
basis of the fundamental assumption of additivity in the group contribution models which
were used for the binary interaction parameters because the group contribution models
also take into account the concentration-dependence of these parameters and, therefore,
the composition of the system. The expression on the right-hand side of eqn. 3.4,
therefore, consists of the simplest and most logical choice of parameters that can be used
to define AX.
From its definition in eqn. 3.4, a smaller value of AX should indicate greater
miscibiUty of the components of system, whUe a larger AX value should favor system
demixing. Since the coagulation value of a polymer solution is also a measure of the
that the coagulation value is related to the AX value of a system if the above hypothesis
is valid. Membrane-forming systems with greater miscibiUty between the components, i.e..
34
with smaU AX values should have large coagulation values. Conversely, systems with
lower miscibiUty, i.e., with large AX values, should have smaU coagulation values.
have reported the existence of a relationship between their coagulation values and the
system miscibiUty, it can also be expected that it is related to tíie transport properties of
be a simple parameter that can correlate the thermodynamic properties of the nonsolvent-
The experiments and computations that were performed as part of this study were
therefore aimed towards achieving two objectives, which were: (a) to verify the existence
of any relationship between the AX and coagulation values of phase inversion membrane-
forming systems and examine the vaUdity of AX as a measure of the miscibiUty of the
membrane-forming system; and (b) more importantiy, to study the effect of AX, or the
The sequence of experiments that were performed involved: (a) preparation and
values of the polymer dopes; and (c) determination of the gas transport rates of these
membranes.
35
The computations involved determination of the concentration-dependent binary
interaction parameters for the nonsolvent-solvent-polymer systems that were used in the
4 and 5.
36
CHAPTER4
EXPERIMENTS
The polymers used in this study were Bisphenol A polysulfone (PSf) and cellulose
acetate (CA), two of the most commonly used polymers in tíie membrane manufacture
industry. The molecular stmctures of these polymers are shown in Schemes 4.1 and 4.2.
The choice of these two polymers was based on their completely differing chemical and
CH, o
II
-o- \ / s- \ / Jn
CH3 II
o
CH2OCOCH3 OCOCH3
-0
OCOCH3 CH.OCOCH3
37
Polysulfone is a rigid, strong, engineered thermoplastic. The polymer backbone
made up of benzene groups with ether linkages. These groups cause polysulfone to be
strongly hydrophobic in nature. Among the properties which qualify PSf as good polymer
for membrane preparation are a glass transition temperature (Tg) of 195 °C, an amorphous
glassy state, thermal and oxidative stability, resistance to extremes of pH, and low creep
unit of the polymer chain consists of cyclic anhydroglucose stmctures to which hydroxyl
and acetyl groups are attached. Cellulose acetate,tíierefore, has both basic (acetyl) and
acidic (hydroxyl) character. The hydroxyl groups are hydrophobic sites which form
hydrogen bonds with water, whUe the acetyl groups are hydrophobic in nature. But
osmosis membranes due to its high permeabiUty rates for water. CA possesses outstanding
a relatively low Tg of 68.6 °C, rendering it inviable in high temperature and high pressure
The choice of two extremely diverse polymers, PSf and CA, in this study, was
based on tíie rationale that if the model developed in Chapter 3 was vaUd for tíiese
38
4.2 Initial experiments
leneurea (DMPU) solvents, and CA membranes were prepared using acetone, dioxane and
4.4. These solvents are the most commonly used ones reported in literature for PSf and
CA. The coagulation values of the binary polymer dopes at 25 °C and the nitrogen
transport rates of these membranes were determined as described in Section 4.5 and 4.6.
The binary interaction parameters for all these systems were estimated by group-
The results of these initial experiments, coupled with the estimated AX values for
these systems, indicated that there is a relationship between their AX and coagulation
values. Also, the visual inspection of these membranes showed that the morphologies of
these membranes varied with the AX of these systems. The morphologies of tiie PSf
membranes ranged from a dense, skinned structure supported by a sublayer with large
macrovoids for the PSf-DMPU system, to a very porous stmcture with a very thm skin
for the PSf-DMSO system; for the CA systems, tiie morphologies ranged from a
completely dense membrane for tiie CA-acetone system to a porous stmcture for the CA-
DMSO system,
and dimethylformamide (DMF) solvents for PSf, and pyridine, methyl acetate (MA) and
39
tetrahydrofuran (THF) solvents for CA. Similar experiments were performed with PSf
The foUowing sections deal with the materials used in the preparation of the
polymer membranes and the procedures used in the membrane preparation, coagulation
4.3 Materials
The UDEL P-3500 polysulfone and ceUuIose acetate (DS=2.3) were obtamed
from Amoco Performance Products, Inc. and Aldrich Chemical Company, respectively.
The solvents NMP, NFP, DMF, MA, acetone, pyridine and dioxane were obtained from
Aldrich Chemical Company. The solvents DMAc, DMSO and THF were obtained from
Fisher Scientific. The solvent DMPU was obtained from Sigma Chemical Company. The
99.5% purity nitrogen used in the gas transport experiments was obtained from Big Three
Industries, Inc. The polymers, solvents and nitrogen gas were used as suppUed.
solvent (or solvent mixture). In most cases, the solvent (or solvent mixture) was preheated
to about 60 °C before adding the polymer to it. The solvent-polymer mixture was further
heated (for up to about 4 h in some cases) and stirred occasionaUy with a glass rod, untU
it formed a homogenous solution completely free of air bubbles. The polymer solution
was cast as a thin film (approximately 200 fxm in thickness) on a glass plate (12.5 cm X
40
20 cm) and aUowed to stand for 1 minute before quenching it in a water bath at 25 °C.
The PSf membranes were washed in mnning water for 24 h and dried in the controUed
environment of a Precision Scientific air dryer for 24 h. The CA membranes were washed
in isopropanol and n-hexane baths for approximately 6 h each. The CA membranes were
For each polymer-solvent system, three membranes were cast using the procedure
described above.
Samples of the PSf and CA membranes (approximately 1.5 mm X 1.5 mm) were
mounted on a steel plate and coated with platinum in a Seevac Hummer V sputter coater.
Scanning electron micrographs (SEMs) membranes were then obtained using a Hitachi
S570 scanning electron microscope in the Department of Biology, Texas Tech University.
The coagulation values for 2% dopes of PSf m DMPU, NMP, NFP, DMAc, DMF
and the (1:1) NMP-DMSO mixture, as weU as coagulation values for 2% dopes of CA
in acetone, dioxane, pyridme, MA, DMSO and THF, were obtained experimentaUy at
25 °C as described below. The coagulation value for the PSf-DMSO dope was taken as
In each case, 2.00 g of polymer was dissolved in 98.00 g of solvent (or solvent
mixture). In some cases, the mixture had to be heated to a temperature sUghtiy above
41
25 °C and stirred to facUitate complete dissolution of the polymer in the solvent, and then
cooled to 25 °C. DistiUed water was slowly added to the homogenous polymer dope,
stirring it constantiy, until the solution yielded the first permanent precipitate (or
persistent turbidity). The temperature of the mixture was held constant at 25 °C. The
coagulation value in each case was the weight of water required to obtain the first
The gas transport experiments in this study were performed with the objective of
obtaining a measure of the openness of the membranes obtained from various solvent-
polymer systems, relative to each other. The aim of these experiments was not to
determine the absolute permeabUities of the membranes; the experimental conditions were
performed were therefore chosen such that any appreciable differences in the gas transport
shown in Figure 4.1. The permeabiUty ceU of virgin grade extmded Teflon^ consisted of
two soUd cylindrical blocks, each of diameter 10 cm and height 2 cm, which formed the
upstream and downstream components of the ceU. Each of these blocks was provided with
a circular opening at the center. The openings, which acted as the gas inlet and outíet on
the upstream and downstream sides respectively, were fitted to Swageloc male connec-
tions (1/2 " NPT X 1/4 " tube). The upstream side of the ceU was connected by 1/4 "
42
Nitrogen gas supplv
Permeability cell
Pressure guage
On-off
valve
Membrane
Gasket
-^To flowmeter
Permeate
43
PVC piping to a nitrogen gas cylinder. The downstream side was connected to a soap-
bubble meter to measure theflowrate of the permeate. The upstream side of the permeab-
iUty cell was also connected to a pressure gauge (0-300 psig) and a simple on-off valve.
The PSf and CA membranes, which were prepared as describ>ed previously, were
cut in the form of circular discs of 7.5 cm diameter. For the nitrogen transport
experiments, the upstream and downstream pressures in tiie ceU were arbitrarUy chosen
as 65 psig and atmospheric pressure, respectively. All these experiments were performed
at room temperature.
The foUowing procedure was repeated with each oftíiethree membranes cast from
The membrane whose nitrogen flux was to be determined was placed between the
two blocks of the ceU, with the skinned surface of the membrane facing the upstream
side. A rubber gasket of 5.5 cm diameter was placed between the blocks, which were then
bolted together. The nitrogen gas inlet flow rate was adjusted so that the upstream
pressure in the ceU, as indicated by the pressure gauge, was 65 psig. The permeate flow
rate through the membrane was continuously monitored by the soap-bubble meter until
it reached a steady state. The nitrogen supply was then switched off. The pressure on the
upstream side was relieved by opening the shut-off valve, before removing the membrane
The next set of experiments was based on the resistance model approach, proposed
by Henis and Tripodi [78]. This model was developed to explain the behavior of
44
substrate of one polymer, and a coating of another polymer. The authors examined the
polysulfone composite fiber for a hydrogen/carbon monoxide gas mixture. They obtained
polysulfone hoUow fiber membranes with a very thin skin. But smaU defects, or pinholes
on the surface of tiie membranes prevented the fuU separation properties of the polymer
form being achieved. By using an appropriate coating such as siUcone, which offers very
low resistance to tiie permeation of gases, the authors were able to effectively plug the
defects or pores on the surface of the substrate, whUe not adversely affectmg its
of n-hexane. In each case, the membrane was dipped into the siUcone solution, removed
and dried in the air dryer for approximately 1 h. The nitrogen fluxes of these siUcone-
coated membranes were also determined under experimental conditions identical to those
45
CHAPTER5
COMPUTATIONS
In the foUowing sections, tiie choice of X^^ values for the PSf-water and CA-water
systems wiU be discussed. This wUI be foUowed the development of the theoretical
equations for estimating the binary concentration-dependent interaction parameters X,^ and
X23.
There are three reported values of Xj^, 5.9, 3.7 and 3.8, for the PSf-water system
[52,58,63]. Shuguang et al. [61] concluded in their study that the value of 5.9 for this pair
is not a reasonable one. However, as there is good agreement between the other two
values, the PSf-water interaction parameters was assumed to be 3.7 in this study.
The Uterature value of X13 for the CA-water paU is 1.4 [58].
46
These interaction parameters can be determined experimentaUy by several methods
Experimentally determined values of Xj^ and X23 reported in Uterature for some
In this study, therefore, aU the Xj^ and X23 values were estimated by the UNIFAC and
UNIFAP methods.
based on Prausnitz's group contribution model [71]. The excess molar Gibbs free energy
G,2^ for a binary solution of nonsolvent (1) and solvent (2) is defined as
=RT [x^ifna^-lnx^^+x^ilna^-lnx^] ,
where x^, a^ and YÍ are the mole fraction, activity and activity coefficient of component
i. The molar Gibbs free energy change of mixmg AG,^^ is then given by
AGI?=GI2+AGS
=RT [x^lna^+x^lna^] .
47
From eqns. 3.3 and 5.2, it follows tíiat
_ [(^G,^/RT)-(x,]ni»,+x^lRÍ,^)]
-^12 T
(53)
_ [Xiln(a^/4)^)+jt^ln(fl^4)^)]
^1*2
where ^., is tíie volume fraction of component i in tiie binary solution and is estimated by
x^m^+x^m^
The molar volume ratio mj = (Vj / V,), where V, is tiie molar volume of component i,
reflects the difference in the molecular sizes of the components i and j . Here, the
[73], a modified UNIFAC method. For polymer solutions, the mole fraction is an
awkward unit of concentration because the molecular weight of the polymer is so much
larger than that of the solvent that mole fractions are always close to 1.0 for the whole
is based on weight fractions. This modified method also takes into account the free-
volume effects in polymer solutions. The complete theoretical equation for solvent activity
48
Ina^^hia^'^+lna^^+lna/^ , (5.5)
where tiie superscripts R, C and FV refer to the residual, combinatorial and free-volume
components of the solvent activity a^. The binary solvent-polymer mteraction parameter
ln.,=i!^
RT (5.6)
=ln(|)/+<|)/-.X^(<t)/)^ ,
where fi^ and 1X2*^ refer to the chemical potentials of the solvent in solution and pure
solvent at 25 °C, respectively, and (j),' is the segment fraction, which is simUar to the
^ (4.3^
on the UNIFAC and UNIFAP methods. The FORTRAN codes of these programs are
Usted in Appendices A and B. The UNIFAC groups that can be used by these programs
49
are listed in Appendix C. The group interaction parameters required by these programs
were obtained from the latest supplement to the UNIFAC program [76,77].
Some of the molecular groups in the PSf and CA repeat units, as shown in Section
4.1, were not available m tiie UNIFAC database (Appendix C). The combination of
molecular groups used to represent PSf and CA in the UNIFAP program, as shown below,
were therefore chosen in such a way that the estimated values for tiie water-PSf and
water-CA interaction parameters were close to the experimental values of 3.7 and 1.4
CH3 2 CH2 2
C 1 CH 6
ACH 16 OH 2
AC 8 CH3COO 4
CHO 4
containing water equivalent to the coagulation value of the polymer dope, and 98.00 g of
solvent. SimUarly, the X23 values were estimated based on compositions corresponding
to 2.00 g polymer dissolved m 98.00 g solvent For the PSf-(NMP-DMSO) system, the
various binary interaction parameters were estimated in a similar fashion (Appendix D).
50
The AX value had to also account for the interaction between the cosolvents NMP and
DMSO.
The free-volume correction term a^^ in eqn 5.5 jdelded a negative value in some
cases. In the other cases, it was not significant when compared to the residual and
51
CHAPTER6
The scanning electron micrographs (SEMs) of tfie cross-sections of the PSf and
CA membranes (magnification 200), which were prepared as described in Section 4.4, are
shown in Figures 6.1 and 6.2, respectively. Figure 6.1 also mcludes SEMs of tiie skins
of the membranes obtamed from the PSf-NMP (magnification 250) and PSf-DMSO (mag-
nificatíon 1000) systems. The coagulation values, X,^, X23 and AX values of tiie PSf and
CA systems are Usted in Tables 6.1 and 6.2, respectively. The average nitrogen fluxes of
the coated and uncoated membranes, along with the standard deviation for the three
membrane samples obtained for each polymer-solvent system, and the flux ratios are also
As expected, the results of the experiments performed with PSf polymer and NFP
and DMF solvents, and CA polymer with pyridine, THF and MA solvents, were
consistent with those obtained from the initial experiments (Section 4.2). The coagulation
values, as weU as the corresponding AX values, of the PSf-NFP and PSf-DMF systems
were found to lie between those for the PSf-DMPU and PSf-DMSO systems. The overaU
morphology of the PSf-NFP and PSf-DMF membranes also varied between the PSf-
DMPU membrane, which had a dense skin and a supporting substmcture with large
macrovoids, and the PSf-DMSO membrane, which had a very thin skin supported on a
sponge-like substmcture. SimUarly for the CA systems, the CA-MA system which had
a larger coagulation value than the CA-acetone system, had a correspondingly lower value
52
of AX, and yielded a dense membrane simUar to the one obtained from the CA-acetone
system. The CA-pyridine system, which had a coagulation value and the corresponding
AX value close to that of the CA-acetone system, also yielded a dense membrane. The
CA-THF system had a coagulation value and a AX value lying between tiiose of the CA-
acetone and CA-dioxane systems. In this case too,tiieresulting membrane was completely
dense. Therefore, aU tiie CA systems with AX lower than tiiat of the CA-THF system,
yielded completely dense membranes. CA systems with AX values greater than that of the
values and the morphology of the membranes obtained from these selected polymer-sol-
vent systems, this model is capable of predicting, a priori, the morphology of membranes
obtained from other polymer-solvent systems once their AX values are known.
The coagulation values of the PSf and CA systems were plotted against the
corresponding AX values, as shown in Figures 6.3 and 6.4 . From these figures, it can be
observed that, for both the PSf and the CA systems, there is a strong correlation between
the coagulation values and the AX values. For both PSf and CA, membrane-forming
systems with low AX values have high coagulation values, and systems with high AX
values had low coagulation values. In both cases, the coagulation values decreased
systematicaUy with increasing values of AX, further consoUdating the results obtained in
Among the various PSf systems, only PSf-NMP system did not foUow this general
trend (Figure 6.3). The high estimated value of AX (3.929) obtained for the PSf-NMP
53
system appears be the result of tiie low value of the binary interactíon parameter
estimated by UNIFAC for tíie water-NMP pair (X,^ = 0.178). The experimentaUy deter-
mmed value of X,^ for this system [62] is 1.20. In tíiis case, if the experimental value of
X,2 were used mstead of tíie estimated value, it would yield a AX^p^ value of 2.907. This
pomt is indicated by a (+) m Figure 6.3. This point appears to foUow the general trend
From Figures 6.3 and 6.4, it appears as if there is strong linear relationship
between coagulation value and AX for the PSf and CA systems examined in this study.
The coagulation value versus AX data were tiierefore fitted to straight lines. For the PSf
systems, the PSf-NMP point was considered an outUer due to the reason discussed above,
and was therefore discarded from the regression calculations for the PSf systems. The
correlation coefficients (R^) obtained for the PSf and CA systems were 94.9% and 85.9%
respectively. The high correlation coefficients obtained for both the PSf and CA systems
indicated that the relationship between coagulation value and AX is indeed linear.
These results therefore vaUdate the hypothesis developed in Chapter 3 that AX can
forming systems.
account for the binary interaction between the cosolvents NMP and DMSO, as discussed
in Section 5.3. The coagulation value and AX for this system Ues between those obtained
54
Figure 6.1. Scanning electron micrographs of various PSf membranes
(a) PSf-DMPU system (magnification 200)
55
Figure 6.1. (Continued): (b) PSf-NMP system (magnification 200)
56
Figure 6.1. (Continued): (c) PSf-DMAc system (magnification 200)
57
Figure 6.1. (Continued): (d) PSf-DMF system (magnification 200)
58
Figure 6.1. (Continued): (e) PSf-DMSO system (magnification 200)
59
Figure 6.1. (Continued): (f) PSf-(NMP-DMSO) system (magnification 200)
60
Figure 6.1. (Continued): (g) Skin of PSf-NMP membrane
(magnification 250)
61
' ^ . •' ^ •ii^'^>.''W '•*;»-«•
62
Figure 6.2. Scanning electron micrographs of various CA membranes
(a) MA-CA system (magnification 200)
63
Figure 6.2. (Continued): (b) THF-CA system (magnification 200)
64
Figure 6.2. (Continued): (c) Dioxane-CA system (magnification 200)
65
m- - ^.-v
66
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System
S "
ro
Flux
ratio
Uncoated Coated
PSf-DMPU 9.5 1.350 0.062 2.412 3.478 0.945 0.27
± 0.0770 ±0.0105
PSf-NMP 8.2 0.178 0.407 3.929 3.758 0.965 0.26
±0.2119 ± 0.0215
PSf-NFP 6.9 0.570 0.030 3.160 4.294 1.525 0.36
67
± 0.2582 ± 0.0243
PSf-DMAc 5.2 0.465 0.330 3.565 4.625 1.618 0.35
±0.1365 ± 0.0429
009*0
PSf-DMF 3.5 0.553 3.653 4.675 2.391 0.51
± 0.2349 ± 0.0730
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±0.1331 ± 0.0757
-.
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DMSO 1:1 ±0.1783 ± 0.0793
mixture)**
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70
for the PSf-NMP and PSf-DMSO systems. The results obtained for this system foUows
the general trend exhibited by other PSf systems, as shown in Figure 6.3.
The effect of AX, or the miscibility, of the PSf systems on the nitrogen fluxes of
these membranes can be observed firom Figure 6.5. The average nitrogen fluxes of the
uncoated and the silicone-coated PSf membranes, obtained from three samples for each
PSf system, increased systematically as the AX values increased from 2.412 to 5.203. The
nitrogen flux versus AX data for the uncoated and coated PSf membranes were fitted to
straight lines. The correlation coefficients obtained for the uncoated and coated PSf
membranes were 74.6% and 90.5% respectively. The slopes of both these lines are
positive, but the low correlation coefficient for the uncoated membranes indicates that the
nitrogen flux versus AX data may not be linear in nature. Therefore, straight lines fitted
to these data points have no other significance other than to show that the flux increases
The flux ratio of the coated to the uncoated membranes also increased from about
27% for the PSf-DMPU membrane to about 58% for the PSf-(NMP-DMSO) membrane
and 61% for the PSf-DMSO membrane, as can be observed in Table 6.1. The effect of
from systems with lower AX values. This behavior of the PSf membranes can be qualita-
tively explained by observing the SEMs of the membrane skins obtained from the PSf-
NMP and PSf-DMSO systems (Figure 6.1). The uncoated PSf-NMP membrane has a
dense skin which has defects through which convective gas flow can occur. It appears that
these defects were effectively sealed by the silicone-coating since the flux of the coated
71
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73
membrane is only 27% of the flux of the uncoated membrane. On the other hand, the skin
of the uncoated PSf-DMSO membrane is extremely thm, to the extent that the porosity
of the supporting substructure is visible through the sldn and appears to destroy the
integrity of the skin. The silicone-coating does not appear to be very effective in plugging
the defects in this case, as indicated by the high ratio of the fluxes for the coated to
uncoated DMSO membranes. These results are consistent with the observations of Henis
and Tripodi [78], who used silicone rubber to coat PSf hollow fiber membranes.
pyridine and THF solvents were extremely small under the experimental conditions used
in this study and could not be measured. This can be qualitatively explained by observing
the SEMs of these membranes. The membranes formed from the CA-MA, -acetone, -
pyridine and -THF systems were completely dense, barrier-like films. The SEMs of the
CA-MA and -THF membrane cross-sections are shown in Figure 6.2 . The permeabilities
of these membranes are therefore probably close to the intrinsic permeability of the
polymer. The nitrogen fluxes of the CA-MA and CA-THF membranes were estimated
using the intrinsic permeability of nitrogen in CA [79]. The effective thickness of the
membrane in each case was obtained from the SEMs. The detailed calculations are shown
in Appendix E.
The CA-dioxane and CA-DMSO systems on the other hand yielded skinned
membranes with porous substructures. The nitrogen fluxes of the uncoated and sUicone-
coated CA-dioxane and CA-DMSO membranes are shown in Table 6.2. The flux ratio
74
increased from about 24% for the CA-dioxane system to about 51% for the CA-DMSO
system. The silicone coating therefore appears to be more effective in the case of the CA-
dioxane membrane than the CA-DMSO membrane, which has a higher AX value than the
former.
membranes were plotted against the corresponding AX values, as shown in Figure 6.6.
The nitrogen flux of the CA membranes increased as AX increased from -0.02 to 1.85.
However, even though the CA-MA system had a lower AX value than the CA-THF
system, it had a marginally higher calculated nitrogen flux than the latter. The SEMs of
these membranes show that the CA-THF membrane is thicker than the CA-ma membrane.
This can probably be explained on the basis of the boiling points of these two solvents.
Methyl acetate and tetrahydrofuran are both extremely volatile solvents, with boiling
it to evaporate from the CA-MA casting solution during the 1 minute evaporation step
(prior to the quenching step), than the corresponding solvent evaporation from the CA-
THF solution. This results in a CA-MA membrane which is thinner than the CA-THF
membrane, and correspondingly greater calculated value of nitrogen flux than the latter.
The calculated and experimentally determined nitrogen flux versus AX data for the
uncoated CA membranes were fitted to a straight line. The low correlation coefficient (R^
= 79.7%) again indicates that a linear regression model may not be the correct model for
this set of data. But the positive slope of the line shows that the nitrogen flux increases
75
VO
o+
00 C/5
B B
on 00
»o
>^ >%
00 00
< ^ ^r* o
J=í
cuU 4_>
Vi
O U
<4-l
ccJ o
»o
irs r^
T3 4 - >
<>
o ^ >i
C/5 -n
p
3 4—>
O 00
>-i
C>0
co co
1) C/3
> *P
c« -4—>
O
'c 3 c
.2 ctí
> -o
'cn
C c>
(U
C c
o
4->
<>» — cd cn
gul
X
+
<l CO
o
00
e
o
4—>
-a C/3
+ c >^
00
• ^
omb
+ u
U T3
C
t^ d
Vt-I
VO
+ o O^
oo
+ t-l
- + 3
Oû
tJU
o o o o o o o o o o
o o\ oo vo »o co <N
76
1 1 1 ll I • l l • 1 l l "T—
1' ' •1— ll 1 • ll • vo
O+ • X
n
PSf uncoated
CA uncoated
CA coated
PSfcoated
— lO
<
U
-o
c
cc3
«*-!
00
fX.
o + ^
o
Æ
$++ v-< oU
*^
o
C4-1 »o
CCÍ < ^
o + ca -^
•ti cd
^ co
-o
»s> >»
m
(D
9-§ 4->
'c C/5 00
sio
o + c
s.-
D X •^ Q-i <D
_. C
X
<3
• X
• ^H
C 00
• ^
-o
0 e
<D
syst
mbin
0
U
— • — o CXJ
vd
<D
>-i
3
CiO
u.
• 1 . 1. . . 1. . . 1 . 1 1 ii . • 1. . . 1. . 1
o <N CO »0 vo
o 0 0 0 0 0 0 0
+ <D <D <D 0 <D <D <D
0 0 0 0 0 0 0
O
77
The combined coagulation value versus AX data and niu-ogen flux versus AX data
for all the systems examined in this study are shown in Figures 6.7 and 6.8 . From Figure
6.7, it can be observed that there is a sharp change in the curvature of the coagulation
value versus AX data, approximately between AX = 1.5 and AX = 3.5 . The nitrogen flux
versus AX curve also showed a corresponding change in curvature for the same range of
AX values, as shown in Figure 6.8. Systems which had AX values lower than about 1.5
yielded completely dense membranes, while systems which had AX values greater than
3.5 yielded porous membranes. CA and PSf systems with AX values in this transition
range yielded asymmetric membranes with dense skins, with the nitrogen fluxes
progressively increasing with AX. The results obtained for the binary solvent-PSf systems
membranes. Systems with low AX values yielded completely dense membranes, while
those with high AX values jdelded porous membranes. Systems with intermediate values
78
CHAPTER7
CONCLUSIONS
AX values had high coagulation values and those with high AX values had low
corresponding PSf and CA phase inversion membranes. PSf systems with lower AX
values resulted in membranes with denser skins and lower fluxes, while those with higher
AX values produced membranes with more porous skins and higher fluxes. The results
obtained for the PSf-(NMP-DMSO) system appear to indicate that this approach can also
possibly be extended to systems with solvent mixtures. CA systems with lower AX values
resulted in completely dense membranes, the nitrogen fluxes of which could not be
measured under the experimental conditions that were used in this study. CA systems with
therefore a useful parameter that can be used to differentiate formation conditions for
porous structures.
79
CHAPTER8
RECOMMENDATIONS
The simplicity and generality of the model that was developed in this study
indicates that further investigation of the potential for its predictive abilities is warranted.
This study utilized PSf and CA, two polymers which are very different in terms
of their physical and chemical properties. However, the scope of this model can be
The model also permits the examination of the effects of numerous other variables
such as, the coagulation bath temperature, initial concentration of solvent in the
39] have shown that membrane skin characteristics are strongly affected by changes in
the quench bath conditions, such as bath composition and temperature. It would be
interesting, therefore, to examine the trends in the coagulation value versus AX data and
gas transport rates versus AX data with varying coagulation bath compositions and
morphology.
81
Often, in commercial membrane manufacture processes, a second solvent
(cosolvent) is used in the polymer casting solution. The cosolvent usually acts as a
poreformer during the membrane formation process. The PSf-(NMP-DMSO) mixture that
was examined in this study is an example of a casting solution where DMSO acts as the
cosolvent poreformer. Other poreformers such as ethylene glycol, glycerol, etc, are
ility of the model can therefore be extended further by performing experiments with
All the transport experiments in this study were performed using nitrogen gas with
the objective of obtaining a measure of the openness of the membrane structures obtained
from various polymer-solvent systems. Transport experiments can also be performed with
gas mixtures. For example, gas transport experiments can be performed using a simple
gas mixture such as air and obtaining not only the flow rate of the permeate but also
analyzing its composition. This would give a better qualitative and quantitative measure
82
REFERENCES
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[48] T. Young and L. Chen, A two-step mechanism of diffusion-controUed ethylene
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of its relation to membrane formation, Polymer, 30 (1989) 2118.
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conditions on stmcture and properties of membranes from aliphatic polyamides,
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Chap.4, pp. 119-120.
[71] D.S. Abrams and J.M. Prausnitz, Statistical thermodynamics of Uquid mixtures:
A new expression for the excess Gibbs energy of partly or completely miscible
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sUoxane) solutions by the UNIFAC group contribution method, Macromolecules,
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separation: The resistance model approach, J. Memb. ScL, 8 (1981) 233.
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membrane materials for solution-diffusion based permeation separations, Prog.
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89
APPENDDC A
This appendix Usts the FORTRAN code for the UNIFAC program used in the
90
C THIS PROGRAM CALCULATES THE INTERACTION PARAMETER FOR A
C BINARY LIQUID SYSTEM. ALL CALCULATIONS AND NON-INTEGER TERMS
C ARE DOUBLE-PRECISIONED.
Q **********************************:|e*j(:**:(c****************************
91
C INmALIZING THE VALUES OF THE SECONDARY GROUP NOS. AND
C NUMBER OF GROUPS OF EACH TYPE FOR BOTH COMPONENTS
35 DO 40 I=1,IMX
DO 50 J=l,10
IARa,J)=0
50 ANaj)=0
40 CONTINUE
C
C THIS PART OF THE PROGRAM IS FOR ENTERING COMPONENT DATA
C
PRINT*,'ENTER COMPONENT DATA IN THE REQUIRED FORMAT'
PRINT*,'ENTER CHARACTER DATA IN APOSTROPHES'
PRINT*,'ENTER FIRST COMPONENT AS NONSOLVENT'
DO 60 1=1,IMX
PRINT*,'ENTER NAME OJPTO 6 CHAR) OF COMPONENT ',1
READ*,C$a)
PRINT*,'INPUT NO.OF SECONDARY GROUP TYPES IN ',C$(D
READ*,ILSa)
PRINT*,'INPUT MAINGR. NAME, SECGR. NAME (UPTO 10 CHAR)'
PRINT*,'MAIN GR. NO.,SEC.GR. NO. AND NO.OF EACH TYPE'
DO 70 J=1,ILS(I)
70 READ*,CM$a,J),CS$a,J),MGNO(IJ),L\Ra,J),ANa,J)
60 CONTINUE
C
C ENTERING COMPONENT INFORMATION INTO OUTPUT FILE
0PEN(UNIT=7,FILE='A:CHINSS.DTA',STATUS='NEW')
WRITE(7,4900)C$(2),C$(1)
4900 FORMAT(20X,'CALCULATION OF INTERACTION PARAMETER FOR'y
1 28X,A,'-',A,' SYSTEM')
WRrrE(7,*)' ',
1 ' '
WRITE(7,*)
WRITE(7,*)
WRITE(7,*)' COMPONENT LIST'
WRITE(7,*)' '
WRrrE(7,*)
DO 80 I=1,IMX
WRITE(7,5000)I,C$a)
5000 FORMAT(30X,I2,5X,A)
80 CONTESrUE
WRITE(7,*)
DO 90 I=1,IMX
WRITE(7,5001)C$a)
5001 FORMAT(23X,'TYPE AND NO.OF GROUPS IN ',A)
92
DO 100 J=1,ILS(I)
100 WRITE(7,5005)CS$a,J),ANa,J)
5005 FORMAT(28X,A,5X,I2)
WRITE(7,*)
90 CONTINUE
C
C ENTERING TEMPERATURE AND DENSITIES OF COMPONENTS
C
PRINT*,'INPUT TEMPERATURE ,DEG C'
READ*,TC
TK=TC+273.15D-FO0
DO 110I=1,IMX
PRINT*,'ENTER DENSITY (gm/cc) OF COMPONENT ',1
READ*,DENS(I)
110 CONTINUE
C
C ENTERING TEMP AND WEIGHT FRACTION DATA ESfTO OUTPUT FILE
C
WRITE(7,5010)TC
5010 F 0 R M A T ( 2 3 X , ' T E M P E R A T U R E = ',D10.4,' C')
WRITE(7,*)
WRrrE(7,*)' DENSITY OF COMPONENTS'
WRITE(7,*)' '
WRITE(7,*)
DO 115I=1,IMX
WRITE(7,5020)I,DENS(I)
5020 F0RMAT(23X,'DENSITY(',I1,') = ',D8.3,' gm/cc')
115 CONTINUE
WRITE(7,*)
C
^:|c4c3ic*******:ic:|c************************************************************
93
R1 a)=R 1 (i)+RaARa,j))* ANa, j)
Q1 (i)=Q 1 a)+QaARa, J)) * A N ^ , J)
122 MWl(I)=MWia)+MW(IARa,J))*AN(I,J)
SPVOLa)=1.0D+00/DENS(I)
MOLARVOLa)=MWl a)*SPVOLa)
Ma)=MOL ARVOL(I)/MOLAR VOL( 1)
PRINT*,'M(',I,') =',M(I)
120 CONTINUE
C
C CALCULATING SHI VALUES
C
IFLAG=0
DO 150 I=1,IMX
DO 160 J=1,ILS(I)
MM=MGNO(I,J)
DO 170 II=1,IMX
DO 180 JJ=1,ILS(II)
NN=MGNO(n,JJ)
AMN(MM,NN)=A(MM,NN)
SHI(MM,NN)=DEXP(-AMN(MM,NN)/TK)
IF (AMN(MM,NN).EQ.O.O) THEN
IF (MM.NE.NN) THEN
WRITE(7,5021)CS$a,J),CS$(n,JJ)
5021 FORMAT(lX,'INTERACTION VALUES NOT AVAILABLE FOR ',A,'-',A,'
1 PAIR')
IFLAG=1
ENDIF
ENDIF
180 CONTINUE
170 CONTINUE
160 CONTINUE
150 CONTDSfUE
C
C
IF aFLAG.EQ.O) THEN
WRITE(7,*)'ALL INTERACTION PARAMETERS ARE AVAILABLE'
ENDIF
WRITE(7,*)
WRITE(7,*)
WRrrE(7,*)' WEIGHT VOLUME MOLE',
CHI'
WRrrE(7,*)' FR. OF FR. OF FR. OF'
WRrrE(7,*)' H20 H20 H20'
WRITEÍ7.*)'
94
C ENTER STEP SIZE FOR WEIGHT FRACTION, INITL^LIZING
C THE WEIGHT FRACTIONS
DW=0.01
W(l)=0.01
124 W(2)=1.0-W(l)
C
C CALCULATING MOLE AND VOLUME FRACTIONS
C
TM0L=(W(1)/MW1(1))+(W(2)/MW1(2))
TVOL=MOLFR( 1 )*M( 1 )+MOLFR(2)*M(2)
DO 125 I=1,IMX
MOLFRa)=(W(I)/MWl a))/rMOL
VOLFR(I)=(MOLFR(I)*Ma))/TVOL
125 CONTINUE
R2=0.0
Q2=0.0
DO 130 I=1,IMX
R2=R2+MOLFRa)*Rl(I)
Q2=Q2+MOLFR(I) *Q 1 (I)
130 CONTINUE
SIGMAXL=0.0
DO 140 I=1,IMX
PH(I)=Ria)*MOLFRa)/R2
TH(I)=Ql(I)*MOLFR(I)/Q2
L(I)=5.0*(R1(I)-Q1(I))-(R1(I)-1.0)
SIGMAXL=SIGMAXL+La)*MOLFR(I)
140 CONT NUE
C
C CALCULATION OF COMBINATORL^L PART GnGAMC) OF ACTIVITY
C COEFFICEENT
DO 145 I=1,IMX
145 LNGAMC(I)=DLOG(PHa)/MOLFRa))+ 5.0*Qia)*
1 DLOG(TH(I)/PHa))+ La)- (PHa)/MOLFRa))*SIGMAXL
C
C CALCULATION OF RESIDUAL PART (hiGAMR) OF ACTIVITY COEFFICIENT,
C CALCULATION OF THETA VALUES FOR EACH GROUP IN EACH COMPO-
C NENT
C
SUMXQ=0.0D+00
DO 200 1=1,IMX
DO 210 J=l,ILSa)
XQaj)=MOLFRa)*ANa,J)*Q(L\RaJ))
210 SUMXQ=SUMXQ+XQ(I,J)
200 CONTINUE
95
DO 220 1=1,IMX
DO 230 J=1,ILS(I)
THETAa,J)=XQ(I,J)/SUMXQ
230 CONTINUE
220 CONTINUE
C
C CALCULATION OF Ui(Tauk) FOR ALL GROUPS IN BOTH COMPONENTS
C
DO 235 1=1,IMX
DO 240 J=l JLS(I)
SUMl=0.0D+00
DO 250 n=l,IMX
DO 260 JJ=l,ILSai)
260 SUMl=SUMl+THETA(njJ)*SHia^GNOaiJJ),MGNOaj))
250 CONTINUE
SUM3=0.0D+00
DO 270 n=l,IMX
DO 280 JJ=l,ILSai)
SUM2=0.0D+00
DO 290 in=l,IMX
DO 300 JJJ=1,ILS(III)
300 SUM2=SUM2+THETAan,JJJ)*SHia^GNOan,JJJ),MGNO(n,JJ))
290 CONTINUE
280 SUM3=SUM3+THETAaiJJ)*SHI(MGNOaJ),MGNOai,JJ))/SUM2
270 CONTINUE
LNTAUKa,J)=Q(L\Ra,J))*(l-DLOG(SUMl)-SUM3)
240 CONTINUE
235 CONTINUE
C
C CALCULATION OF UiTaukl VALUES WITHIN EACH MOLECULE
C
DO 350 1=1,IMX
IF(ILS(I).EQ.1)THEN
LNTAUKl a, l)=0.0D+00
GO TO 345
ENDIF
C CALCULATION OF THETAl VALUES FOR EACH GROUP WTTHIN EACH
C MOLECULE
SUMXQ1=0.0
DO 301 J=1,ILS(I)
xQia,j)=ANa,j)*QaARa,J))
SUMXQl=SUMXQl+XQia,J)
301 CONTESfUE
DO 302 J=1,ILS(I)
96
THETAl(I,J)=XQia,J)/SUMXQl
302 CONTINUE
DO 310 J=1,ILS(I)
SUMl=O.OD+00
DO 320 JJ=l,ILSa)
320 SUMl=SUMl+THETAl(I,JJ)*SHI(MGNOa,JJ),MGNO(I,J))
SUM3=0.0D+00
DO 330 JJ=l,ILSa)
SUM2=0.0D+00
DO 340 JJJ=1,ILS(I)
340 SUM2=SUM2+THETAl(I,JJJ)*SHia4GNO(I,JJJ),MGNO(I,JJ))
330 SUM3=SUM3+THETAiajJ)*SHI(MGNOa,J),MGNO(I,JJ))/SUM2
LNTAUKia,J)=Q(L\Ra,J))*(l-DL0G(SUMl)-SUM3)
310 CONTINUE
345 CONTDSrUE
350 CONTINUE
C
DO 360 I=1,IMX
LNGAMR(I)=O.OD+00
DO 365 J=1,ILS(I)
365 LNGAMR(I)=LNGAMRa)+ANa,J)*a-NTAUKa,J)-LNTAUKl (I, J))
360 CONTDSfUE
C
C CALCULATDSfG LN(ACnVITY COEFFICIENT) AND LN(ACTIVITY) FOR
C EACH COMPONENT
C
DO 370 I=1,IMX
LNGAMa)=LNGAMCa)+LNGAMRa)
LNA(I)=LNGAM(I)+DLOG(MOLFR(I))
370 CONTINUE
C
C CALCULATING BINARY INTERACTION PARAMETER Xj^
C
CHI=( MOLFR(l)*a'NA(l) -DL0G(V0LFR(1))) + MOLFR(2)*(LNA(2)-
1 DLOG(VOLFR(2))) ) / (M0LFR(1)*V0LFR(2))
WRITE(7,6100)W(1),VOLFR(1),MOLFR(1),CHI
6100 FORMAT(4X,4(D12.6,6X))
C
C INCREMElSÎTESfG WEIGHT FRACTION
W(1)=W(1)+DW
IF (W(1).LT.1.0) GO TO 124
CLOSEaJNIT=7)
PRINT*,' JUST A REMEsfDER TO CHANGE OUTPUT FILE NAME!!'
END
97
APPENDDC B
This appendix Usts the FORTRAN code for the UNIFAP program used in the
98
C THIS PROGRAM CALCULATES THE BESÍARY ESfTERACTION PARAMETER
C FOR A SOLVENT-POLYMER SOLUTION. ALL CALCULATIONS AND NON-
C ESJTEGER TERMS ARE DOUBLE-PRECISIONED.
Q * * * * * * * * * * * * : | c : J c :(£*:(: : j c * : ( : : j c * * * * * * * * * : J c * * * * * * * : | c * * * : f . : ( : : ^ ; j c * * * * * * * * * * * * * * * * * * * * *
99
35 DO 40 I=1,DVDC
DO 50 J=l,10
L\R(U)=0
50 ANaj)=0
40 CONTDSfUE
C
C THIS PART OF THE PROGRAM IS FOR ENTERDSfG COMPONENT DATA
C
PRD^*,'ENTER COMPONENT DATA DSf THE REQUIRED FORMAT'
PRDSfT*,'ENTER CHARACTER DATA JN APOSTROPHES'
PRDSÍT*,'ENTER FIRST COMPONENT AS SOLVENT'
DO 60 I=1,IMX
PRDVÍT*,'ENTER NAME OJPTO 6 CHAR) OF COMPONENT ',1
READ*,C$(I)
PRDSfT*,'DSfPUT NO.OF SECONDARY GROUP TYPES Dvf ',C$(I)
READ*,ILSa)
PRDSÍT*,'DSfPUT MADSf GR.NAME,SEC GR.NAME (UPTO 10 CHAR)'
PRINT*,'MAIN GROUP NO.,SEC.GROUP NO. AND NO.OF EACH
1 TYPE'
DO 70 J=1,ILS(I)
70 READ*,CM$a,J),CS$(I,J),MGNOa,J),IARa,J),ANa,J)
60 CONTINUE
C
C ENTERD^G COMPONENT EsfFORMATION E^O OUTPUT FILE
C
0PEN(U]SÍIT=7,Fn.E='A:S0LP0LY.DTA',STATUS='NEW')
WRITE(7,4900)C$(2),C$( 1)
4900 FORMAT(20X,'CALCULATION OF DSfTERACTION PARAMETER FOR'y
1 25X,A,'-',A,' SYSTEM')
WRITE(7,*)
WRITE(7,*)' COMPONENT LIST'
DO 8 0 1=1,IMX
WRITE(7,5000)I,C$a)
5000 FORMAT(30X,I2,5X,A)
80 CONTDWE
WRITE(7,*)
DO 90 I=1,DV1X
WRITE(7,5001)C$a)
5001 FORMAT(23X,'TYPE AND NO.OF GROUPS IN ',A)
DO 100 J=1,ILS(I)
100 WRITE(7,5005)CS$(U),AN(I,J)
5005 FORMAT(28X,A,5X,I2)
WRrrE(7,*)
90 CONTDSfUE
100
105 PRINT*,'DSfPUT TEMPERATURE ,DEG C'
READ*,TC
TK=TC+273.15D+00
WRITE(7,5010)TC
5010 FORMAT(23X,'TEMPERATURE = ',D10.4,' C')
WRITE(7,*)
WRITE(7,*)
^ * * * * * * * * * * * : i c * * * : i c * * * * * * : i c 4::): 4: : ( : * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * *
101
ENDff
180 CONTTNUE
170 CONTINUE
160 CONTDSfUE
150 CONTDsfUE
IF aFLAG.EQ.O) THEN
WRITE(7,*)'ALL INTERACTION PARAMETERS ARE AVAILABLE'
EISÍDIF
WRITE(7,*)
WRITE(7,*)
C
WRITE(7,*)' WEIGHT WEIGHT',
1' CHI'
WRITE(7,*)' FR. OF FR. OF'
WRITE(7,*)' LIQUro POLYMER'
C
C DSfmALIZD^G WEIGHT FRACTIONS
C
DW=0.01
W(l)=0.01
110 W(2)=1.0-W(l)
c
C SOME PRELIMDSfARY CALCULATIONS
C
R2=0.0D-K)0
Q2=0.0D+00
DO 135 I=1,EVDC
R2=R2+Wa)*RlPRIMEa)
Q2=Q2+W(I)*Q1PRIME(I)
135 CONTDWE
DO 140 I=1,IMX
PHPRDVlE(I)=RlPiaME(I)*W(I)/R2
THPRIMEa)=QlPRIMEa)*W(I)/Q2
140 CONTINUE
C
C CALCULATION OF COMBDSfATORIAL PART (bialc) OF SOLVENT ACTIVITY
C
LNCOMB1=DLOG(PHPRIME(1))+(1-PHPRIME(1))+5.0D+00*Q1(1)*
1 (DLOG(THPRDV1E(1)/PHPRDV[E(1))+(PHPRIME(1)/THPRIME(1))-1.0D+00)
C
C CALCULATION OF RESDDUAL PART Onalr) OF SOLVENT ACnVITY
C CALCULATION OF THETAPRDVIE VALUES FOR EACH GROUP DSf EACH
C COMPONENT
C
102
SUMQPRW=O.OD+00
DO 200 I=1,IMX
DO 210 J=l JLS(I)
QPRWa,J)=W(I)*AN(I,J)*Q(L\R(I,J))/MWl(I)
210 SUMQPRW=SUMQPRW+QPRWa,J)
200 CONTDSfUE
DO 220 I=1,DÆX
DO 230 J=1,ILS(I)
THETAPRa,J)=QPRWa,J)/SUMQPRW
230 CONTINUE
220 CONTDSfUE
C
C CALCULATION OF bi(Tauk) FOR ALL GROUPS IN SOLVENT SPECIES
C
1=1
DO 240 J=1,ILS(1)
SUMl=0.0D+00
DO 250 n=l,D4X
DO 260 jj=i,n.sai)
260 SUMl=SUMl+THETAPR(n,JJ)*SHI(MGNO(n,JJ),MGNO(l,J))
250 COlSfTDSfUE
SUM3=0.0D+00
DO 270 n=l,IMX
DO 280 JJ=l,ILSai)
SUM2=0.0D+00
DO 290 ni=l,IMX
DO 300 JJJ=l,ILS(ni)
300 SUM2=SUM2+THETAPR(m,JJJ)
1 *SHiavlGNO(m,JJJ),MGNOai,JJ))
290 CONTDSÍUE
280 SUM3=SUM3+THETAPR(n,JJ)*SHI(MGNO(l,J),MGNOai,JJ))/SUM2
270 CONTINUE
LNTAUK(l,J)=QaAR(l,J))*(l-DL0G(SUMl)-SUM3)
240 CONTDWE
C
C CALCULATION OF UiTaukl VALUES WITHm SOLVENT MOLECULE GROUPS
C
IF aLS(l).EQ.l) THEN
LNTAUKl(l,l)=0.0D+00
GO TO 350
ENDIF
C
C CALCULATION OF THETAPRIMEl VALUES FOR EACH GROUP D^ SOLVENT
C MOLECULE
103
SUMQPRWl=O.OD+00
DO 301 J=1,ILS(1)
QPRWl(l,J)=AN(l,J)*QaAR(l,J))/MWl(l)
SUMQPRW1=SUMQPRW1+QPRW1(1,J)
301 CONTDWE
DO 302 J=1,ILS(1)
THETAPRl (1 ,J)=QPRW1 (1 ,J)/SUMQPRW1
302 CONTDSÍUE
C
DO 310 J=1,ILS(1)
SUMl=O.OD+00
DO 320 JJ=l,n.S(l)
320 SUMl=SUMl+THETAPRl(l,JJ)*SHia4GNO(l,JJ),MGNO(l,J))
SUM3=0.0D+00
DO 330 JJ=1,ELS(1)
SUM2=0.0D+00
DO 340 JJJ=1,ILS(1)
340 SUM2=SUM2+THETAPRl(l,JJJ)*SHI(MGNO(l,JJJ),MGNO(l,JJ))
330 SUM3=SUM3+THETAPR1 (1 ,JJ)*SHI(MGNO( 1 ,J),MGNO( 1, JJ))/SUM2
LNTAUKl(l,J)=Q(IAR(l,J))*(l-DLOG(SUMl)-SUM3)
310 CONTDsfUE
C
350 LNRESl=O.OD+00
DO 360 J=1,ILS(1)
LNRES 1=LNRES l+AN^l^J^^O-NTAUK^l^J^-LNTAUKUl^J))
360 CONTINUE
C
C CALCULATDSfG SOLVENT ACTIVITY
C
LNAl=LNCOMB 1+LNRES1
C
C CALCULATDsfG INTERACTION PARAMETER
CHIPAR=(LNA1-DLOG(PHPRDV1E(1))-PHPRDV1E(2))/((PHPRDV[E(2))**2.0)
WRITE(7,6100)W(1),W(2),CHIPAR
6100 FORMAT(2(13X,D8.3),13X,D12.5)
C
C INCREMENTDSfG WEIGHT FRACTION W(l)
W(1)=W(1)+DW
IF (W(1).LE.0.99) GO TO 110
CLOSEaJNIT=7)
PRINT*,' JUST A REMDSfDER TO CHANGE OUTPUT FILE NAME!!'
END
104
APPENDDC C
and UNIFAP programs Usted in Appendices A and B. The UNIFAC interaction para-
meters between the 48 molecular groups Usted here were obtained from the Supple-
ment to Program UNIFAC, Fifth Revision : January 1992 by John P. Baker (Refs. 76,77).
105
P ***********4c***********************************************************
"CH2",1,"CH3M,.9011,.848,15.034
"CH2",1,"CH2",2,.6744,.54,14.026
"CH2",1,"CH",3,.4469,.228,13.018
"CH2",1,"C",4,.2195,0,12.010
"C=C",2,"CH2=CH",5,1.3454,1.176,27.044
"C=C",2,"CH=CH",6,1.1167,.867,26.036
"C=C",2,"CH2=C",7,1.1173,.988,26.036
"C=C",2,"CH=C",8,.8886,.676,25.028
"C=C",2,"C=C",9,.6605,.485,24.020
"ACH",3,"ACH",10,.5313,.4,13.018
"ACH",3,"AC",11,.3652,.12,12.01
"ACCH2",4,"ACCH3",12,1.2663,.968,27.044
"ACCH2",4,"ACCH2",13,1.0396,.66,26.036
"ACCH2",4,"ACCH",14,.8121,.348,25.028
"OH",5,"OH",15,1,1.2,17.008
"CH3OH",6,"CH3OH",16,1.4311,1.432,32.042
"H2O",7,"H2O",17,.92,1.4,18.016
"ACOH",8,"ACOH",18,.8952,.68,29.018
"CH2CO",9,"CH3CO",19,1.6724,1.488,43.044
"CH2CO",9,"CH2CO",20,1.4457,1.18,42.036
"CHO",10,"CHO",21,.998,.948,29.018
"CCOO",11,"CH3COO",22,1.9031,1.728,59.044
"CCOO",11,"CH2COO",23,1.6764,1.42,58.036
"HCOO",12,"HCOO",24,1.242,1.188,45.018
"CH2O",13,"CH3O",25,1.145,1.088,31.034
"CH2O",13,"CH2O",26,.9183,.78,30.026
"CH2O",13,"CH-O",27,.6908,.468,29.018
"CH2O",13,"FCH2O",28,.9183,l.l,30.026
"CNH2",14,"CH3NH2",29,1.5959,1.544,31.058
"CNH2",14,"CH2NH2",30,1.3692,1.236,30.50
"CNH2",14,"CHNH2",31,1.1417,.924,29.042
"CNH",15,"CH3NH",32,1.4337,1.244,30.50
"CNH",15,"CH2NH",33,1.207,.936,29.042
"CNH",15,"CHNH",34,.9795,.624,28.034
"(C)3N",16,"CH3N",35,1.1865,.94,29.042
"(C)3N",16,"CH2N",36,.9597,.632,28.034
"ACNH2",17,"ACNH2",37,1.06,.816,28.034
106
"pyridine",18,"C5H5N",38,2.9993,2.113,79.098
"pyridine",18,"C5H4N",39,2.8332,1.833,78.090
"pyridine",18,"C5H3N",40,2.667,1.553,77.082
"CCN",19,"CH3CN",41,1.8701,1.724,41.052
"CCN",19,"CH2CN",42,1.6434,1.416,40.044
"COOH",20,"COOH",43,1.3013,1.224,45.018
"COOH",20,"HCOOH",44,1.528,1.532,46.026
"CCr,21,"CH2Cr,45,1.4654,1.264,49.483
"CCI",21,"CHCI",46,1.238,.952,48.475
"CCr,21,"CCl",47,1.006,.724,47.467
"CC12",22,"CH2C12",48,2.2564,1.988,84.940
"CCI2",22,"CHC12",49,2.0606,1.684,83.932
"CC12",22,"CC12",50,1.8016,1.448,82.924
"CC13",23,"CHC13",51,2.87,2.41,119.389
"CC13",23,"CC13",52,2.6401,2.184,118.381
"CC14",24,"CC14",53,3.39,2.91,153.838
"ACC1",25,"ACC1",54,1.1562,.844,47.467
"CNO2",26,"CH3NO2",55,2.0086,1.868,61.042
"CNO2",26,"CH2NO2",56,1.7818,1.56,60.034
"CNO2",26,"CHNO2",57,1.5544,1.248,59.026
"ACNO2",27,"ACNO2",58,1.4199,1.104,58.018
"CS2",28,"CS2",59,2.057,1.65,76.142
"CH3SH",29,"CH3SH" ,60,1.877,1.676,48.108
"CH3SH",29,"CH2SH",61,1.651,1.368,47.100
"furfural",30,"furfural",62,3.168,2.481,96.090
"DOH",31,"(CH2OH)2",63,2.4088,2.248,60.052
"r,32,"I",64,1.264,.992,126.92
"Br",33,"Br",65,.9492,.832,79.916
"C-C",34,"CH'-C",66,1.292,1.088,25.028
"C'-C",34,"C~C",67,1.0613,.784,24.020
"Me2SO",35,"Me2SO",68,2.8266,2.472,78.131
"ACRY",36,"ACRY",69,2.3144,2.052,53.06
"aCC",37,"Cl(C=C)",70,.791,.724,35.45
" ACF",38," ACF",71 ,.6948,.524,31.01
"DMF",39,"DMF-1 ",72,3.0856,2.736,73.09
"DMF",39,"DMF-2",73,2.6322,2.12,71.09
"CF2",40,"CF3",74,1.406,1.38,69.01
"CF2",40,"CF2",75,1.0105,.92,50.01
"CF2",40,"CF",76,.615,.46,31.01
"COO",41,"COO",77,1.38,1.2,44.010
"SiH2",42,"SiH3",78,1.6035,1.2632,31.110
"SiH2",42,"SiH2",79,1.4443,1.0063,30.102
"SiH2",42,"SiH",80,1.2853,.7494,29.094
"SiH2",42,"Si",81,1.047,.4099,28.086
107
"SiO",43,"SiH20" ,82,1.4838,1.0621,46.101
"SiO",43,"SiHO",83,1.303,.7639,45.093
"SiO",43,"SiO",84,1.1044,.4657,44.085
"NMP",44,"NMP",85,3.981,3.2,99.13
"Tert-N",45,"-N=" ,86,0.2854,0.0920,14.008
"N,N-Amide",46,"CON(CH3)2",87,2.859,2.428,72.086
"Amide",47,"CONH2",88,1.466,1.336,44.034
"OCCOH",48,"C2H5O2",89,2.1226,1.904,57
108
APPENDK D
The AX value for the PSf-(NMP-DMSO) system was calculated as foUows. The
PSf-solvent mixture system consisted of 2 g of the polymer and 98 g of the (1:1) solvent
mixture ie., 54.78 g of NMP and 43.22 g of DMSO. The coagulation value of the system
was 1.1 g water. Based on this overaU composition, the binary concentration-dependent
UNIFAP. The values of Xj^ and X^j in this case are then given by
In addition to these interactions, the binary interaction between NMP and DMSO
must also be accounted for by Xf^.D^so- Therefore, the AX value in this case is given
by
where Sl and S2 represent the components of the solvent mixture, NMP and DMSO.
From the UNIFAC and UNIFAP calculations, the AX value in this case was estimated to
be
= 5.108
109
APPENDDC E
gaseous species across a polymer membrane with effective thickness (1) is given by
N = P.(Ap/l) (El)
where P is the permeability coefficient of the species in the polymer material, and Ap is
the partial pressure driving force the gas across the membrane interphase.
The nitrogen fluxes of the dense membranes obtained from the CA-MA and CA-
THF systems were, therefore, calculated as foUows, based on the permeabUity coefficient
conditions as those used in this study, and the thickness of the membranes, which were
= 336.05 cm Hg
= 67.5 X 10-^ cm
110
flux across CA-MA membrane, (N) = [0.23 X 10"^° (cc(STP).cm)/(cmls.cm Hg)]
= 75 X lO^ cm
111