Desalination 183 (2005) 375382

Novel porous poly (vinylidene fluoride) membranes for

membrane distillation

A. Bottino*, G. Capannelli, A. Comite

Dipartimento di Chimica e Chimica Industriale, Universita di Genova, Via Dodecaneso 31, 16146 Genova, Italy
Tel. +39 010 3538724; Fax +39 010 3538733, 3536199; email: bottino@chimica.unige.it, capannel@unige.it

Received 22 February 2005; accepted 10 March 2005

Abstract
Polyvinylidene fluoride (PVDF) membranes were prepared by water immersion of a binary PVDF-solvent
solution cast on the outer surface of a porous tubular support. During immersion the free shrinkage of the cast
solution was hindered by the support and consequently the nascent membrane was subjected to a stretching action that
caused pore formation. A laboratory scale device was realized for casting operation and some preparative parameters
were studied to control the deposition of the PVDF solution on the porous support. Membranes were characterized
through scanning electron microscope observations, air permeability measurements, ultrafiltration tests and mem-
brane distillation experiments. These latter were carried out with a laboratory unit fed with 3 w/v% aqueous NaCl
solution at 69 C. The membranes were housed in a tubular cell with the feed flowing on the shell side and the sweeping
air in the membrane lumen. The effect of feed and gas velocity on the membrane performance was investigated and the
obtained results were compared with those of commercial tubular membranes tested on the same unit. The influence of
casting parameters on the morphology and permeation properties of the membranes was also studied.

Keywords: PVDF tubular membranes; Preparation and characterization; Air permeability; Ultrafiltration;
Membrane distillation

1. Introduction
Hydrophobic porous membranes have Hydrophobic membranes for these technologies
received increasing attention in the recent years are usually made from three polymers: polypro-
for their potential use in new membrane technol- pylene (PP), polytetrafluoroethylene (PTFE)
ogies like membrane contactors [1]. and polyvinylidene fluoride (PVDF) [2,3].
Among these polymers PTFE represents an
ideal trunk material for membrane contactors
*Corresponding author.

Presented at the Conference on Desalination and the Environment, Santa Margherita, Italy, 2226 May 2005.
European Desalination Society.
0011-9164/05/$ See front matter 2005 Elsevier B.V. All rights reserved
doi:10.1016/j.desal.2005.03.040
376 A. Bottino et al. / Desalination 183 (2005) 375382
manufacturing since it exhibits beside the highest
hydrophobic character also the best chemical
resistance and thermal stability. The basic
disadvantage of PTFE lies on its difficult pro-
cessability and at present, commercial PTFE
membrane are usually produced through com-
plicate extrusion, rolling and stretching proce-
dures [4]. Polypropylene can be transformed
into porous membranes through the more acces-
sible molten extrusion technique followed by
stretching or by the so-called thermal phase
separation process that, however, needs polymer
dissolution at high temperature in less common
solvents [4]. PVDF easily dissolves at room
temperature in a variety of solvents and
consequently porous membranes can be easily
produced by phase separation through simple
immersion of the casting solution in a non-sol-
vent (water) bath [4,5]. Membrane porosity is
controlled by introducing into the starting cast-
ing solution proper additives (the so-called pore
forming agents) or by replacing water in the
coagulation bath with a different polymer non-
solvent media [6]. Unfortunately pore forming
agents when remained entrapped into the mem-
brane may lower its hydrophobic character or
represent a source of chemical or thermal
instability while the use of a non-solvent differ-
ent from water increases disposal or recovery
problems of the coagulation bath.
This presentation deals with the prepara-
tion of PVDF porous membranes by water
coagulation of a binary polymer-solvent solu-
tion cast on the outer surface of a porous
tubular support that acts as pore forming
agent through a simple stretching action on
the forming membrane during immersion in a
water bath. A very cheap glass fiber braid was
choose as support. The effect of some casting
parameters, used to control the deposition of
the polymer solution on the braid, on the
structure, porosity, air permeability, flux
and retention properties of the membranes is
presented and discussed.
Table 1
Kinematic viscosity at 20 C of PVDF solutions in
NMP
PVDF concentration Kinematic viscosity
(wt%) (cSt-mm2/s)
10 417
12.5 941
15 2043
20 7587
2. Experimental
Casting solutions were prepared by dissol-
ving the PVDF (Foraflon 1000 HD, Atofina) in
reagent grade N-methyl-2-pyrrolidone (NMP).
Solution viscosities measured at 20 C by means
of a Cannon-Fenske viscometer are reported in
Table 1. Solutions were cast onto the external
surface of the tubular glass fiber braid shown in
Fig. 1b by using the simple device reported in
Fig. 2. A stainless steel bar was inserted into the
lumen of the braid in order to impart it a given
stiffness (Fig. 1a). After a proper immersion
Fig. 1. Braid and membranes: abraid (wall thickness
ca. 0.5 mm, inner diameter ca. 4.5 mm); bstainless
steel bar; csupported membrane (PVDF coating on
outer surface the braid); d1Accurel PP-Membrana
membrane (nominal pore size 0.5 mm; wall thickness
1 mm, inner diameter 5 mm); d2Accurel PP-Mem-
brana membrane (nominal pore size 0.2 mm; wall thick-
ness 450 mm, inner diameter 1800 mm.
 A. Bottino et al. / Desalination 183 (2005) 375382
Fig. 2. Device used for the preparation of PVDF
supported membranes: aPVDF casting solution;
bbraid coated with the PVDF solution film (in course
of extraction from the casting solution); crunning
water bath; dmotor to control braid extraction speed.
period into the polymer solution (Fig. 2a) the
braid was extracted at constant speed (Fig. 2b)
and then immersed in running water (Fig. 2c)
to precipitate the polymer and form the
membrane. After two hour rinsing time the
supported membrane was easily separated
from the metallic bar and kept overnight in
demineralized water prior to be dried in a
oven at 40 C. The length of the supported
membranes (Fig. 1c) prepared by the above
described procedure was of ca. 25 cm. Detailed
information of the structure of the glass fiber
braid can be obtained by the scanning electron
micrographs reported in Fig. 3. In order to
Fig. 3. SEM micrographs of the braid: asurface of
the braid (the bottom part of the micrographs shows
the PVDF coating); bglass fibers of the braid.
377
control the amount of PVDF coating along
the braid pieces of 5 cm length were cut and
weighted. Membranes with length of 15 cm
were used for air permeability measurements,
dextran ultrafiltration tests and membrane
distillation experiments. In order to properly
house the membrane in the tubular transparent
test cell both membrane ends were potted into a
small plastic rigid tube by using a polyurethane
resin. Air permeability was determined at 20 C
by measuring the pressure corresponding to an
increasing air flow rate set by a mass flow con-
troller and further checked by a soap bubble
flow meter. Ultrafiltration tests were carried
with an aqueous solution of Blue Dextran
(Pharmacia, MW 2,000,000 Da). The Dextran
concentration, 100 ppm, was kept constant by
recirculating both retentate and permeate to the
feed reservoir. Before UF test the membrane
were completely wetted by immersion first in
methanol and then in water. The feed flowed
along the outer surface of the membrane (shell
side of the test cell) at 1 m/s, 30 C and 0.1 bar
while the permeate was collected in the mem-
brane lumen. The duration of each tests was
90 min. The same unit was used for membrane
distillation experiments with 3 w/v% NaCl
solution at 69 C. The sweeping air flowed in
the membrane lumen with a velocity varying
from 0.03 up to 0.4 m/s and a pressure just
lower than the bubble point (air bubbles were
directly seen through the transparent test cell)
[7]. The feed velocity of the brine was in the
range 0.040.16 m/s. Accurel PP commercial
membranes (Fig. 1d1 and d2) supplied by
Membrana (Germany) were also tested
under the same operating conditions for com-
parison purpose. In order to obtain a proper
amount of distillate to determine salt reten-
tion the duration of membrane distillation
experiments was ca. 4 h. Cross-section and
surface of gold coated membrane samples
were examined under a scanning electron
microscope (SEM, Leica Stereoscan 440). In
378 A. Bottino et al. / Desalination 183 (2005) 375382

0.04 0.04
PVDF weight (g/cm)

PVDF weight (g/cm)

0.03 0.03

0.02 0.02

0.01 0.01

0.00 0.00
0 5 10 15 20 25 0 5 10 15 20 25
Braid length (cm) Braid length (cm)

Fig. 4. PVDF deposited as a function of the braid Fig. 6. PVDF deposited as a function of the braid
length. (PVDF concentration in the casting solution: length. (PVDF concentration in the casting solution
10 wt%; 20 wt%. Braid immersion time: 60 s; 10 wt%; Braid immersion time: 20 s; Braid extrac-
Braid extraction speed: 1.2 cm/s). tion speed: 1.2 cm/s, 1.7 cm/s, 2.1 cm/s).

order to obtain suitable cross-sections for
SEM observation the PVDF coating was
detached from the braid and fractured at
liquid nitrogen temperature.
3. Results and discussion
A large variety of membranes was pre-
pared by varying casting parameters such as
casting solution concentration, immersion
period of the braid and its extraction speed
0.04
PVDF weight (g/cm)
from the solution. Figs. 46 shows the
amount of PVDF coated on the braid as a
function of the above mentioned casting
parameters. Each point represents the PVDF
weight deposited on the previous 5 cm of
braid. As Fig. 4 indicates the PVDF weight
depends on the polymer concentration of the
casting solution and linearly increases from
the top (i.e. the part first extracted from the
polymer solution) to the bottom of the braid.
It is also shown that the slope is higher for
the more concentrated solution. Figs. 5 and 6
reveal that the amount of the deposited
PVDF increases by increasing the immersion

0.03
period of the braid and lowering the extrac-
tion speed. Even in these cases linear plots are
0.02
observed but the slope is slightly lower for
braids immersed in the solution for shorter
0.01 periods and more rapidly extracted.
Figs. 7 and 8 show the results of air perme-
0.00 ability measurements. Fig. 7 reports the beha-
0 5 10 15 20 25
viour of the air flux as a function of the applied
Braid length (cm) pressure for membranes cast from braids
Fig. 5. PVDF deposited as a function of the braid immersed for 60 s in different PVDF solutions
length. (PVDF concentration in the casting solution and extracted at 1.7 cm/s. An increase of the
10 wt%; Braid immersion time: 20 s, 60 s, 160 s; polymer concentration in the casting solution
Braid extraction speed: 1.2 cm/s). leads to less permeable membrane. The linear
 A. Bottino et al. / Desalination 183 (2005) 375382 379

7 permeability. A similar result was found for

6 membranes cast from other polymer solutions
(10 and 15 wt%).
5
Air flux (L/m2s)

Ultrafiltration tests with Blue Dextran

4
3 only to obtain an appraisal of water permea-
2
1
0
0 5 10 15
Pressure (mbar)
Fig. 7. Air flux vs. pressure (PVDF concentration in
the casting solution: 10 wt%, 12.5 wt%, 15 wt%;
Braid immersion time: 60 s; Braid extraction speed:
1.7 cm/s).
behaviour of the air flux as a function of the
applied pressure indicates that the gas transport
through the membrane is practically governed
by the Hagen-Poiseuille flow. Linear plots were
observed by investigating the air flux of the
membranes as a function of the other casting
parameters. Fig. 8 shows, as an example, the air
flux vs. pressure plot for membranes obtained
by braids immersed in a 12.5 wt% PVDF
solution for different times and extracted at 1.7
cm/s. As it can be seen a variation of the immer-
sion time has only a limited effect on the air
solution were carried out with the aim not
bility and large macromolecule retention but
also to have indication on the homogeneity of
the PVDF coating since the intensity of the
20 25 30
blue colour on membrane surface was higher
in those area where preferential permeation
of the dextran occurred. Even in this case
membranes prepared from different casting
conditions were tested and the results con-
firmed a higher dependence of the membrane
permeability from the PVDF solution con-
centration rather than from immersion time
and extraction speed of the braid. The effect
of casting solution concentration on the
permeate flux and dextran retention of the
membrane is shown in Fig. 9. At the begin-
ning of the test a given difference in the flux of
the various membranes are observed but by
increasing the operating time the membranes
cast from more dilute PVDF solutions exhibit
a higher tendency to compact and/or to
foul. As a consequence their permeate flux
decreases more rapidly with the operating

140
7
120
6
100
Flux (L/m2 h)

5
Air flux (L/m2s)

80
4
60
3
40
2
20
1
0
0 30 60 90 120
0
0 5 10 15 20 25 30 Operating time (min)
Pressure (mbar)
Fig. 9. Permeate flux as a function of the operating
Fig. 8. Air flux vs. pressure (PVDF concentration in the time. (PVDF concentration in the casting solution:
casting solution 12.5 wt%; Braid immersion time: 20 s, 10 wt%, 12,5 wt%, 15 wt%; Braid immersion
60 s, 160 s; Braid extraction speed: 1.7 cm/s). time: 60 s; Braid extraction speed: 2.1 cm/s).
380 A. Bottino et al. / Desalination 183 (2005) 375382

100 practically observed. It is worth noting that

membrane distillation tests were mainly aimed
80
at comparing the performance of the membrane
prepared in this work with that of commercial
Retention (%)

60
40
20
0 results are in good agreement with those of
0 30 60
Operating time (min)
Fig. 10. Blue Dextran retention as a function of the
operating time. (PVDF concentration in the casting
solution: 10 wt%, 12.5 wt%, 15 wt%; Braid
immersion time: 60 s; Braid extraction speed: 2.1 cm/s).
time so at the end of the test all membranes
behave similarly. Also the initial differences
in the retention of the various membranes
become progressively smaller with increasing
the operating time (Fig. 10).
Figs. 11 and 12 show the results of mem-
brane distillation experiments with the 3 w/v%
NaCl solution flowing in the shell side of the cell
with a velocity of 0.12 m/s. During the experi-
ments (4 h) no change in the distillate flux was
membranes and not at finding the process
operating conditions to obtain optimal mem-
brane performance. Fig. 11 shows that for all
types of membrane the flux is deeply affected by
the air velocity in the membrane lumen. These
90 120
Basini et al. [8] who found that the flux signifi-
cant increased in the low gas velocity range
prior to level off. Fig. 11 also indicates that the
flux of the PVDF membranes is slightly higher
than of the commercial membranes and does not
practically depend on the immersion time of the
braid in the polymer solution. Fig. 12 reveals
that the salt retention is always very high and
ranges from ca. 99.5 to ca. 99.9, depending on
the type of membrane. The effect of the varia-
tion of the brine velocity in the cell shell was also
investigated but the obtained results (not
reported in the present paper) indicated that
this process parameter did not practically affect
the membrane performance or at the most
slightly increased the flux. A scarce effect of the

100
3.0

2.5 99.9
Retention (%)

2.0
Flux (L/m2h)

99.8

1.5
99.7
1.0

99.6
0.5

0.0 99.5
0.0 0.1 0.2 0.3 0.4 0.5 0.0 0.1 0.2 0.3 0.4 0.5
Air velocity (m/s) Air velocity (m/s)

Fig. 11. Distillate flux as a function of the air velocity
for PVDF and commercial membranes. (PVDF mem-
branes: Concentration of the casting solution 15 wt%;
Braid immersion time: 20 s, 60 s, 160 s; Braid
extraction speed: 1.2 cm/s. Accurel PP membranes:
* d1 in Fig. 1;
d2 in Fig. 1).
Fig. 12. NaCl retention as a function of the air velo-
city for PVDF and commercial membranes. (PVDF
membranes: Concentration in the casting solution
15 wt%; Braid immersion time: 20 s, 60 s, 160 s;
Braid extraction speed: 1.2 cm/s. Accurel PP mem-
branes: d1 in Fig. 1; d2 in Fig. 1).
 A. Bottino et al. / Desalination 183 (2005) 375382
a b
10 m
Fig. 13. SEM micrographs of the cross-section of
PVDF membranes (Concentration of the casting
solution 15 wt%. aBraid immersion time:
20 s; Braid extraction speed: 1.2 cm/s. bBraid
immersion time: 60 s; Braid extraction speed: 1.7
cm/s).
a b
10 m
Fig. 14. SEM micrographs of the cross-section of
Accurel PP membranes (ad1 in Fig. 1; bd2 in
Fig. 1).
a b
400 nm
Fig. 15. SEM micrographs of the outer surface of
Accurel PP membranes (ad1 in Fig. 1; bd2 in
Fig. 1).
a b
400 nm
Fig. 16. SEM micrographs of the outer surface of
PVDF membranes (Concentration of the casting
solution 15 wt%. aBraid immersion time: 20 s;
Braid extraction speed: 1.2 cm/s. bBraid immer-
sion time: 60 s; Braid extraction speed: 1.7 cm/s).
381
feed velocity on the vapour permeation through
the membrane pores was also observed by Gos-
toli and Brodard et al. [9,10].
SEM micrographs of PVDF membranes and
commercial ones are compared in Figs. 1316.
PVDF membrane cross-sections exhibit a
typical asymmetric structure with large voids
beneath the outer surface layer (Fig. 13) while
commercial membranes present a structure
formed by a very uniform array of small cavities
(Fig. 14). Since commercial membranes are very
thick (Fig. 1) SEM micrographs in Fig. 14 refer
to the area near to the outer surface of the
membrane. However by other micrographs
(not reported in the present paper) taken in the
central part of the membrane as well as in the
area near to the membrane lumen no particular
change of cavities size and shape was observed.
As far as PVDF membranes is concerned a var-
iation of the casting parameters does not practi-
cally affect the structure of the membrane cross-
section since it is largely controlled by the poly-
mer solvent and in particular by the exchange
rate between the solvent and water during the
final immersion step of the cast solution [5].
From Figs. 15 and 16 a variety of pores are
clearly observed on the surface of the various
membranes. Although the pores of the commer-
cial membrane of Fig. 15b appear larger than
those of the membrane of Fig. 15a it seems very
difficult to find a strict connection between the
pore size examined by SEM and the nominal
values reported in the legend of Fig. 1. The
SEM surfaces of PVDF membranes (Fig. 16)
deserve to be discussed. In a previous study on
the preparation of flat sheet PVDF membranes
supported by a non-woven fabric [11] it was
found that the stretching action of the porous
support on the forming membrane during
immersion in the polymer non-solvent (water)
bath lead to the formation of new pore families.
The particular shape of the pores shown in
Fig. 16 suggests that even in this case the porous
support plays an important role on the
382 A. Bottino et al. / Desalination 183 (2005) 375382
membrane porosity formation. In fact after
immersion in running water the thin layer of
polymer solution coated on the outer surface of
the braid tends to shrink while the braid main-
tains its form also due to the presence of the
metallic bar in the lumen. The support stretch-
ing action depends on the characteristics of
the PVDF coating that in turn are con-
trolled by the concentration of the casting
solution. Dilute and less viscous solutions
tend to penetrate into the braid and form
thinner and more fragile coatings that are
more affected by the stretching action of the
braid and consequently more porous and
highly permeable membrane are formed.
4. Conclusions
A large variety of membranes with different
structure, porosity and permeation properties was
prepared from PVDF solutions cast on the outer
surface of a braid support. The advantage of using
this support lies in its very low cost with respect to
other (plastic, ceramic, metal) porous tubes and
tubulets. Of the casting parameters investigated
only the PVDF solution concentration seems to
have the most relevant role on the membrane
properties. Dilute and less viscous solutions lead
to a more homogeneous distribution of the PVDF
coating on the braid support and yield membranes
with higher permeability. The stretching action of
the support on the forming membrane during
water coagulation may be responsible for the for-
mation of pore with sizes in the range of a few
hundred of nanometers. These sizes along with the
hydrophobic character of the polymer make the
developed membranes potentially useful for mem-
brane distillation application. An additional
advantage of these membrane lies in their
improved mechanical properties due, obviously,
to the support. Work is in progress to better con-
trol the distribution of the PVDF coating along
the braid length especially in order to prepare
longer membrane for industrial application.
Acknowledgements
The authors wish to acknowledge Miss
Fiorenza Ferrari and Dr. Matteo Magnano
for their help in membrane preparation and
characterization test.
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