European Polymer Journal 66 (2015) 492501

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Inuence of different solvent and time of pre-treatment

on commercial polymeric ultraltration membranes applied
to non-aqueous solvent permeation
Frederico Marques Penha a, Katia Rezzadori a, Mariane Carolina Proner a, Vanessa Zanatta a,
Guilherme Zin a, Daniel Walker Tondo b, J. Vladimir de Oliveira a, Jos Carlos Cunha Petrus a,
Marco Di Luccio a,
a
b

Department of Chemical and Food Engineering, Federal University of Santa Catarina, 88040-970 Florianpolis, SC, Brazil
Technological Federal University of Paran, 85884-000 Medianeira, PR, Brazil

a r t i c l e

i n f o

Article history:
Received 23 July 2014
Received in revised form 6 March 2015
Accepted 8 March 2015
Available online 13 March 2015
Keywords:
Polymeric membranes
Non-aqueous systems
Organic solvents
Membrane conditioning
n-Hexane
Alcohols

a b s t r a c t
Several pre-treatments and solvents were tested through permeation in commercial polymeric membranes (UH004, UP005, UP010 and UH050 Microdyn-Nadir) with different
molar mass cut-offs (4 kDa, 5 kDa, 10 kDa and 50 kDa, respectively), in order to evaluate
their efciency and stability through non-aqueous solvent permeation. After pre-treatments and permeations, membranes were characterised with contact angle, Fourier
Transform Infrared Spectroscopy (FTIR), and Field Emission Scanning Electronic
Microscopy (FESEM) to evaluate structural integrity. The results of solvent permeation suggest that selectivity of the polymeric matrix depends not only on pore size, but also, in
great extent, on the interaction between solvent and polymer. A strong relation can be
noted between the conditioning length and permeability for ethanol pre-treatments.
Permeability to n-hexane increased from 4 to 18 times after pre-treatment, depending
on the time of exposure to ethanol and n-hexane. Characterisation analyses show no signicant changes on the membranes surface. In some cases, discrepancies observed among
permeate uxes and contact angles might be an indicative of the occurrence of swelling
and plasticisation. However, results suggest the feasibility in the use of these membranes
for the recovery of solvents in the oil industry, if suitable process parameters are chosen.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
The use of polymeric membranes is already a feasible
technology for water and aqueous solutions treatment.
Although there are many studies on the preparation of solvent resistant membranes, only few are commercially
available as Borsig, PolyAn, Duramem, Puramem and
SolSep membranes. Most of the commercial available
polymeric membranes are produced for aqueous systems
Corresponding author. Tel.: +55 48 3721 2529.
E-mail address: di.luccio@ufsc.br (M. Di Luccio).
http://dx.doi.org/10.1016/j.eurpolymj.2015.03.010
0014-3057/ 2015 Elsevier Ltd. All rights reserved.

and they present some drawbacks to industrial implementation in non-aqueous solvent-based processes. The
problems are generally related to membrane lack of stability, due to the changes caused by the solvents in its structure, and low permeate uxes [13]. Therefore, studies in
this eld could benet industry segments from edible oil
processing to pharmaceuticals and petrochemical for its
reduced energy consumption and process simplication.
Many authors suggest that the pre-treatment of polymeric membranes by immersion in organic solvents can
prevent the pore collapse during permeation and enable
the solvent entrance into the pores. This enhances the

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F.M. Penha et al. / European Polymer Journal 66 (2015) 492501

permeate ux and promotes better stability to non-polar

solvents. Besides, the conditioning step can also change
the surface polarity by grouping hydrophilic and
hydrophobic sites, improving the permeability to organic
solvents [47]. In addition, according to Coutinho et al.
[8] and Yang et al. [9] studies, the efciency of membranes
in organic solvent permeation is not only function of pore
size (size exclusion), but also function of chemical interactions between the solute and/or solvent and membrane
active layer.
Several pre-treatment solvents and pre-treatment times
have been proposed for different polymeric membranes.
Firman et al. [10] ooded the membranes with pure solvents
of decreasing polarities (ethanol, iso-propanol, n-hexane)
for 24 h. Araki et al. [7] used conditioning times of 30 min
in n-hexane before its permeation in polymeric ultraltration (UF) membranes (PVDF polyvinylidene uoride, PES
polyethersulfone, PC polycarbonate, CME mixed cellulose esters). Darvishmanesh et al. [11] used immersion
treatments in various organic solvents for one week before
permeation in nanoltration (NF) membranes produced
with polyamide (PA). Van der Bruggen et al. [5] also reported
treatments of 24 h by immersion in ethanol and n-hexane in
their study with NF membranes, and conclude that the
permeate uxes can be inuenced by the pre-treatment
solvent.
However, to the best of our knowledge, membrane pretreatments were evaluated concerning solely solvent
immersion, without mentioning the inuence of the binomial solvent and exposure time. Therefore, the present
work aims to evaluate the permeability of different solvents (ethanol, iso-propanol and n-hexane) and the inuence of these solvents and time of exposure in the
permeation of n-hexane through four commercial polymeric membranes with different molar mass cut-offs
(MMCO). Permeate uxes of the pure solvents were also
investigated as well as surface hydrophilicity and structural changes.

Table 1
Manufacturers data for the membranes tested.
Membrane

UH004

UP005

UP010

UH050

Material
MMCO (kDa)
T max (C)
pH range
Retention (%)

PESH
4
95
014
9299a

PES
5
95
014
9198a

PES
10
95
014
6385b

PESH
50
95
014
7588c

PESH Hydrophilic polyethersulfone.

PES Polyethersulfone.
a
Tested solute Dextran 10.
b
Tested solute PVP K17.
c
Tested solute PVP K30.

with pressure variation from 1 to 6 bar, in intervals of

0.5 bar. The temperature was maintained at 25 C.
For permeation with the treatment solvent (Fig. 1),
membranes were pre-treated with the respective solvents
for 2 h. Then, permeation assays were performed by the
ltration of the solvent used in the conditioning. For
n-hexane permeation (Fig. 2), the conditioning consisted
in sequential immersion of each membrane in solvents
whereas the rst is either ethanol or iso-propanol and
the second n-hexane, for 2 or 12 h. Figs. 1 and 2 summarise
the experimental strategy used in the study.
Both new and used membranes were characterised to
check for the structures integrity and changes in
hydrophilicity by contact angle measurements (sessile
drop method, Ram-Hart Instrument Co., USA), Fourier
Transform Infrared Spectroscopy with Attenuated Total
Reection (FTIR-ATR, Frontier, Perkin Elmer, USA) and
Field Emission Scanning Electronic Microscopy (FESEM,
JEOL JSM-6701F, Japan). All the characterisation analyses
were performed with membranes dried at room temperature for at least 72 h.

3. Results and discussion

3.1. Solvent permeability evaluation

2. Materials and methods

Permeation experiments were carried out in a bench
scale dead-end stainless steel ltration unit. The at sheet
membranes tested were from Microdyn-Nadir, and are
listed in Table 1. The effective surface area was 9.08 cm2
and the working volume of the cell was 250 cm3.
Membranes were submitted to different pre-treatments. The experimental procedure for all the membranes
initiated with immersion in ethanol for 15 min to remove
preservatives and ll the pores with the solvent. Then,
the conditioning started with immersion in the solvent
(deionised water, ethanol, iso-propanol or n-hexane) at different exposure times. Each treatment was performed with
a new membrane. Permeate uxes are an average of ve
measurements with the same membrane sheet at each
pressure. All the experiments were carried out at least in
duplicates. All solvents used in conditioning were analytical grade.
All the assays started with membrane compaction at
8 bar for 45 min, after which, permeation was carried out

The measurement of pure solvent (water, ethanol,

iso-propanol and n-hexane) permeate uxes through
pre-treated membranes allowed the calculation of
permeability (Table 3), as well as the evaluation of membrane performance in contact with the solvents. Since both
pressure and solvent can inuence the permeate ux, the
values for these parameters can be chosen to increase the
efciency of the ltration process [6]. Permeabilities were
normalised by the viscosity of each solvent for better
assessment of other factors that may have inuenced
membranes performance with the different solvents.
Solvent viscosities used are showed in Table 2.
Most of the studies concerning membranes in nonaqueous systems point out the inuence of viscosity on
the mass transport through the active layer and in membrane permeability and selectivity. According to
Sarmento et al. [12], a uid can be considered as a resistance to mass transport that promotes load losses between
the interfaces of the separation process. For ows in which
Reynolds number (Re) is very low, the ow rate is directly

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F.M. Penha et al. / European Polymer Journal 66 (2015) 492501

Fig. 1. Schematic diagram of the permeation assays with the solvents used in pre-treatment.

Fig. 2. Schematic diagram of n-hexane permeation assays.

Table 2
Solvent viscosities.
Solvent

Viscosity at 20 C [5] (mPa s)

Water
Ethanol
iso-Propanol
n-Hexane

1.002
1.078
1.960
0.326

proportional to the applied pressure differential, and inversely proportional to uid viscosity and bed length. This is
the basis for Darcys Law, given by the Eq. (1).

Q K  DP

A l  DL

where Q is the permeate ow rate (m3 s1); A, the membrane area (m2); K is the permeability of ltration media;
DP is the pressure differential (Pa); l is the uid viscosity
(Pa s); and L is the bed length (m).
Eq. (1) can be simplied to Eq. (2). The plot of experimental solvent ux (J) vs the pressure difference applied
to the process (DP) yield the membrane permeability,
obtained by the plot slope, usually expressed in
L m2 h1 bar1. Thus, we can note that the permeability
depends on the solvent viscosity. If the solvent permeability is multiplied by solvent viscosity (Table 2), expressing
both in the appropriate units, the normalised permeability
is obtained, which corresponds to K/DL.

J Lp  DP

Table 3
Membrane permeability to different solvents studied.
Normalised permeability (1014 m)

Permeability (L h1 m2 bar1)

Water
Ethanol
iso-Propanol
n-Hexane

UH004

UP005

UP010

UH050

UH004

UP005

UP010

UH050

20.7 2.1
11.0 0.9
4.4 0.9
3.0 0.8

27.8 3.8
29.6 6.7
3.6 1.2
6.1 1.3

97.8 10.0
41.2 3.8
8.4 0.9
52.1 3.2

250.3 17.0
118.4 8.2
29.4 3.1
81.8 6.4

5.7 0.6
3.3 0.3
2.4 0.5
0.3 0.1

7.7 1.0
8.9 2.0
1.9 0.7
0.5 0.1

27.2 2.8
12.3 1.1
4.6 0.5
4.7 0.3

69.7 4.8
35.5 2.5
16.0 1.7
7.4 0.6

F.M. Penha et al. / European Polymer Journal 66 (2015) 492501

where J is the membrane ux usually expressed in

L m2 h1, Lp is the solvent permeability, expressed in
L h1 m2 bar1; DP is the pressure difference, expressed
in bar.
It can be seen that the viscosity exerts substantial inuence on permeability. The solvent viscosity does not inuence normalised permeabilities, and thus we can account
the differences to solvent interaction with the membrane.
It is noteworthy that the permeability drops with the
increase in solvent hydrophobicity for all the membranes
studied. The difference between the water and n-hexane
permeabilities is higher for the membranes with smaller
pores (UH004 and UP005) than for the membranes with
higher pores (UP010 and UH050). This behaviour shows
that the interaction between the solvent and the membrane matrix plays an important role in membranes with
low molecular cut-off. For instance, water permeability is
1.9 and 6.9 times higher than ethanol and n-hexane
permeability for UH004, respectively. When we compare
the normalised values, water permeability is 1.7 and 19
times higher than ethanol and n-hexane permeability,
respectively. This difference occurs due to the low viscosity
of n-hexane when compared to the other solvents.
Permeate uxes for solvent treatment permeation
assays are shown in Fig. 3 for all the membranes.
Regardless of the solvent, the permeate ux increases as
the applied pressure increases, which is an expected behaviour. An exception can be observed for UP010 (Fig. 3c) and
UP005 in ethanol (Fig. 3b), in which at higher pressures,

495

uxes goes to a plateau. That behaviour suggests that the

compaction condition (8 bar45 min) was not enough for
this membrane. As there is no solute in the solvent, there
are no reasons for ux reduction. On the other hand, plateaus were also observed by other authors [1315] and
were related to the retention of solvent on the polymeric
matrix due to strong interaction amongst them, thus
reducing the permeate ux. It was also reported that high
pressures would intensify this phenomenon.
In addition, independently on the solvent, the larger the
pore sizes the higher the permeate ux. In the same way,
as the membranes in this study are originally proposed
for aqueous systems, the water uxes are higher than the
organic solvent uxes for all membranes, except for
UP005, in which the ethanol ux overcomes the water ux
in almost all pressures. Based on the physico-chemical
properties of the solvents (viscosity, surface tension), we
could predict that the ethanol ux would stay between
the water and iso-propanol ux. Thus, the unexpected
behaviour of ethanol permeation can be attributed to
membrane conditioning.
According to Araki et al. [7], the conditioning can possibly rearrange the hydrophilic and hydrophobic sites of the
polymeric matrix, turning the membrane more permeable
to ethanol. A clustering effect can explain the increase in
the ux. Clustering can be dened as a reorganisation of
the polymer chains in the membrane active layer. Several
authors, based on polymer chemistry, conrm such phenomenon [1618]. Clustering, in hydrophilic membranes,

Fig. 3. Permeate uxes for pre-treatment solvent permeation assays in (a) UH004, (b) UP005, (c) UP010 and (d) UH050, respectively.

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F.M. Penha et al. / European Polymer Journal 66 (2015) 492501

results in grouping and enlargement of hydrophobic clusters, thus it might affect the pore sizes as well. Therefore,
the clustering effect results in a slight decrease of total
pore number but with a small enlargement of pores, thus,
increasing non-polar solvent uxes.
On the other hand, swelling and plasticisation are to
some extent opposing phenomena, yet coexistent and
interdependent. Swelling phenomenon is the penetration
of the solvent in the polymeric matrix. According to Ebert
and Cuperus [19], when dense membranes swell, the free
volume increases. This would make dense membranes
more open, resulting in lower rejections and higher uxes.
On the contrary, in porous membranes, since the solvent
penetrates in the polymeric matrix, it swells and tends to
press the pore walls, resulting in narrower pores. In turn,
the phenomenon of plasticisation can be attributed to
swelling stresses on the polymeric matrix. The addition
or sorption of some species, in this case, the organic solvent, causes an enhancement of local segmentation motion
of the polymer chains, which leads to a weakening or softening effect characterised by a reduction in glass transition
temperature and modulus. This increase in local segment
motion results in enhanced transport rate of all the penetrants to be separated, resulting in losses in membrane
selectivity. Furthermore, plasticisation also leads to
acceleration in polymer physical aging rate, with thickness
decrease and thus, signicant ux reduction [20].
However, if swelling and plasticisation takes place, the
effect on the ux is hardly predictable and the membrane
can even become unstable [21].
To summarise, clustering effect, swelling and plasticisation are phenomena that can coexist and, although it
seems that swelling and plasticisation are opposing phenomena, they can both lead to lower uxes, yet only plasticisation results in less selectivity. As to clustering, it is
desirable that it may occur mainly on pre-treatment stage.
However, while exposed to the solvents, depending on
their interaction with the polymer, membranes are susceptible to all the aforementioned phenomena.
Only UH004 (Fig. 3a) showed the expected behaviour of
uxes (water > ethanol > iso-propanol > n-hexane). For the
other membranes, iso-propanol presented the lowest
uxes. In UP010, at 6 bar, it was almost seven times lower
than n-hexane ux and almost ve times lower in UH050,
at 1.5 bar. For UP010, n-hexane ux is higher than ethanol
and iso-propanol uxes. This fact does not occur for UP005
neither for UH050. This fact might be a considerable indication that not only is pore size playing an important role
in non-aqueous solvent ux, but also the interaction
between the solvent and membrane material. Whereas
UH050 has the largest pore size from all the membranes
tested, its material is slightly different (UP010 PES;
UH050 PESH, more hydrophilic).
According to Coutinho et al. [8], the two determining
factors for membrane efciency are size exclusion and
chemical interactions between the solvent and/or solute
and the membrane active layer. Studies by Yang et al. [9]
with non polar solvents using polymeric membranes also
showed that the transport mechanism through these was
not only function of solvent viscosity or diffusion through
membrane pores, afrming that there is some interaction

between the solvent and the membrane, which is determinant for permeate ux. These ndings corroborate with
data in the present study. Although the iso-propanol molecule is smaller than n-hexanes, the latter had greater
uxes.
The results for permeation of treatment solvent are also
corroborated by the contact angle measurements (Fig. 4).
The highest increases in contact angles were noticed for
membranes pre-treated and permeated with n-hexane.
Thus, the membrane afnity with non-polar molecules
increased and facilitated their mass transport through the
pores. However, although the hydrophobic character with
n-hexane treatment is greater than that obtained with
other solvents, the permeate uxes for this solvent were
not the highest, probably due to pore size inuence on permeation. The highest contact angle was observed for
UP010 after treatment and permeation with n-hexane.
This membrane also presented n-hexane uxes higher than
ethanol and iso-propanol. Therefore, an increase in UP010
afnity with n-hexane is again highlighted.
The interaction mechanisms between solvent and
membrane are thought to undergo a reorganisation of
the polymeric chains, resulting in larger pores and
correspondingly lower rejections of dissolved components
[16].
The polymer/solvent interactions can be expressed in
terms of their solubility parameters. The overall solubility
parameter (Hansen solubility parameter), d, can be calculated as a function of the individual contributions related
to dispersive forces, polar interactions (dipoledipole
forces) and hydrogen bonding, respectively dd, dp and dh:

d d2d d2p d2h

0:5

The three dimensional Hansen solubility parameter are

often used to predict a tendency regarding to the solubility
of solvents in polymeric materials. Values used for the
calculations are shown in Table 4. The more the solubility
parameters match not only the overall solubility, but also
all parameters, more likely it is for the polymer to be soluble on the solvent [22].
As proposed by Buonomenna et al. [21], to obtain an
indication of the mutual afnity and swelling behaviour

Fig. 4. Contact angles for pre-treatment solvent permeation assays.

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F.M. Penha et al. / European Polymer Journal 66 (2015) 492501

Table 4
Hansen solubility parameters, solubility difference parameters and interaction parameters calculated for solvent/PES interaction.
Solvent/polymer

Water
Ethanol
iso-Propanol
n-Hexane
PES
a

Hansen solubility parameters (MPa0.5)

dd

dp

dh

15.6
15.8
15.9
14.9
19.6

16.0
8.8
6.8
0.0
10.8

42.3
19.4
16.4
0.0
9.2

47.8
26.5
23.8
14.9
24.2

Vm (cm3 mol1)

v (dimensionless)

DdSP (dimensionless)

18.0
58.4
76.5
130.8

4.4
0.5
0.3
4.9

33.7
11.1
9.0
14.9

[22].

of the membrane in each solvent, the solubility parameter

difference (DdSP) can be calculated as follows:

DdSP

q
dd;P  dd;S 2 dp;P  dp;S 2 dh;P  dh;S 2

On the same way, Jansen et al. [22] reports an interaction parameter (v), to verify the matching between solvent
and polymer. This parameter can be calculated through the
equation:

v 0:34

Vm
dP  d2
RT

where Vm, R and T stand for molar volume, universal gas

constant and absolute temperature, respectively. In general, polymers may be soluble in the solvent if v 6 0.5.
These interactions between membrane and solvent may
also affect the pores wettability, altering membrane surface energy by clustering the hydrophilic and hydrophobic
sites. Results for solubility parameter difference are shown
in Table 4.
As demonstrated by the solubility parameter difference
and the interaction parameter, among all the solvents
tested, iso-propanol interacts the most with the polymer.
However, the polymer is not soluble in it. Therefore, this
alcohol may only cause the polymeric matrix to swell.
Since the permeate ux in ultraltration membranes
occurs via pore ow mechanism, and since swelling in porous membranes lead to a narrowing of pores [19,23], uxes
would tend to be lower for this solvent rather than others.
If, in addition to swelling, plasticisation also occurs, then
the effect on the ux is more unpredictable and depends
on the specic situation and membrane might even
become unstable. The effect of hydratation/solvation of
the pore walls also results in narrowing of the pores and
is driven by two factors: afnity between solvent and

membrane polymer, and the size of the solvent molecule

[21]. The afnity determines the strength of the interaction
and the solvation bonds, which in this case is higher for isopropanol and ethanol, rather than for n-hexane. As ethanol
molecule is smaller than iso-propanol, the number of ethanol molecules attracted to the pore wall would be higher,
probably implicating in higher pore wettability and higher
permeate uxes. The importance of these non-covalent
interactions depends only on the type of solvent. As
n-hexane presents lower interaction with the polymer
and higher sized molecule than the alcohols, its uxes
are hindered by membrane molar mass cut-off, which
explains the differences between uxes on the pair ethanol/n-hexane on UP005 and UP010; and on iso-propanol/
n-hexane on UH004 and UH050; since their main difference rely on pore size.
3.2. Inuence of conditioning time and solvent on n-hexane
permeation
Membrane permeabilities to n-hexane after solvent
pre-treatment are shown in Table 5. For ethanol pre-treatments, a relation can be noticed between exposure times
to the solvent and permeate uxes and permeability, i.e.
longest exposure to ethanol leads to higher n-hexane
uxes. For UH004, UP005 and UH050, conditionings by
immersion in ethanol for 2 h showed less expressive differences in sequential immersion in n-hexane for 2 or 12 h.
The same can be observed for these three membranes
when conditioned by 12 h immersion in ethanol: slight differences are noted between the complementary treatment
in 2 or 12 h in n-hexane. Therefore, it can be inferred that,
for these membranes, it is the time exposure to ethanol
more than the exposure to n-hexane that determines the
permeate uxes and permeability to n-hexane.

Table 5
Permeability of each tested membrane to n-hexane after pre-treatments 58, with ethanol and iso-propanol.
Permeability (L h1 m2 bar1)

Pre-treatment

UH004

UP005

UP010

T5
T6
T7
T8

2 h ethanol + 2 h n-hexane
2 h ethanol + 12 h n-hexane
12 h ethanol + 2 h n-hexane
12 h ethanol + 12 h n-hexane

4.5 0.4
7.7 0.3
14.3 0.6
16.4 0.5

4.5 0.3
5.8 0.5
13.3 1.2
18.3 1.1

21.8 1.5
52.0 2.5
68.7 3.7
117.2 5.8

UH050
15.2 1.3
33.4 1.4
189.6 5.2
272.3 6.5

T5
T6
T7
T8

2 h iso + 2 h n-hexane
2 h iso + 12 h n-hexane
12 h iso + 2 h n-hexane
12 h iso + 12 h n-hexane

14.0 0.9
11.2 1.0
14.4 1.1
29.4 1.7

13.1 1.2
11.3 0.8
8.7 0.7
11.0 0.9

49.3 4.2
69.0 2.8
104.7 7.8
29.4 2.2

5696.4 8.5
3466.5 12.7
5128.9 25.2
4817.6 22.2

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F.M. Penha et al. / European Polymer Journal 66 (2015) 492501

Nevertheless, for UP010 membrane, the differences

are only evident for the mildest and the harsh treatments
in ethanol (Treatment 5: 2 h in ethanol + 2 h in n-hexane,
and Treatment 8: 12 h in ethanol + 12 h in n-hexane).
Permeability to n-hexane after Treatment 8 is around 6
times that obtained after Treatment 5. Here, intermediate treatments yielded permeabilities with very close
values, in comparison to the other ones. According to
Darvishmanesh et al. [24], this behaviour deviation can
be possibly due to occurrence of swelling or shrinking
of the polymeric matrix, which promotes changes on
membranes performance. On the other hand, UP005
and UP010 have the same polymer constitution and that
does not occur in UP005, which again proves that the
solvent permeation through polymeric membranes is a
function of solvent-membrane interactions and size
exclusion.
In pre-treatments with iso-propanol, it can be observed
that, in general, there are no relations between exposure
times to the solvent and the permeate uxes or permeability. Only for UH004, the harsh conditioning (Treatment 8)
promotes the higher uxes and permeability. For UP005
and UH050, better results for permeability were obtained
in Treatment 5, which in runs with UH050 overcomes the
lowest found value (Treatment 6) in 64%.
For UP010 membrane, four different curves, for each
pre-treatment with iso-propanol, can be observed.
However, the order of these curves has no correlation with
exposure time to the solvent. The highest uxes and
permeabilities were obtained in Treatment 7, whilst the
lowest was obtained with Treatment 8.
The contact angle measurements (Fig. 5) corroborate
with uxes and permeabilities found for all membranes
pre-treated in ethanol. Except for UP005, in which the
highest angle after treatment was obtained with
Treatment 7, whilst the highest permeability is related to
Treatment 8. For pre-treatments with iso-propanol, no
correlation was found between the increase in contact
angles and the permeate uxes or permeability.
According to Firman et al. [10], permeability of non-polar
solvents in polymeric membranes is strongly related to
the hydrophilic/hydrophobic character of the membrane
and the solvent used. Therefore, the hydrophobicity of
the active layer would determine, to great extent, the
permeate ux through the membrane. Nevertheless, the
variation found on permeabilities of tested membranes,
especially with iso-propanol conditionings, can be
explained based on solvent-polymer interactions plus the
pore size inuence. The immersion of polymeric membranes in alcohols can promote the clustering of hydrophilic and hydrophobic sites at membranes active layer with
slightly increase on the pore size [5].
The clustering effect is responsible for changing or
reducing the hydrophilic character of the commercial polymeric membranes designed for aqueous systems, turning
them into permeable to organic solvents. Therefore, clustering is not only expected, but also desired in all cases.
Although the interactions between solvent and polymer
may result in plasticisation, swelling and dissolution of the
active layer, in porous membranes, swelling of the polymeric matrix can cause the narrowing of pores and

Fig. 5. Contact angles for the membranes pre-treated with ethanol (a)
and iso-propanol and (b) after n-hexane permeation assays.

consequently increase the retention, decreasing the

permeability, as described by Buonomenna et al. [21].
The discrepancies observed between contact angles and
n-hexane uxes phenomena can be an indicative of swelling and plasticisation, corroborated by the results of solubility and interaction parameters. In UH050, for example,
uxes are higher in pre-treatments with iso-propanol than
with ethanol. However, contact angle measurements indicate higher angles, i.e. stronger hydrophobic character, for
ethanol. Again, if swelling and plasticisation takes place,
the effect on the ux is not predictable and the membrane
can even become unstable.
In UH050, pre-treatments T5-T8 with iso-propanol,
which led to much higher uxes in comparison to all other
membranes, are probably inuenced by the occurrence of
swelling and plasticisation that caused unexpected uxes.
Membranes that presented contradictory uxes and contact angles are probably under inuence of swelling
low uxes and high angles, e.g. UP010 and UH050 in T6
with ethanol.
Micrographs obtained by FESEM analysis are shown in
Fig. 6, for new UH050 membranes and pre-treated with
the harsh conditioning (Treatment 8). Figure shows typical
characteristics of ultraltration membranes, as the presence of macrovoids at the membrane sub layer, which

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499

Fig. 6. FESEM micrographs of UH050, new membrane and after Treatment 8 with ethanol.

helps reducing permeation resistance [25]. Only a slight

difference in thickness can be noticed after n-hexane permeation, probably due to membrane compaction. Yet,
these differences do not present expressive inuence in
membrane performance.
Through FTIR analysis it was possible to verify the presence of bands that can be related to functional groups and
enables a qualitative identication of polymeric blends. As
the base polymer is the same for all membranes (PES), the
obtained spectra for the membranes without conditioning
are alike. The changes in transmittance also occurred in the
same bands for all tested membranes, although with various intensities. Therefore, only spectra for UP010 before
and after the pre-treatments are shown in Fig. 7.
Sulfonic group presence can be observed in the spectra
of the membranes prior to the pre-treatment through
bands between 1000 and 1500 cm1, as a strong band at
1150 cm1 related to the symmetric O@S@O stretching
vibrations. Also, bands around 1070, 1050 and 1020 cm1
can be related to the stretching of S@O bonds and to the
stretching of CAOAC vibrations, since both groups are present in the base polymer [2630]. Tang et al. [31] also
reported in their studies, peaks around 1150 cm1 referring to sulfones. According to Lobo and Bonilla [29], in

polyethersulfones, asymmetric vibrations of SO2 group

appear divided into bands 1324, 1299 and 1289 cm1.
These conrm the membrane composition informed by
the manufacturer (PES). However, the increase on the
transmittance of such bands, with consequently reduction
of the peaks, indicates possible degradations or rearrangement of the polymer chains on the active layer. Changes or
extinctions on the bands around 1100 to 1500 cm1 may
be related to the occurrence of swelling [32].
In the new membrane, peaks around 1240 cm1, representative of aromatic ethers band, i.e. asymmetric
AC6H4AOAC6H4 vibrations [26,29] are present. Prominent
bands of the functional group @CAH of the aromatic ring
in the region of 900690 cm1 are related to out-of-plane
bending [26,30]. Bands around 1585 cm1 with small
peaks at 1605 cm1, a peak at 1488 cm1 and 1169 cm1
are also present and are indicative of the aromatic ring
[29]. After the pre-treatments and permeations, an
increase in transmittance was observed for these peaks,
which could possibly indicate that conditioning may be
promoting leaching or rearrangement of such groups on
the membrane surface.
Bands located around 2880 and 2935 cm1 are related
to sp3 CAH stretching vibrations, i.e. aliphatic groups.

Fig. 7. FTIR spectra for UP010 membrane before and after the pre-treatments.

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F.M. Penha et al. / European Polymer Journal 66 (2015) 492501

These groups are not present in the base polymer, and their
intensity decrease after pre-treatment. Thus, they suggest
the presence of preservative agents. Belfer et al. [33] also
found these peaks in Millipore PES membranes and
concluded that they were related to preservatives existing
on the new membranes, as the peaks disappeared after
several washing procedures, with water and ethanol.
Vibrational bands around 3300 cm1 were also expressive in new membranes, with drastic reductions after pretreatments. According to Hajatdoost et al. [32], this region
is assigned to the stretching of OH groups and hydrogen
bonds, and is related to membranes water absorption.
Socrates [30] afrms that polyethersulfone may exist in
equilibrium with up to 2% of water, thus, bands due to
water will normally also be observed in the spectra of this
polymer. Therefore, after conditioning, the extinction of
these peaks can be noticed, which indicates the removal
of membranes humidity, making it more hydrophobic.
These results corroborate with contact angle increases
after conditioning, as seen in Figs. 4 and 5.
4. Conclusions
The membrane pre-treatment and permeation with
various solvents suggests that the permeability of the polymer depends not only on the pore size, but also on the
interaction of solvent and polymer. The lowest uxes and
permeabilities were obtained with iso-propanol permeations. On the other hand, ethanol uxes were high for
UP005 (ethanol uxes were higher than water uxes),
UP010 and UH050. Hence, the tested membranes present
potential for use with non-aqueous solvents with relatively
brief pre-treatments.
The study of the inuence of exposure time and solvent
on pre-treatment of polymeric commercial ultraltration
membranes shows the possibility of increasing permeate
uxes through the increase of the immersion times in a
combination of different solvents. Each membrane exhibits
better permeability results with a different pre-treatment,
which are, only in some cases, corroborated by the increase
in contact angles. The results evidenced that the ux
increase is strongly inuenced by the time of exposure to
ethanol than by the time of exposure to n-hexane. It can
be stated that the pre-treatment increased the contact
angle for all the membranes tested, consequently increasing hydrophobicity. Moreover, characterisation showed
no substantial changes in membrane structure
morphology.
Furthermore, given the correlation of permeability and
contact angles only in a few cases, it is believed that other
variables affect the conditioning efciency, such as polymeric constitution, molar mass cut-off, and the interactions between solvent and membrane. Therefore, the
efciency of the process would be a balance of all these
variables.
Acknowledgements
Authors are grateful to CAPES and CNPq for nancial
support, Central Laboratory for Electronic Microscopy

(LCME/UFSC) for the FESEM analyses, and Laboratory of

Process Control and Polymers (LCP/UFSC) for contact angle
measurements.

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