DESALINATION

ELSEVIER Desalination 100 (1995) 139-148

Characterization of membrane distillation membranes prepared

by phase inversion*
J . M . O r t i z d e Z f i r a t e * * , L. Pefia, J.I. M e n g u a l
Departmento de Ffsica Aplicada I. Facultad de Ffsica. Universidad Complutense, 28040 Madrid, Spain

Received 25 January 1995; accepted 28 June 1995

Abstract
In this paper, flat membrane distillation membranes have been successfully manufactured from PVDF/DMAc
and PVDF/DMF blends by using phase inversion induced by an immersion precipitation technique. The structure
of the membranes is asymmetric with a porous top layer and macrovoids, as assessed by SEM. The existence of
MD fluxes in these membranes is established by performing various pure water flux experiments. A maximum
in the MD fluxes for a particular value of the polymer content in the casting solution from which the membrane
is manufactured has been observed. The dependence of the magnitude of the fluxes on the membrane thickness
is also discussed and the influence of temperature polarizatton evaluated.

Keywords: Membrane distillation; Membrane preparation; Membrane characterization; Polyvynilidine fluoride

memt~ranes

1. Introduction used various Gelman and Millipore polytetra-

Up to now membrane distillation (MD) opera-
tions have been generally carried out with com-
mercial porous hydrophobie membranes, initially
manufactured for microfiltration purposes. For
example, in pioneer papers, Pagliuca et al. [1]
*Presented in a previous form at the X Summer
School of the ESMST, Valladolid, Spain, September,
1993.
**Corresponding author.
fluoroethilene (PTFE) membranes; Schneider and
Van Gassel [2], Drioli and Wu [3] and J6hnson
et al. [4] used ENKA polypropilene (PP) mod-
uies, etc. As a matter of fact, even in most recent
papers on the subject, commercial filtration mem-
branes continue being used. This is, for instance,
the case of Drioli et al. [5], who used commercial
Gelman and Millipore polyvynilidene fluoride
(PVDF) membranes, Ortiz de Zfirate et al. [6],
who used Gelman PTFE membranes, or Seho-
field et al. [7], who used Durapore membranes,
etc. As far as we know, just one attempt has been

0011-91(~/96/$15.00 63 1996 Elsevier Science B.V. All rights reserved

PII SO011-9164( 96)00015-X
140 J.M. Ortiz de Z_,drate et al. / Desalination 100 (1995) 139-148

recently made in order to manufacture a mem- possible mechanisms (Knudsen, Poiseuille and
brane specifica,'ly for MD [8]. In that paper, diffusion) which may govern the transport pro-
tubular membranes were prepared by the dry-jet cess. Their arguments could be summarized in
wet spinning technique. Also recently [9], a new the following equations:
method to develop tailored membranes for MD
has been reported using surface modification of
~ydrophilic porous partitions. It is clear that the j cA~,v c [dev] aTM (1)
prospects of improvement are very great in this
field.
where J is the molar flux per unit area, ~ is the
It is known that the polymeric material used
membrane thickness, C is a phenomenological
to produce MD membranes must be hydrophobic,
constant called the true membrane mass transfer
and it is generally thought that the magnitude of
coefficient, AP r is the vapor pressure difference
the MD fluxes obtained through such membranes
between the two sides of the membrane, which is
depends mainly on the porosity [10] and, of
expressed in terms of the interfacial temperature
course, on the thickness. Therefore, phase inver-
difference A T u in the second part of Eq. (1). Our
sion with hydrophobic polymers seems to be a
present definition of C is slightly different from
reasonable method to obtain MD membranes. In
that of Schofield because we have extracted from
this work we have used different flat PVDF
C the thickness dependence in order to be able to
porous membranes manufactured by phase inver-
discuss separately this dependence later. So, in a
sion from casting of concentrated solutions of
first approximation, coefficient C should only
that polymer. The solvents used were dimethyl-
depend on the mean temperature at which the
acetamide (DMAc) and dimethylformamide
MD is carried out and on some geometric param-
(DMF). In order to characterize the ability of
eters of the membrane, mainly the porosity (be-
these membranes to give MD fluxes, we have
ing independent of membrane thickness and
measured the water flux for different temperature
temperature difference).
gradients at the same mean temperature. We have
Eq. (1) requires an adequate knowledge of the
also taken various SEM microphotographs to
transmembrane temperature difference (ATM), but
complete the characterization of our membranes.
due to the well-known phenomenon o~"tempera-
The dependence of MD fluxes on two geometric
ture polarization, this may vary markedly from
parameters of the membranes, the thickness and
the measurable bulk temperature (ATB). The
the porosity (related with the polymer content in
analysis of temperature polarization was also
the casting solution), is studied. The effect of
performed in [11]. By studying the heat transfer
temperature polarization is discussed and eval-
problem in steady state it is possible to arrive at:
uated.
2 J M AHv

2. Theory
am h
,,r,,, o (2)
Porous hydrophobic membranes separating
two aqueous phases can give significant fluxes
when a temperature gradient is imposed through
l -rrJ
them. The driving force for this transport process where M is the molar mass of water, AH r the
is the water vapor pressure difference between heat of vaporization of water, LM the effective
the edges of each one of the pores (APt). The thermal conductivity of the membrane and h the
theory of MD has been extensively analyzed by heat transfer coefficient of the unstirred layers
Schofieid et al. [11]; they discussed the three adjacent to the membrane.
 J.M. Ortiz de Z~rate et al. / Desalination I00 (1995) 139-148
By combining Eqs. (1) and (2), it is possible
to get the following expression:
h c t_~_ j T
j .... aT B (3)
h a+2 XM+2 C M ~ z [-'~-i r
or, in a shorter form:
J--B ATn (4)
where B is a new phenomenologicai coefficient,
which is called the global non-isothermal mass
transport coefficient. Coefficient B measures the
global ability of the membrane to give MD flux-
es, and it is that in which we are interested. Coef-
ficient B depends on the porosity of the mem-
brane (through C), on the temperature polariza-
tion (through h), on the thickness of the mem-
brane and, finally, on the mean temperature at
which the MD is carried out (through both C and
the vapor pressure temperature derivative).
3. Membrane preparation and characteri-
zation
Fiat PVDF membranes were prepared as de-
scribed elsewhere [12,13] where these kind of
membranes were manufactured for using in mi-
cro- and ultrafiltration or gas separation process-
es. In the present ease, five PVDF/DMAc and
three PVDF/DMF solutions were made. The
polymer was purchased from Aldrich and the
solvents from Merck. The concentration of the
solutions was 10%, 13.2%, 15%, 20% and 25%
w/w for PVDF/DMAc and 10%, 15% and 20%
w/w for PVDF/DMF blends. It was observed that
the solubility of the polymer is better for the
DMAc solvent than for the DMF one. The dope
was cast onto a glass plate using a doctor blade.
The depth of the casting was 400 gtm for most of
the membranes, although membranes were pre-
141
pared, in some cases from the same solution but
with different casting thicknesses. After a short
residence time at ambient conditions (295 K,
20% rh) the solfilm was immersed in a water
bath at 295 K. The phase inversion took place
and a polymeric film was obtained, completely
imbibed in water. After v~ashing and prior to use,
the membranes were dried by putting them in an
oven at 318 K overnight. The resulting partitions
appeared quite homogeneous and hydrophobie
(drops of water over its surface do not wet it) and
had good mechanical properties, tn order to
check reproducibility, at least two specimens of
membrane were manufactured from each solution
to make a total of 13 membranes from the
PVDF/DMAc solutions and nine from the PVDF/
DMF ones.
The membrane thicknesses were measured
with a micrometer. It was observed that, as ex-
pected, ti'..e membrane thickness was always
smaller than the cast thickness, and for the same
cast depth it decreased as the polymer content in
the solution became lower. For instance, for the
DMAc solution: with a casting depth of 400 lain,
the membrane thicknesses varied from 85 pro,
for the membrane with 25% PVDF content, to
54 pan, for that of 10%. A geod reproducibility
for the membrane thickness prepared from the
same solution and casting depth was found. This
can be seen in Tables 1 and 2 where the mea-
sured thicknesses are explicitly displayed for
each membrane. The membranes for which the
casting depth was different from 400 lain are
marked.
Some SEM microphotographs were taken in
order to visualize the membranes. The first fea-
ture revealed in the pictures is the membrane
asymmetry. Thus, in Fig. 1, the two faces of the
same membrane (15% PVDF content, DMAc as
solvent) are shown. There a difference in the
pore diameters, around 0.1 ~tm in one face and of
the order of I ~ in the other, is shown. It was
also observed that the pore diameters on both
sides gradually increase as the polymer content in
the casting solution decrease. The SEM inspec-
tion of membrane sections reveals a structure
142 J.M. Ortiz de Z~rate et al. /Desalination 100 (1995) 139-148

Table !
Measured values o f the global non.-isothermal mass transfer coefficient (B) with the corresp.~nding calculated values
o f the true mass transfer coefficient (C) for the different membranes manufactured from PVDF/DMAc blends. In
all cases the casting depth was 4(i0 p.m except for * where the casting depth was 300 p.m and ** where it was
500 ~tm

Membrane PVDF weight Thichness, Bxl04 measured Cxl07 calculated Mean Cxl07 mol
content, % pm mol s - I m -2 K -I mol s -~ m - I kPa - I s - I m -~ kPa - I

DMAcl 10 54 5.616 1.0

DMAc2 I0 60 5.811 1.2 1.1 +__0.3
DMAc3* 13.2 56 11.78
DMA¢4 13.2 74 9.552
DMAc5 13.2 68 10.39
DMAc6** 13.2 126 4.762
DMAc7** 13.2 145 6.852 3.0 a 3.0 -+ 0.8
DMAc8 15 75 9.850 2.5
DMAc9 15 70 10.42 2.5 2.5 _+ 0.1
DMAcl0 20 80 8.482 2.3
DMAcl I 20 79 8.173 2.2 2.2 4. 0.2
DMAcI2 25 91 6.031 1.8
DMAcl3 25 87 6.331 1.9 !.8 -+ 0.1

aThe C value was calculated by fitting to Eq. (5). In the other cases the correction was done as indicated in the text.

Table 2
Measured values o f the global non-isothermal mass transfer coefficient (B) with the corresponding calculated values
o f the true mass transfer coefficient (C) for the different membranes manufactured from PVDF/DMF blends. In all
cases the casting depth was 400 p.m except for * where the casting depth was 300 p.m and ** where it was 500 pm

Membrane PVDF weight Thickness, Bxl04 measured Cxl07 calculated Mean Cxl07 mol
content, % ~tm mol s - I m -2 K -I mol s - I m - I kPa - I s - ! m - I kPa - I

DMF 1 10 45 15.96 i. 1
DMF2 IC 51 9.570 0.5 0.8 + 0.4
DMF3 15 68 10.40 4.6
DMF4 15 62 13.89 6.7
DMFS** 15 93 7.674 2.5 3.6 - 2.1
DMF6* 20 55 7.584
DMF7 20 75 4.188
DMF8 20 70 5.114
DMF9 20 105 3.439 i.3 a 1.3 4- 0.4

aThe C value was calculated by fitting to Eq. (5). In the other cases tile correction was Oone as indicated in the text.

w i t h a s p o n g y t o p layer a n d w i t h m a c r o v o i d s . It m e r c o n t e n t in the c a s t i n g solution, in s u c h a w a y

c a n also b e o b s e r v e d that the t h i c k n e s s o f the that the porosity b e c o m e s lower. In Fig. 2 t w o
l a y e r free o f m a c r o v o i d s i n c r e a s e s w i t h the poly- pictures o f m e m b r a n e sections appear. T h e m e m -
 J.M. Ortiz de Zdrate et aL / Desalination I00 (1995) 139-148 143

Fig. I. Two faces of the

same membrane, produced
from a casting solution
with 15% weight content
of PVDF in DMAc. Mag-
nification xS000. The dif-
ference in pores diameters
~ppears evident. The sur-
face in contact with the
glass plate during phase
inversion conesponds to
the top part of the figure.

brane on the right side was manufactured from a DMAc. The two features mentioned above can be
casting solution with 25% PVDF content, the clearly shown. It is important to notice that the
membrane on the lei~ was from a 10% PVDF two pictures were obtained with different magni-
content solution. In both cases the solvent was fications (see wbite bars in the photos). On the
144 J.M. Ortiz de Zdrate et al. / Desalination 100 (1995) 139-148

Fig. 2. Left: Section of a membrane produced from a casting solution with 10% PVDF content in DMAc. Right:
Sect;.,~r: of a membrane produced from a casting solution with 25% PVDF content in DMAc. The length of the
white bar in the photos corresponds to 10 p.m. The structure: asymmetric with porous top layer and macrovoids
appears evident. In both cases the surface in contact with the glass plate during phase inversion is at the right side
of the pictures.

other hand, it was impossible to manufacture Membrane

membranes from solutions with a weight polymer
content lesser than 10% because the resulting
membranes became inconsistent. Even in the
10% case little holes can be seen when the mem-
brane is observed against the light; this fact will
be important later when dealing with the trans-
port coefficients o f these membranes.
The main characterization technique used in
Measurement Cell
this paper is the flux measurements. In order to
measure the M D fluxes, a double cell apparatus Fig. 3. Schematic of the experimental setup.
was used, as described elsewhere [14]. The mem-
brane is placed in a PVC holder between two temperature inside each chamber, very close to
stainl~zs steel chambers filled with bidistilled the membrane surfaces, it was observed that the
water. The membrane area exposed to the flow temperature difference between both liquid phas-
was 12.6 cm 2. Each chamber had a thermostated es was always 1 K lower than the one pro-
jacket connected to a circulation thermostat. Two grammed in the thermostats. In order to measure
Ptl00 probes were used in order to measure the the fluxes, the liquid leaving the cold chamber
 J.M. Ortiz de Zdrate et aL / Desalination 100 (1995) 139-148 145

was allowed to drop onto the weighing pan of an

electronic balance interfaced with a computer. In
Fig. 3 a diagram of the experimental setup can be
seen. 1 5 % / 10%

8.0

4. Discussion of flux measurement results

4.1. Vah'dity of Eq. (4)

The first fact verified is the fitness of Eq. (4),
which is the definition of coefficient B. MD
fluxes were measured for all the membranes
prepared at a mean temperature of 308 K, and I , , :"0.0," , I ' ' I '
with temperature differences of 4, 9, 14, 19, 24 -15.0 15.0 AT(K) 30.0

and 29 K. In some cases negative gradients were

also applied. In Fig. 4 the results for some of the
4.O
PVDF/DMF membranes are presented. In two
cases the fluxes are displayed with a negative
gradient, so it is possible to observe that the Fig. 4. Experimentally measured non-isothermal fluxes
asymmetry presented in the membranes structure vs. temperature difference between the chambers. The
is not exhibited in the fluxes. values for three of the PVDF/DMF membranes are
From data as those displayed in Fig. 4, the displayed, and the PVDF content in the casting solu-
non-isothermal mass transport coefficient can be tion is explicitly drawn. The fitness of Eq. (4) and the
symmetry in the fluxes are shown.
obtained by adjusting the experimental pairs of
data {ATB,J} to a straight line going through the
origin (see Eq. (4)). In all cases the agreement 4.2. Dependence on thickness
was good, as evidenced by a visual inspection of
From Eqs. (3) and (4), and for the particular
Fig. 4. This means that the definition of a global
temperature conditions of our experiments, it is
coefficient B makes sense.
easy to arrive at:
The B values obtained from these fitting pro-
cedures are displayed in the fourth column of
Table I (DMAc solutions) and Table 2 (DMF
solutions), with the respective thicknesses. Tables c --~" 35
1 and 2 show that membranes produced from
DMAe solutions give, more or less, the same where
fluxes as the DMF ones. Also a rather good
reproducibility is observed between the B and 8
values obtained for different membranes prepared
from the same solution and casting depth. In
addition, it is observed that the dispersion in the
8°=h
, ~ 3
i +
B values increases as the polymer content in the Eq. (5) means that B - I should depend linearly on
casting solution decreases. This result might be thickness 6. From the slope of this straight line,
interpreted by saying that the number of defects it is possible to obtain coefficient C, provided the
(holes) grows when the polymer content is re- temperature derivative of the vapor pressure is
duced. known. The value of the intercept, 5 0, does de-
146 J.M. Ortiz de Zttrate et aL / Desalination 100 (1995) 139-148
pend on C itself, on the effective thermal conduc-
tivity of the membrane and on the polarization
(through h).
Unfortunately, we have only very few points
to study the thickness dependence of the global
coefficient. In Fig. 5 are plotted the B - I values
obtained for the membranes manufactured from
PVDF/DMAc 13.2% and PVDF/DMF 20%
blends where membranes were manufactured
with different thicknesses. There is a great dis-
persion in the data, but it seems that the straight
line fitting might be considered as valid. In the
fitting procedure for the DMF membranes, the
point with the smaller thickness was rejected
because it departs a lot from the linearlity.
With the values for C obtained from the
slopes of the lines in Fig. 5, it is possible to see
that the second term inside the brackets in Eq. (6)
is two orders of magnitude lower than the effec-
tive membrane thermal conductivity. This con-
ductivity mary be estimated as the thermal con-
ductivity of the polymer multiplied by one minus
the void volume fraction of the membrane, be-
cause the contribution of the pores, filled with
steam, is much lower. Therefore, it is expected
that the value of ~0 will increase with the poly-
mer content in the casting solution, as shown in
Fig. 5.
Multiplying the slope of the fittings of Fig. 5
by B and by the thickness, it is possible to obtain
the quotient (ATM/ATB), which is around 70-
75% for all the membranes that appear in the
figure.
We can use these results in order to account
for temperature polarization in all the membranes
by supposing that the ~0 value is almost the same
throughout the runs. We have assumed that this
constant value is equal to the mean of the two
intercepts appearing in Fig. 5, that is 4 ~tm. With
this approximation we may determine the C
value corresponding to a given B. The fifth col-
umn of Tables 1 and 2 show the values for C
obtained by this procedure. It should be taken
into account that this procedure only produces an
estimated value for C because certainly ~o does
30.00 --
PVDF/D20%
M:
20.00 •
m
E O .4"
~ 10.00.
0.~
0 ' / O ' I o ' I '
120 '1
160
Thickness (pm)
Fig. 5. Plot of B -I vs. the thickness for sets of mem-
branes manufactured from solutions with the same
concentration, thus with an equivalent porosity.
depend on membrane porosity. But as porosity
does not vary very much in the set of membranes
we have manufactured, ~0 will change only a few
microns. As the thickness of the membranes
ranges from 50-150 I.tm, the error that this small
change in ~0 introduces in the calculations with
Eq. (5) is not expected to be very important.
4.3. Dependence on polymer content in the cast-
ing solution
The data appearing in Tables 1 and 2 allow us
to study the dependence of the MD fluxes with
the PVDF content in the casting solution, which
would be correlated '~othe membrane porosity. In
Fig. 6, the true transport c.nefficient of the mem-
brane, C, is shown vs. the initial casting solution
concentration, for the DMF and DMAc solvents.
In both cases a maximum is observed near the
15% w/w of PVDF. The appearance of this maxi-
mum can be interpreted by thinking that over this
value, the top layer becomes more dense and so
the fluxes are reduced. On the other hand, under
the 15% value, the membrane matrix seems to be
rather inconsistent and big holes ap~ear sporadi-
cally, as it was discussed before. Consequently
 J.M. Ortiz de Zdrate et al. / Desalination I00 (1995) 139-148
8.00-
..... 6.00-
~[[ 4.00.
o tubular membranes specifically prepared for MD
E
~o
v¢
¢J
2.00.
0.00
' I ' t" ' I '
a.O0 12,00 16.00 20.00
% PVDF Content
Fig. 6. True membrane mass transfer coefficient (C)~
for different polymer concentrations in the casting
solution. The solvent employed is drawn. The exis-
tence of a maximum for a particular polymer content
is shown.
the membrane matrix cannot completely reject
the liquid water and some pores became wetted.
The filled pores do not contribute to MD as was
a,',ply discussed in [15]; therefore, the membrane
surface proficient for transport is reduced and so
are the fluxes.
5. Comparison with the literature
The B values obtained for our membranes
may be compared with the ones appearing in
[16]. There, MD fluxes were measured for a
commercial microfiltration PVDF membrane
manufactured by Miilipore with the name GVHP.
The methodology and apparatus used in that
research were close to those used in this paper,
so the effects of temperature polarization may be
considered similar. In [16] membranes were
characterized by a transport coefficient which is
our present B multiplied by the thickness. In the
series of experiments with the closer temperature
conditions to the present ones, from the data of
[16] a B value of 1.2x10 -3 mol m - I s - ! K - I is
obtained, which is a little bit larger than the val-
147
ues measured in the present work. It seems that
we have not been able to improve the fluxes
already obtained through commercial filtration
membranes; therefore, more effort appears to be
necessary in this field.
On the other hand, our results may be also
compared with those of Fujii et al. [8] where
were used. They manufactured the membranes by
c
phase inversion from PVDF solutions in dimeth-
ylsuifoxide (DMSO) with a concentration1 ranging
from 27-30%. Thereafter they measured the
fluxes by arranging the tubular membranes in
modules. In their Table 10, they summarize the
I ' I
24,00 28.00 results for MD experiments. Unfortunately, they
characterize the membranes by the equivalent
pore radius as measured by dialysis Rp; the poly-
mer content does not appear in their table. We
may guess that the larger the Rp, the lower ",he
polymer content should be in the spinning solu-
tion. It can be observed that as Rp grows, what
they call water permeation rate, a w (equivalent to
our J) passes through a maximum. Thus their re-
sults may be considered qualitatively similar to
ours. On the other hand, the numerical compari-
son of the magnitude of measured fluxes is very
poor. They reported water fluxes of the order o f
10 - s Kg m -z h - l , which are two orders o f mag-
nitude below the ones reported in the present
paper. This discrepancy may be explained be-
cause their water fluxes are measured in experi-
ments where ethanol is simultaneously passing
through the membrane. As is well known, the
ethanol causes a loss of hydrophobicity in PVDF
membranes. Therefore, it is reasonable that their
fluxes were much lower.
6. Conclusions
• It is possible to manufacture MD membranes
from PVDF,q~MAc and PVDF/DMF solutions
by the phase inversion technique. An asym-
metry is presented in the membrane structure.
• A good reproducibility is found for the global
non-isothermal coefficient B (as defined in
148 J.M. Ortiz de ZArate et al. /Desalination I00 (1995) 139-148
Eq. (4)) for various membranes, prepared
from the same solution.
• The membrane asymmetry is not correlated to
the fluxes. The dependence o f fluxes on mem-
brane thickness may be used to guess the
influence of temperature polarization.
- A maximum appears in the true mass trans-
port coefficient C (as defined in Eq. (1)) for a
particular value of the polymer content in the
casting solution from which the membrane is
prepared.
Acknowledgments
We wish to sincerely acknowledge Alfonso
Rodrfguez, from the Servicio de Microscopia
Electr6nica - UCM, who took the SEM micro-
photographs. We also wish to acknowledge fi-
nancial support from the Comunidad Aut6noma
de Madrid.
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