Journal of Membrane Science 207 (2002) 139141

Short communication

The wet phase separation: the effect of cast solution thickness on

the appearance of macrovoids in the membrane forming
ternary cellulose acetate/acetone/water system

Nua Vogrin a,b, , Crtomir

Stropnik a , Vojko Musil b , Milan Brumen c,d
a

Faculty of Chemistry and Chemical Engineering, University of Maribor, Smetanova 17, SI-2000 Maribor, Slovenia
b Faculty of Business and Economics, University of Maribor, Razlagova 14, SI-2000 Maribor, Slovenia
c Faculty of Education, University of Maribor, Koroka 160, SI-2000 Maribor, Slovenia
d Josef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia
Received 27 November 2001; received in revised form 13 March 2002; accepted 21 March 2002

Abstract
We report on novel observations on the appearance of macrovoids in the ternary cellulose acetate (CA)/acetone (ACE)/water
membrane forming system. The membranes are prepared by the wet phase separation whereby the cast solution is composed
of ACE and polymer, and the coagulation bath is pure water only. It is found that the macrovoid formation in a 12.5 wt.% cast
solution strongly depends on the cast solution thickness: macrovoids appear at the thickness of 500 m but not at 150 and
300 m. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Wet phase separation; Macrovoid; Cellulose acetate/acetone/water; Cast thickness

1. Introduction
Polymeric membranes are used in various industrial
applications for microfiltration, ultrafiltration, reverse
osmosis and gas separation [1]. Each implication demands specific requirements on the membrane material and structure. The wet phase separation technique
is the most common method for preparation and production of polymeric membranes. A cast thin layer of
a polymer solution is immersed in a liquid nonsolvent
for polymer that is miscible with polymer solvent. The
exchange of the solvent from a thin layer of polymer
solution with a nonsolvent from the coagulation bath
produces thermodynamic instability in now ternary
Corresponding author. Tel.: +386-2-229-4422;
fax: +386-2-2527-774.
E-mail address: n.vogrin@uni-mb.si (N. Vogrin).

membrane forming system. The thermodynamic instability is resolved by the separation into polymer-rich
and polymer-lean phases and the polymer-rich phase
forms a solid membrane matrix while the polymer-lean
phase leaves a porous structure by leaching out of the
system. In some ternary membrane forming systems,
parts of the porous structure include macrovoids. In
most cases, the porous substructure supports a dense
top-layer. By varying conditions of the wet phase separation technique (polymer concentration, the thickness of the cast solution, the coagulation medium and
temperature) polymeric asymmetrical porous membranes with a very large variety of properties can be
made.
During the preparation of asymmetric porous membranes by the wet phase separation technique from
the ternary system cellulose acetate (CA)/acetone
(ACE)/water, we observed that their cross-section

0376-7388/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 6 - 7 3 8 8 ( 0 2 ) 0 0 1 1 9 - 9

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N. Vogrin et al. / Journal of Membrane Science 207 (2002) 139141

morphology, especially the formation of macrovoids,

is strongly dependent on the cast solution thickness
when the membranes are prepared from a 12.5 wt.%
solution of CA in ACE.

2. Experimental
Experiments were performed at the room temperature. A solution of 12.5 wt.% polymer was prepared
by weighting CA (Aldrich, 18.095-5, M w = 30 000)
and ACE (J.T. Baker) into a 250 cm3 Erlenmeyer flask
and subsequent mixing for about 12 h on a mechanical
stirrer. We did not check the pure CA and commercial
ACE as well the cast solution to the water content.
The polymer solution was cast on a grind glass plate
with the knives with the precisely dimensioned slit.
All membranes were prepared from the same solution
at a cast solution thickness of 150, 300 and 500 m.
The glass plate with a thin cast layer was quickly
immersed in a coagulation bath of pure water. After
10 min the (proto)membrane was transferred to pure
water for 2448 h before it was dried in air between
sheets of filter paper for 3 days. The cross-section morphology of the membrane was obtained by a scanning
electron microscope (SEM, JEOL JSM-840A).

3. Results and discussion

The SEM pictures showed changes in the crosssection morphology with increasing nominal cast
thickness (see Fig. 1). The absence of macrovoids is
evident from the cross-section morphology of membranes formed from casts of 150 and 300 m. In
contrast, membranes, prepared from cast of 500 m
clearly had macrovoids, and the structured skin is
also well distinguished. Macrovoids had a classical
drop-like shape and extended entirely across the
cross-section of membranefrom the skin to the
bottom of the membrane. Importantly, macrovoids
only formed in the membranes prepared by the wet
phase separation technique from the ternary system CA/ACE/water at 12.5 wt.%, and a cast film
that is 500 m thick. We found no other reports
on macrovoid formation dependence on cast solution thickness. There is also no report on formation of such classically formed macrovoids in

Fig. 1. The cross-section morphology of the membranes formed

from the 12.5 wt.% CA/ACE solution by the wet phase separation
(nonsolvent: water). The cast thickness: (a) 150 m, (b) 300 m,
and (c) 500 m.

membranes prepared by the wet phase separation

from CA/ACE/water ternary system in the case of
binary polymer solution (nonsolvent or additives absent) and one component coagulation bath (water
only) [27]. Because macrovoids evidently appear at
various conditions and systems and are significant

N. Vogrin et al. / Journal of Membrane Science 207 (2002) 139141

characteristics of the porous structure of polymer

membranes, further studies will contribute to the elucidation of the membrane formation mechanisms. In
particular, the relation of macrovoid formation on
the thickness of the cast solution and presumably on
concomitant shrinkage of the layer upon formation of
the (proto)membrane can be integrated as a property
to the system of the elementary processes postulated
for the polymeric membrane formation mechanisms
[5].

4. Conclusions
We report a dependence of macrovoid formation
on the cast solution thickness in membranes formed
by the wet phase separation in the ternary system
CA/ACE/water where the solution is composed only
of ACE and polymer and the coagulation bath is only
pure water. Classical drop-like macrovoids appear
at the cast thickness of 500 m, at 150 and 300 m
only scarce cellular structure without macrovoids is
formed. This finding may be investigated as an impor-

141

tant part of elementary processes in polymeric membrane formation mechanism.

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