Progress in Polymer Science 34 (2009) 969–981

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Progress in Polymer Science

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Crosslinked poly(vinyl alcohol) membranes

Brian Bolto ∗ , Thuy Tran 1 , Manh Hoang 1 , Zongli Xie 1
CSIRO Materials Science and Engineering, Private Bag 33, Clayton South MDC, Victoria 3169, Australia

a r t i c l e i n f o a b s t r a c t

Article history: The inherent hydrophilicity of poly(vinyl alcohol) (PVA) makes it an attractive polymer for
Received 13 April 2009 water treatment applications based on membranes. Thermal and chemical resistance and a
Received in revised form 19 May 2009
high anti-fouling potential are accompanied by high water permeability. The large swelling
Accepted 29 May 2009
capacity requires that the PVA be adequately crosslinked to ensure that the contaminants
Available online 7 June 2009
in water can be retained, and that compaction under pressure can be minimised. There is a
challenge to achieve this and still obtain economical permeate fluxes.
Keywords:
Poly(vinyl alcohol) The literature on crosslinking of PVA is reviewed. Many reagents have been explored. Glu-
Crosslinking agents taraldehyde is a more effective crosslinking agent than formaldehyde or glycidyl acrylate,
Reverse osmosis which in turn gives a less swollen product than that obtained by increasing the crystallinity
Pervaporation by heating. Toluene diisocyanate and acrolien give similar results in the preparation of
Ultrafiltration reverse osmosis membranes, but at an extremely high applied pressure. Crosslinking with
Microfiltration maleic anhydride/vinyl methyl ether copolymers gives as good a result, but at even higher
pressure. Thus the high swelling of PVA can be overcome by crosslinking reactions, but
with the consumption of some of the OH groups responsible for the hydrophilicity. What
is really needed is network formation that provides a tight restraining without serious
loss of hydrophilic behaviour. Similar membranes are used for the separation of organic
compounds from one another or from water by pervaporation, where the vapor of one com-
ponent is selectively transferred through the membrane on the basis of polarity differences.
Here PVA membranes would be especially suited to dehydration procedures.
The high swelling behaviour can be countered also by forming the active PVA component
inside the pores of a microporous membrane. Crosslinked PVA inside such membranes
has its swelling suppressed, and can function as salt removal membranes. By only coating
the pore walls, leaving some porosity, microfiltration or ultrafiltration membranes can be
prepared. In both situations a degree of grafting to the host membrane would be beneficial.

Crown Copyright © 2009 Published by Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 970
2. Crosslinking methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 970
2.1. Freeze–thaw inducement of crystallisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 970
2.2. Heat treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 970
2.3. Acid-catalysed dehydration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 971
2.4. Irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 971

∗ Corresponding author. Tel.: +61 3 9545 2037; fax: +61 3 9545 1128.
E-mail addresses: brian.bolto@csiro.au (B. Bolto), thuy.tran@csiro.au (T. Tran), manh.hoang@csiro.au (M. Hoang), zongli.xie@csiro.au (Z. Xie).
1
Fax: +61 3 9545 1128.

0079-6700/$ – see front matter. Crown Copyright © 2009 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2009.05.003
970 B. Bolto et al. / Progress in Polymer Science 34 (2009) 969–981

2.5. Radical production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 971

2.6. Formaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 971
2.7. Glutaraldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 972
2.8. Other aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 973
2.9. Di-, tri- and polycarboxylic acids, anhydrides or acid chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 974
2.10. Alkoxysilanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 975
2.11. Other chemical crosslinking agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 976
3. Grafting of PVA onto support membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 976
4. Commercial PVA membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 978
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 978

1. Introduction 2. Crosslinking methods

Crosslinked poly(vinyl alcohol) or PVA has good chem- 2.1. Freeze–thaw inducement of crystallisation
ical, thermal and mechanical stability. It is appropriate
for pressure-driven membranes designed for a variety of PVA can be physically crosslinked by methods that intro-
water treatment applications, such as microfiltration (MF) duce crystalline regions that act as crosslinks [12]. Cycling
for removing particulate material, microbial cell residues at −20◦ /+25 ◦ C for up to 10 times yields membranes that
and turbidity, ultrafiltration (UF) for taking out large contain from 5.2 to 11.6% of crystalline PVA on a swollen
organic molecules, nanofiltration (NF) for small organic basis. Size exclusion effects are observed with theophylline
molecules removal and softening, and reverse osmosis (RO) (MW 180 Da) and a dextran derivative (MW 4400 Da).
for desalination. The highly polar nature of PVA minimizes Although there was no apparent change in properties after
fouling in such applications, as it is well established that several months, the physical crosslinks were not as strong
non-polar surfaces encourage adsorption of water con- or as stable as chemical ones. The water content has been
taminants because of hydrophobic interactions, whether shown to decrease with increasing crystallinity [13].
natural organic compounds such as humic and fulvic acids
[1] or microbial matter [2]. 2.2. Heat treatment
Because of their oleophobic properties, PVA membranes
are useful in wastewater treatment. They are also used for Fully hydrolysed PVA samples of MW 86 and 115 kDa
product recovery and for the separation of organic com- have been heated over the range of 120–175 ◦ C for
pounds from one another or from water by pervaporation 30–80 min and the products tested as RO membranes [14].
(PV), where the vapor of one component is selectively Water and salt permeabilities decreased abruptly on heat
transferred through the membrane on the basis of polar- treatment in operations at 6.7 MPa, with the salt result
ity, not the volatility difference. PVA membranes would be decreasing greater than that for water, indicating that
especially suited to dehydration procedures. the membrane structure became tighter on more intense
The membranes cover a wide range of porosities and heating. Higher temperatures are known to produce unsat-
permeation properties, reflecting a spectrum of degrees uration, chain scission and chemically bonded crosslinking.
of crosslinking, from the minimum necessary to lessen The water contents of the membranes were not reported.
swelling in the more porous membranes to the highly Earlier work showed that PVA membranes baked at 145 ◦ C
crosslinked PVA necessary for rejection of small inorganic gave 22 and 26% salt rejection at 4 and 5.2 MPa respectively
ions in tighter, non-porous RO membranes. However, the [15].
more swollen membranes can become compacted when Interpolymer anionic composite RO membranes have
high pressures are applied, so that flux through the mem- been made from PVA (MW 75 kDa) and poly(styrene sul-
brane is markedly reduced over time. phonic acid) or PSSA (MW 123 kDa) by heat treating cast
Because of its hydrophilic nature, PVA must be modified membranes at 120 ◦ C for 2 h [16]. The optimum ratio of
to minimise swelling in water when fabricated for aqueous PVA to PSSA was 1.5, when the salt rejection was 93% at an
applications. A burgeoning literature exists on this aspect applied pressure of 8 MPa. Infrared studies showed that a
[3–5]. The stability of crosslinked PVA in highly acidic or dehydration reaction produced –O–SO2 – bridges between
highly alkaline environments has been demonstrated [6]. the molecules. Water fluxes were 9–28 L/m2 h, decreasing
While the literature on applications as membranes or sup- with longer heat treatment times and higher PVA con-
port material in water treatment is spasmodic [7], there tents.
has been a continuing effort in the biotechnology area Heat treatment of PVA (99% hydrolysed and MW 75 kDa)
to use PVA membranes for protein recovery [8–10]. As at temperatures up to 160 ◦ C has shown that hygroscop-
well, PVA gels have been studied extensively as bioma- icity diminishes and the rate of water vapor transmission
terials for artificial kidney and pancreas, glucose sensors, decreases, as does the permeability [17]. This was ascribed
immuno-isolation membranes, artificial cartilage, contact to a change in crystallinity rather than the introduction of
lenses and drug delivery systems [11]. Methods of improv- covalent crosslinks.
ing the mechanical integrity of PVA include freezing, heat To avoid the possible leaching of unreacted crosslinker,
treatment, irradiation, and chemical crosslinking. studies have been made of UF membranes made from PVA
 B. Bolto et al. / Progress in Polymer Science 34 (2009) 969–981
crosslinked by heat treatment at 100 ◦ C for 1 h [11]. Mem-
brane selectivities and fouling by protein were compared
with polyether sulphone (PES) and regenerated cellulose
membranes. The PVA membrane was more resistant to
fouling and was considered a viable replacement for the
other membranes.
The flux for pure water passage through porous UF
membranes made from heat treated PVA have been
compared with those prepared with a chemical crosslink-
ing agent in the form of glutaraldehyde [18]. Solutions
10% in PVA (99% hydrolysed and MW 77 kDa) and 0.5%
in poly(ethylene glycol) were cast into membranes and
immersed immediately into an acetone coagulation bath.
The dried membranes were kept in a 120 ◦ C oven for dif-
ferent times, giving products with increasing crystallinity
longer heat treatment times: 18.7% after 1 h, 27.9% after 2 h
and 48.9% after 3 h. The porosity decreased from 0.48 to
0.39. For the membrane of highest crystallinity the water
flux decreased from 0.8 to 0.4 L/m2 h after 3 h operation
at 200 kPa, versus 0.7–0.4 L/m2 h for the glutaraldehyde-
crosslinked membrane. This was ascribed to swelling of the
membrane in water, then further deformation because of
the transmembrane pressure, causing irreversible changes
to the morphology. The heat-treated membranes were
claimed to have better anti-compression properties than
the crosslinked membranes because of the supporting
function of the crystal regions versus the fragile acetal
bonds at the points of crosslinking. In the wet state the
tensile strength and strain ratio both increase for the heat-
treated membranes, but both decrease for the crosslinked
membranes. For the former membranes the elasticity was
greater also.
2.3. Acid-catalysed dehydration
Coating PES or polytetrafluoroethylene support mem-
branes with a solution of PVA and sulphuric acid, heating
to 150 ◦ C, then coating with a solution of poly(acrylic acid)
and sulphuric acid and heating to 160 ◦ C, produces a com-
posite membrane that is capable of high salt rejections, but
relatively low fluxes at a pressure of 0.4 MPa [19], as quoted
by Immelman et al. [4].
A PVA solution (86–89% hydrolysed and MW 72 kDa)
containing a dehydration catalyst in the form of con-
centrated sulphuric acid has been deposited on an
asymmetrical PES support membrane, then heated at
100–125 ◦ C for 10–30 min to effect insolubilisation [4].
Ether crosslinks were formed between the PVA chains, but
water elimination within the chain could produce olefinic
double bonds, a reaction favoured by higher temperatures
and indicated by discolourisation. The products were tested
on 2000 mg/L NaCl at 2 MPa and gave salt rejections of up
to 70–85% at a flux of 29–33 L/m2 h for the tightest mem-
brane prepared under more forcing conditions, versus 55%
rejected at 63 L/m2 h for one with a more open network that
was prepared under milder conditions.
2.4. Irradiation
Cast PVA films have been irradiated by a 60 Co irradiation
unit at doses of 0.5–40 Mrad, at a dose rate of 153 krad/h
971
[20]. The swelling ratio (swollen/dry) of the samples in
water was lowered from 5.7 to 2.6 by the treatment. As
RO membranes at 6.7 MPa, the water permeability and salt
rejection were comparable to those of untreated PVA, but
although the water permeability was considerably higher
than obtained with chemically crosslinked PVA, the salt
rejection was much lower at 20–50%. The radiation prod-
ucts hence had a looser, more open structure. Their water
contents were over 10 times that of chemically crosslinked
PVA.
2.5. Radical production
Persulphate treatment of PVA in the form of K2 S2 O8 has
been used to insolubilise the polymer [21]. This strongly
oxidising radical producer promotes coupling between
polymer radicals, leading to a crosslinked structure. The NF
membrane formed had rejections of up to 80% in treating
1000 mg/L MgSO4 . Manipulating the variables can produce
membranes with RO properties, as when aqueous solu-
tions of PVA and K2 S2 O8 are deposited on PES support
membranes [22]. Crosslinking was completed by heating
at 60–100 ◦ C. Operation was possible at 2 MPa, when the
salt rejection was 45% at 42 L/m2 h.
2.6. Formaldehyde
PVA (99% hydrolysed) has been used to prepare
membranes that have been crosslinked with excess
formaldehyde in a bath at room temperature for 20 h, then
heat treated [23]. The degree of formalisation was esti-
mated to be not greater than 50% because of the difficulty of
formaldehyde penetrating crystallites formed during dry-
ing. Heat treatment at temperatures up to 200 ◦ C for 10 min
before the formalising step decreased the water absorption
and water permeability of the membrane. With no prior
heating, formalising at 50 ◦ C for 2 h gave membranes with
93–97% salt rejection in RO tests at 4 MPa. Similar experi-
ments were carried out later to give a membrane that had
90% salt rejection from simulated seawater at 10 MPa [24].
PVA of MWs 45 and 90 kDa have been made from films
placed in a precipitating bath of various salts for an hour,
then 2–3 days in a crosslinking bath of strongly acidic 30%
formaldehyde [25]. In RO tests at 5 MPa, rejections of mono-
valent salts were 25–28% at a flux of 35–54 L/m2 h. For
divalent cations the figures were 23–27% at 41–69 L/m2 h,
and for sulphates 69–70% at 42–70 L/m2 h. The results sug-
gest that the membranes are negatively charged. This could
arise from incorporation of sulphonic acid groups from the
sulphuric acid catalyst. Salt rejections of 85% are reported
for similar membranes operated at 4 MPa [26].
PVA crosslinked with formaldehyde/HCl is useful in
PV of aqueous acetic acid for dehydration purposes
[27]. The membranes produced had greater fluxes but
lower selectivities than those formed by crosslinking with
glutaraldehyde, which was ascribed to more efficient
crosslinking in the case of glutaraldehyde. The degree of
formaldehyde reaction with PVA (99.5% hydrolysed and
MW 77 kDa) has been studied in regard to PV behaviour in
the dehydration of benzene [28]. It was postulated that the
reaction could also result in intramolecular acetal forma-
972 B. Bolto et al. / Progress in Polymer Science 34 (2009) 969–981
tion, producing six-membered rings rather than inter-chain
crosslinking, although no evidence was presented to sub-
stantiate this. With fewer OH groups present after reaction
with formaldehyde there was a decrease in hydrophilicity
and in the swelling of the membrane. PVA (MW 31–50 kDa,
98–99% hydrolysed) has been crosslinked with varying
amounts of formaldehyde and the silver nitrate complex
of the membrane produced tested for the separation of
benzene and cyclohexane [29]. Blend membranes of PVA
(MW 125 kDa) and chitosan, with the PVA content rang-
ing from 20 to 60%, have been made by solution casting
and crosslinking with a urea formaldehyde/sulphuric acid
mixture [30]. The mixture was made up of 2.5 wt% urea,
2.2 wt% formaldehyde and 2.5 wt% sulphuric acid contain-
ing 50 wt% aqueous ethanol. Highest permeability was
obtained with the 60% PVA product, and the highest selec-
tivity with the 20% PVA membrane. The membranes were
tested for PV dehydration of isopropanol and tetrahydrofu-
ran.
2.7. Glutaraldehyde
PVA (88% hydrolysed, very high MW) has been used to
make a matrix to bind micro (5–10 ␮m) ion-exchange resin
particles into beads of conventional size (300–1200 ␮m),
with hydrochloric acid as the catalyst and enough glu-
taraldehyde or GA, OHC–(CH2 )3 –CHO, to react with 40% of
the OH groups, or 0.1 mole of GA per mole of PVA repeat unit
[31]. It should be noted that this is only approximate as GA is
susceptible to self condensation via an aldol condensation,
especially at high pH [32].
The crosslinked matrix was readily permeable to both
water and salts. Similarly crosslinked PVA has since been
reported for making membranes for studying diffusive
properties and selective separation of flavonoids [33,34].
Membranes for PV of ethanol/water mixtures are
reported, made from PVA (98% hydrolysed and MW 75 kDa)
and GA, with varying degrees of crosslinking [35]. Swelling
in water decreased with increased crosslinking, as did the
selectivity and permeability of the membrane, but swelling
in ethanol was not altered.
Lightly crosslinked PVA (99+% hydrolysed and MW
50 kDa) has been deposited on asymmetric regenerated
cellulose UF membranes, having a molecular weight cut
off (MWCO) of 10 kDa, by spin coating a PVA/GA mixture
onto them, followed by completion of the crosslinking reac-
tion [10]. The reaction could well include the OH groups
on the cellulose substrate, to give covalent binding of the
PVA to the support membrane. The extent of crosslinking
was from 0.005 to 0.01 mole of GA per mole of PVA repeat
unit. The lower level gave a layer that was too compress-
ible for thickness measurement. The effect of doubling the
amount of crosslinking was not significant in fouling and
flux tests with bovine serum albumin (BSA), a result that
was attributed to a limiting polymer volume under hydro-
static pressure. Irreversible fouling was reduced markedly
for membranes with a coating thickness of 3 ␮m or more
under hydrostatic pressure. Any protein layer on the surface
could be removed readily. Pure water flows were reduced
as the thickness of the PVA layer was increased, with rel-
ative water fluxes varying from 97 to 47% as the coating
was increased from 0.8 to 5.2 ␮m, which was ascribed to
some pore blocking by polymer chains. In UF of 1 wt% BSA
of MW 66.5 kDa there was 100% retention of the protein at
0.34 MPa pressure.
PVA (99% hydrolysed and MW 50 kDa) was crosslinked
with sufficient GA to react with 0.003 mole of the OH
groups, and then further reacted under a GA concentration
gradient to produce an asymmetry in crosslink density [36].
Excellent selectivities were obtained for creatinine (MW
113 Da) over immunoglobulin (150 kDa) relative to results
with a homogeneous membrane of equivalent crosslinking
to the modified surface network.
Lightly crosslinked PVA was reacted with GA in the
pores of mixed cellulose ester MF or polysulphone UF
membranes, the amount of reagent again corresponding
to only 0.003 mole per mole of PVA repeat unit [37]. The
gel-impregnated membranes had potential application in
biohybrid artificial organs. The most practical configuration
was the hollow fibre mode because of nutrient transport
advantages.
UF membranes have been made from PVA (>98% hydrol-
ysed and MW 72 kDa) crosslinked with GA in a 1:1 mole
ratio (enough to react just one of the aldehyde groups with
the OH groups), and a lipase enzyme covalently bonded
to the surface through the pendant–CHO group [38]. Effi-
cient immobilisation of the enzyme within the pores was
claimed in testing of the hydrolysis of p-nitrophenyl lau-
rate, with the filtration mode avoiding product inhibition
of the enzyme.
Macroporous PVA (87.7% hydrolysed and MW 67 kDa)
crosslinked with GA has been made by carrying out the
crosslinking reaction under acidic conditions at a sub-
zero temperature of −18 ◦ C overnight [39]. The product,
in monolithic form, had interconnected macropores up to
150 ␮m in size, with microporosity of the gel walls. The
material was elastic and sponge-like, with the pore size
decreasing with increase in the concentration of polymer
in the reaction mixture and with decrease in the degree of
crosslinking, which varied from 0.05 to 1.0% (w/v) in a reac-
tion mixture that was 5% (w/v) PVA, giving levels of 2–40%
crosslinking.
The development of high performance UF membranes
centred on PVA is based on an electrospun nanofibrous
(150–300 nm diameter) scaffold on which is deposited a
very thin (∼1.8 ␮m) layer of PVA, both crosslinked with GA
[40,41]. The degree of hydrolysis and MW were optimised
for best performance and mechanical durability of the scaf-
fold. The range explored was 88–89, 96, 98 and 98–99%
hydrolysed, with MWs of 13–23, 78 and 85–124 kDa. The
96% hydrolysed PVA of highest MW gave the best result.
After crosslinking there was a small volume shrinkage of
<5%, but the porosity was relatively high at >80%. Crosslink-
ing of the added layer of PVA with GA, which would have
bonded it to the primary PVA, was varied and the flux and
rejection characteristics determined. For UF of an oil/water
emulsion containing soybean oil (1350 mg/L), a GA/PVA
repeat unit ratio of above 0.06 was needed to achieve a
high rejection (>99.5%), when the permeate flux was then
130 L/m2 h, whereas for the 90% rejection obtained with
a ratio of 0.02 the flux was 360 L/m2 h. Thus the size of
the mesh of hydrophilic chains connected by crosslink-
 B. Bolto et al. / Progress in Polymer Science 34 (2009) 969–981
ing points can be controlled by the degree of crosslinking,
with highly crosslinked membrane layers giving much
decreased flux rates. The flux obtained with the optimum
membrane was superior to that for a commercial composite
UF membrane. Even better results should be possible with
membranes having a thinner or more hydrophilic coating
layer.
Similar UF membranes have been made from part
acetalised PVA to control their hydrophilicity [42]. The
PVA (99% hydrolysed and MW 1.8 MDa) was reacted with
acetaldehyde under acidic conditions to produce a range
of products having 49–57% acetal groups. The polymers
were cast into membranes from dimethylacetamide solu-
tion. The wet membranes were then crosslinked with GA
in acid at room temperature. The modified PVA mem-
branes were hydrophilic and in the UF of BSA they had
substantially reduced fouling compared to commercial
membranes. Membrane properties were dependant on the
degree of acetalisation, the presence of poly(ethylene gly-
col) in the casting solution, and other casting conditions.
The higher the deacetalisation the more hydrophilic the
membrane, giving a better level of water permeation and
good retention of BSA, and with less fouling.
A composite membrane approach is a three-tiered com-
posite with a non-woven microporous support, electrospun
nanofibrous PVA/GA substrate as the middle layer and then
a PVA/GA thin coating which contained surface-oxidised
multiwalled carbon nanotubes (CNTs) [43]. The CNTs had
an outer diameter of 20–40 nm, an inner diameter of
5–10 nm and a length of 5–15 ␮m. This unique filtration
medium gave a high flux rate of up to 330 L/m2 h at a feed
pressure of 0.68 MPa in the UF of an oil/water emulsion,
with a rejection of 99.8% and no appreciable fouling after
operation for 1 month. An increase in the CNTs in the coat-
ing layer enhanced the flux rate, which was ascribed to the
presence of more effective hydrophilic nanochannels for
water transport through the composite membrane.
PVA/GA membranes containing CNTs are reported,
using ␤-cyclodextrin as a dispersant [44]. They showed
improved permeate flux and separation efficiency in the
PV of benzene/cyclohexane mixtures, as well as better
mechanical properties, than unfilled membranes. The work
follows similar studies where graphite flakes or carbon
molecular sieves were introduced into the membrane
to give analogous improvements in both flux and selec-
tivity [45–47]. With crystalline flake graphite particles
of 1–15 ␮m size as the filler, there was a simultaneous
increase in both permeation flux (4-fold) and separation
factor (6-fold) [48]. The results were attributed to a higher
free volume and more relaxed polymer chain packing
which could reduce the mass transfer resistance and facil-
itate permeation of benzene. However, excessive filling
could inhibit permeation.
Membranes for PV of ethanol/water mixtures have
been made from similarly crosslinked PVA (99% hydrol-
ysed and MW 75 kDa), but the amount of GA used was
not specified [49]. Also present in the membrane was ␤-
cyclodextrin oligomer crosslinked with epichlorohydrin to
enhance water permeability and water selectivity (lightly
crosslinked, 1 h reaction time). More crosslinked versions
gave increased ethanol permeability as well (8 h reaction
973
time). The crosslinking reaction was hindered by the pres-
ence of the ␤-cyclodextrin oligomer, which competed for
the crosslinker. The introduction of charged groups into
a GA-crosslinked PVA membrane increases the selectivity,
but decreases the flux [50].
Varying levels of crosslinking of PVA (94% hydrolysed
and MW 66 kDa) and its effect on PV of acetic acid/water
mixtures have been tested [51]. Acetone was used as a
non-solvent for the PVA to prevent it dissolving during the
reaction. A minimal amount of 5 vol.% of the GA crosslinker
gave a water insoluble product, with 10 vol.% giving the
lowest swelling and slowest flux, the separation factor
decreasing steadily to the highest level used, 30 vol.%. The
best separation was hence at 5 vol.% when reasonable fluxes
were obtained.
PV membranes have been made from PVA (60 wt%)
and poly(allylamine hydrochloride) (35 wt%), crosslinked
with GA (5 wt%) and shown to give excellent perfor-
mance in the dehydration of acetone [52]. The dehydration
of ethanol/water mixtures has been explored with PVA
crosslinked with GA [53]. The cast membranes had two dis-
tinct surfaces, the air-side and glass-side, and performance
was very dependant on which surface faced the feed. Sur-
face reconstruction of the membrane did not occur with
the glass-side format during PV, so there was no change in
water selectivity. The contact angle for the air-side format
decreased with contact time against the feed.
Catalytic ceramic disks containing H3 PW12 O40 in the
pores have been spin-coated with PVA (MW 75 kDa),
crosslinked with GA to an undisclosed degree [54]. There
was good catalytic stability for the dehydration of butane-
diol to form tetrahydrofuran, with coupled PV to remove
water.
A summary of relevant published information on PVA
crosslinked with GA and its applications is given in Table 1.
2.8. Other aldehydes
Crosslinking PVA with acrolein, CH2 CH–CHO, in the
form of its bisulphite salt, with the idea of adding the –OH
groups across the active double bond of acrolein, has been
carried out in the presence of sulphuric acid, followed by
curing at 135 ◦ C for 15 min after coating the mixture on a
polysulphone support [24]. In RO experiments, salt rejec-
tions of 96.5–96.7% from synthetic seawater were achieved
at 10 MPa. A drawback was the compaction of the mem-
brane that was observed at this high operating pressure.
Experiments on PVA membranes made for removal of
phenol and other components have shown that greater
rejection is obtained for membranes crosslinked with GA
Table 1
PVA membranes crosslinked with GA.
Moles GA per OH Application Reference
1 Pendant enzyme [38]
0.1 Resin matrix [31]
0.1 PV membrane [51]
0.005–0.1 Chromatography [39]
0.06 UF membrane [41]
0.005–0.01 UF membrane [10]
0.003 Biohybrids [37]
974 B. Bolto et al. / Progress in Polymer Science 34 (2009) 969–981
than those prepared with glyoxal or adipic aldehyde [55].
GA has been compared with other aldehydes as crosslink-
ers in the preparation of thin-film composite membranes
made by coating a polysulphone UF membrane (MW cut
off >15 kDa) with PVA [56]. The PVA (98% hydrolysed and
MWs ranging from 2 to 65 kDa) on the coated membrane
was dried and contacted with various crosslinking agents,
then heat treated. In RO experiments with 2000 mg/L NaCl
at 1.7 MPa the salt rejection was as high as 95% for GA, but
only 55% for methacrolein crosslinking, with performance
being dependant on the solvent used for the crosslinking
reaction. Other experiments showed salt rejections of 46%
for glyoxal, 67% for formaldehyde and 90% for GA. Diffu-
sion studies of PVA crosslinked with terephthaldehyde are
reported [57,58]. A similarly crosslinked PVA has been used
to immobilise enzymes [59].
2.9. Di-, tri- and polycarboxylic acids, anhydrides or acid
chlorides
A study has been made of crosslinking PVA with the
dicarboxylic acids oxalic, malonic and citric acids with
sulphuric acid as catalyst at 90–120 ◦ C [26]. Thin film com-
posite membranes have been made from polysulphone
membranes, with the PVA as the top layer. Increasing
temperatures gave greater salt rejections, which were sig-
nificantly affected by the degree of crosslinking. Increasing
the number of carbon atoms in the crosslinker increased
the water flux, but the salt rejection was decreased. The
best results were obtained with oxalic acid, with about 95%
salt rejection at a pressure of 4 MPa, but the water flux
was low. Other work on dibasic acids was reviewed, listing
membranes with salt rejections of 74–85%.
Asymmetric membranes using PVA (98% hydrolysed
and MW 90 kDa) crosslinked with dicarboxylic acids con-
taining 2–10 carbon atoms have been made for the isolation
of phenol and solvents like methyl isobutyl ketone and
acetate esters [60]. The reaction was preceded or followed
by crosslinking with metal compounds such as chromic
salts. Carbonyl compounds from phenyl ketones to acetone
and higher aliphatic ketones were also tested and found to
give membranes of exceptional mechanical properties. In
tests at 5 MPa, retention of phenol from 2000 mg/L solu-
tions ranged from 25 to 74%, when malonic and succinic
acids were the crosslinkers respectively, while sodium sul-
phide rejection was 92–95% (suberic and sebacic acids).
With ketone crosslinkers the phenol rejection was 56–75%
for benzoylacetone and diphenyl ketone.
Malic acid, HO2 C–CH2 –CH(OH)–CO2 H, has been shown
to be a more effective crosslinking agent than GA or other
aldehydes and acids in the preparation of thin-film com-
posite membranes made by coating a polysulphone UF
membrane with PVA [56,61]. The PVA used (98% hydrolysed
and MWs ranging from 2 to 65 kDa) was dried after coat-
ing the support and contacted with the crosslinking agent,
then heat treated. In RO experiments with 2000 mg/L NaCl
at 1.7 MPa the salt rejection was up to 99% and depended
on the curing temperature, 120 ◦ C in this case. However, the
production rate was severely reduced to impractical levels
of <5 L/m2 h, versus 29 L/m2 h and 60% rejection when cur-
ing was at 70 ◦ C. Rejection was 95% for GA, the best of the
aldehydes. With trimesic acid (benzene-1,3,5-tricarboxylic
acid) as the crosslinker, an 88% salt rejection was obtained
at a permeate flux of 8 L/m2 h. PVA (>98% hydrolysed and
MW 72 kDa) has been crosslinked with malic acid and the
membranes produced tested for the separation of acetic
acid–water mixtures by PV [62].
PVA can be crosslinked effectively with maleic acid,
cis-HO2 C–CH CH–CO2 H to give membranes useful in the
separation of acetic acid–water mixtures, with 5 mol% of
the crosslinker resulting in membranes giving higher sepa-
ration than membranes based on 10 mol% crosslinker [63].
There are more flexible interlinks between PVA chains
than occur with the more crystalline PVA obtained by
heat treatment [64]. Crosslinking of PVA (99% hydrol-
ysed and MW 75 kDa) with maleic acid or citric acid,
HO2 C–CH2 –(OH)CH(CO2 H)–CH2 –CO2 H, has been used to
prepare membranes for permeation studies of water-lower
aliphatic alcohol mixtures [65]. Citric acid gave more selec-
tive behaviour than maleic acid, and the selectivity was
highest for water–isopropanol and water–isobutanol sys-
tems.
PVA (MW 50 kDa) has been crosslinked with
poly(acrylic acid) (MW 2 kDa) by heat treatment at
150 ◦ C for 1 h [66]. The products have been used for PV
of methanol/methyl tert-butyl ether mixtures, and later
ethanol–water mixtures [67]. Considerable effort has
gone into producing crosslinked PVA membranes for
both PV separations and fuel cell use, a recent example
being membranes containing sulphonic acid groups [68].
PVA (MW 89–98 kPa) solutions were mixed with varying
amounts (5–30% by weight) of sulphosuccinic acid, cast
and heat treated at 120–130 ◦ C for 2 h. The proton conduc-
tivity and methanol permeability were very dependant
on the sulphosuccinic acid content and the crosslinking
temperature.
The crosslinking of PVA (99.5% hydrolysed and MW
77 kDa) with maleic anhydride in the presence of sulphuric
acid catalyst is reported [28]. After drying the membrane
was heated at 120 ◦ C for 2 h. Unlike the parallel study
reported above that was carried out with formaldehyde, the
reaction led to mainly inter-chain crosslinking, but there
was an analogous decrease in hydrophilicity when greater
amounts of reagent were used, as OH groups were still con-
sumed. The water content varied from 2 g/g of membrane
at 1% crosslinking to 1.3 g/g at 15% crosslinking. The prod-
uct was tested in PV experiments, where low water fluxes
but high separation factors were obtained.
Maleic anhydride has been used to crosslink PVA
(98.4% hydrolysed, MW 189 kDa), using just 0.05 mole
of the anhydride per mole of PVA [69]. The product
was formed on ceramic (␥-Al2 O3 ) hollow fibre supports.
It showed a high water flux in the dehydration of 2-
propanol and 1-butanol, plus a simultaneous increase in
the separation factor, contradicting the flux-selectivity
paradigm, much as had been observed for nanoparticles of
fuming silica (<50 nm, 30 wt%) in the stiff-chain polyacety-
lene poly(4-methyl-2-pentyne), which increased both the
mixed gas n-butane/methane selectivity and the n-butane
permeability [70]. It was suggested that the presence of
the nanoparticles resulted in a greater polymer/particle
interfacial area, disrupting the packing of the rigid and
 B. Bolto et al. / Progress in Polymer Science 34 (2009) 969–981
bulky polymer chains and enhancing molecular trans-
port.
A composite membrane has been made from a hol-
low fibre polysulphone UF membrane by coating it with
a PVA (95% hydrolysed, MW 1.8 MDa)–sodium alginate
(4:1) blend, and using maleic acid in mineral acid as the
crosslinking agent [71]. The membrane was tested in the
PV dehydration of aqueous aliphatic alcohol solutions,
where high separation factors and permeation fluxes were
obtained. Crosslinked PVA/maleic anhydride membranes
have also been fabricated by electrospinning [72].
Poly(vinyl methyl ether) alternating copolymers with
maleic anhydride have been used to crosslink PVA in inter-
polymer membranes [73]. The membrane also contained
sodium poly(styrene sulphonate), but this made the mem-
brane fragile and weak. UF of erythrosin showed that
increased crosslinker content gave higher rejections. In RO
at 40 MPa, salt rejections of up to 98% have been recorded
[74]. With ratios of PVA:copolymer of 3.5:1 salt rejections
were >60% with 2000 mg/L NaCl at 2 MPa [75]. Highest
rejection was obtained at pH 11, the lowest at pH 3, as would
be expected from ionisation of the carboxylic acid groups
present in the membranes.
Fumaric acid, trans-HO2 C–CH CH–CO2 H, has been
employed as the crosslinking agent at 0.05 mole per mole
of PVA in multilayer membranes formed on a polyacryloni-
trile support membrane, during which the PVA was filled
with various zeolites [76]. The multilayered product was
used in the PV of aqueous ethanol.
An amic acid has been used as a crosslinker for
PVA [77]. Imidisation at 150◦ gave an improved mem-
brane for PV of aqueous ethanol when there was 12 wt%
crosslinker present. More crosslinker showed the reverse
effect because of the dispersion of unreacted crosslinker
within the membrane.
Thin film composite membranes have been prepared by
coating a porous polysulphone membrane with an aqueous
PVA solution containing hydroquinone and a surfactant,
and then contacting it with trimesoyl chloride (TMC) in
an organic solvent to give an interfacially polymerised
membrane [78]. After drying and heating, a further coat-
ing of PVA solution was applied and the product heated
to give a low flux membrane that rejected salt to a high
degree.
TMC has been used to crosslink PVA (99% hydrolysed,
MW 133 kDa), in the preparation of PV membranes [79].
The membranes were cast from aqueous PVA solution and
the water removed by natural drying. Different volumes of a
2.5% (w/v) TMC/hexane solution were added to the bunded
membranes which were left to dry again at 25 ◦ C overnight,
then rinsed with isopropanol and water. The membrane
thickness was 50–60 ␮m. The crosslinked membranes had
higher thermal stability than plain PVA film. An appropri-
ate degree of crosslinking was found for best performance
in the dehydration of isopropanol.
2.10. Alkoxysilanes
Membranes made from PVA crosslinked with 25 wt%
of tetraethoxysilane (TEOS) have been prepared for the
PV of aqueous ethanol, with the aim of minimising the
975
swelling of the PVA [80]. Annealing of the membranes
under nitrogen at temperatures of 100, 130 or 160 ◦ C was
needed to complete the condensation reaction that intro-
duced bridging, when higher permselectivity resulted. It
was postulated that the crosslinking reaction took place in
the non-crystalline parts of the PVA membrane, forming
denser non-crystalline regions. Annealing also improved
the selectivity of similar membranes made from poly(vinyl
alcohol-co-acrylic acid) [81]. Similar membranes have been
reported, with the observation that too much crosslinker
makes the membrane hydrophobic [82]. Performance was
enhanced by modifying the membrane by the incorpora-
tion of chitosan [83]. Poly(ethylene glycol) has also been
blended with PVA in such membranes to enhance perme-
ation properties [84].
PVA has been crosslinked with ␥-glycidoxypropyl-
trimethoxysilane to produce PVA-silica hybrid membranes,
with the aim of improving both permeability and selectiv-
ity in PV [46]. Bridges such as
may be formed as links between the oxygen atoms in the
PVA. The permeation flux for benzene from a mixture with
cyclohexane increased from 20.3 g/m2 h for an unfilled PVA
membrane to 137 g/m2 h for the hybrid membrane, while
the separation factor increased from 9.6 to 46.9. This was
attributed to an increase in the size and number of both
network pores and aggregate pores, and an elongation of
the diffusion path.
A mixture of ␥-glycidoxypropyltrimethoxysilane and
TEOS has been employed in the crosslinking of PVA for
dehydration of ethylene glycol [85]. The ␥-glycidoxypropyl-
trimethoxysilane facilitated the dispersion of silica
particles throughout the membrane, enhanced the
mechanical properties and gave the best selectivity results.
A more compact crosslinked structure was obtained
with membranes made from PVA and ␥-mercaptopropyl-
trimethoxysilane [86]. There was no improvement
when the mercaptol groups were oxidised to sul-
phonic acid groups. PVA membranes crosslinked with
␥-aminopropyltriethoxysilane have been examined in the
separation of ethanol/water mixtures [87]. The incorpo-
ration of polysilisesquioxane (PSS) into PVA membranes
gives hybrid membranes that have increased permse-
lectivity and flux at low PSS levels when tested in the
pervaporation dehydration of tetrahydrofuran [88].
Another highly hydroxylated polymer, chitosan or
poly(2-amino-2-deoxy-d-glucose), has been used to make
silica hybrid membranes with ␥-glycidoxypropyltrimet-
hoxysilane as the crosslinking agent [89,90]. The primary
reaction was through the amino group in chitosan, with
crosslinking occurring via hydrolysis and condensation
of the methoxy groups, to produce O–Si–O bridges. The
hybrids showed better thermal stability and a low degree
of swelling in water. Likewise, in the preparation of PV
membranes for ethanol dehydration, chitosan has been
976 B. Bolto et al. / Progress in Polymer Science 34 (2009) 969–981
crosslinked with 3-aminopropyltriethoxysilane to form
chitosan-silica hybrid membranes [91]. The hydrophilic-
ity of the membranes increased with increasing amounts
of the crosslinker, reaching a maximum when the con-
tent was 10 wt%. The flux and water selectivity increased
as a result. The crosslinking limited the swelling of the
polymer. It was claimed that there were strong hydrogen
bonds as well as covalent bonds formed, along with a low-
ering of crystallinity. Thus the FTIR spectrum showed an
intense absorption band at ∼1072 cm−1 , indicating that a
reaction took place between the OH groups in the polymer
and the silanol groups in the crosslinker, to form C–O–Si
bonds. If the second ethoxy group reacts with the OH in
another chain, bridges can occur. The crosslinking makes
the polymer chains in the amorphous regions more com-
pact, resulting in less space for species to permeate through
the membrane and making the resistance higher for the
larger species.
2.11. Other chemical crosslinking agents
Composite RO membranes have been constructed from
Millipore filters with an ultrathin layer of PVA crosslinked
with toluene di-isocyanate (TDI) [92]. Operation at 10 MPa
yielded salt rejections of 98% and a water flux of 21 L/m2 h.
TDI has also been used to surface modify a PVA UF mem-
brane that had been crosslinked with GA, using 0.005 moles
of GA per OH group [93]. Compared to the unmodified
membrane the new product had a 4.5-fold improvement
in selectivity for lysozyme (MW 14.1 kDa) over BSA (MW
66.5 kDa). The barrier layer provided a higher level of size
exclusion. There was a small reduction in lysozyme flux to
76% of the original value. Mixed cellulose ester MF mem-
branes of 0.3 ␮m pore size have been impregnated with
such gels to provide a support and give a thinner, less frag-
ile membrane [94]. A di-isocyanate terminated oligoether
made from tri(ethylene glycol) and TDI has been used to
crosslink cellulose that had grafts of poly(ethylene oxide)
[95]. The products have application as separators in lithium
ion batteries.
In what amounts to crosslinking with glycidyl acry-
late, macromers have been made by reacting PVA
(99% hydrolysed, MW 13–23 kDa) with the epoxy com-
pound under acidic conditions to form the PVA ether
containing pendant acrylate groups [96]. A photoinitia-
tor, 2-hydroxy-1-[4-(hydroxyethoxy)phenol]-2-methyl-1-
propanone, was added to aqueous solutions of the polymer
which were polymerised by exposure to ultraviolet light.
The degree of swelling in water was a function of the reac-
tant concentration, ranging from 5.5 to 15 to 18 as the
concentration was changed from 50 to 30 to 20 wt%, with
complete reaction occurring at all levels. The more water
present in the reaction mixture, the greater the amount of
intramolecular reaction of the pendant double bonds. It was
found that the resulting network in the best case was looser
than that obtained for networks crosslinked with a compa-
rable amount of GA at the 2 and 7 mole% levels. Physical
crosslinking via the introduction of crystallinity gave even
looser networks.
The crosslinking of PVA with divinyl sulphone under
alkaline conditions at 70 ◦ C has been reported [97]. When
tested on 1500 mg/L salt a rejection of 15% was obtained
at 0.7 MPa, but a good permeate flux of 14 L/m2 h resulted
even at the very low test pressure. Divinyl sulphone has
been used to crosslink PVA coatings of solvent impreg-
nated resins [98]. The PVA (98–99% hydrolysed and MW
124–186 kDa) was treated with 1 M sodium carbonate prior
to addition of the crosslinker.
PVA has been treated with boric acid and then immersed
in polyvalent ion solutions such as Ba(OH)2 , AlCl3 or
KCr(SO4 )2 [6]. The products are chemically stable and show
product fluxes of 6.3–10.4 L/m2 h in RO at 5 MPa. The reac-
tion of boric acid or its salts with PVA has been thoroughly
explored [99], and although they do not crosslink PVA,
gelation does occur in the presence of cations. Complex
formation with metal ions has also been utilised [100],
followed by crosslinking with acidic glutaraldehyde. The
diffusion properties of these membranes have been tested
with theophylline and vitamin B12 .
Gaseous 1,2-dibromoethane was the crosslinker chosen
for the polymer matrix of interpenetrating polymer net-
works forming an ion-exchange membrane from PVA (99%
hydrolysed and MW 124–186 kDa) at 130 ◦ C [101].
Epichlorohydrin has been employed in the crosslinking
of hydrolysed starch-g-polyacrylonitrile/PVA blend films
by reaction at pH 10 at 40 ◦ C for 2 h [102]. The hydrol-
ysed graft polymer contains carboxylic acid and amide
groups which can be linked to the OH groups of PVA by
the crosslinker. Tests on RO behaviour have been made
[103].
It is interesting to note that macroporous PVA mem-
branes can be made by an electrospinning technique
from a solution of PVA (98% hydrolysed and MW 77 kDa)
containing an ethoxylated nonylphenol surfactant [104].
Stabilising the film against dissolution in water can be
achieved by crosslinking with bifunctional reagents such as
sodium borate, boric acid or GA, as well as via irradiation
or alternating freeze–thaw conditions.
PVA has been crosslinked with 1,1,1-tris(hydroxy-
methyl)propane by heating at 150 ◦ C for 30 min in the pres-
ence of an acid catalyst [105]. An insoluble film is formed,
the porosity of which can be enhanced by incorporating
sodium poly(styrene sulphonate) within the film as an
interpenetrating polymer. Swelling in water ranged from
50 to 60%, and erythrosin rejection in UF operation from 81
to 88%.
A recent article is devoted to the preparation of adsor-
bent membranes from chitosan. The membranes were
formed with a macro open pore structure using salt par-
ticles of size 150–250 ␮m, and genipin as the crosslinking
agent [106]. Genipin is an aglycone derived from an iridoid
glycoside present in fruit of Gardenia jasmindides Ellis. It
is much less toxic than other chemical crosslinkers, and is
used for pharmaceutical purposes. The reaction is carried
out in 5 vol.% acetic acid solution at ambient tempera-
ture for 10 h, and then evaporated at 50◦ . The membrane
swelling in water ranged from 2.5 to 4.2.
3. Grafting of PVA onto support membranes
PVA, and also hydroxyethyl cellulose and dextran, have
been covalently linked to polyamide membranes that had
 B. Bolto et al. / Progress in Polymer Science 34 (2009) 969–981
been activated with bis-oxirane (1,6-hexanediol diglycidyl
ether), then a dye immobilised on the surface to form dye-
affinity membranes [107]. The membranes were used to
separate an enzyme from fermentation broth by retention.
The permeability of the membranes was reduced by about
half compared to that of the original polyamide membrane
because of the extension of polymer coils into the pores. The
presence of cell debris caused only a slight decrease in per-
formance, indicating minimal attachment of these particles
to the hydrophilic surface.
A simple method of grafting PVA onto porous hydropho-
bic membranes such as polyethylene, polypropylene or
poly(vinylidene fluoride) involves pretreating the mem-
brane with chromic acid solution then dipping it in a PVA
(99+% hydrolysed and MW 85–146 kDa) solution that had
been crosslinked with maleic acid or GA [108]. In the case
of GA the amount of crosslinker was 0.0025– 0.01 moles
per PVA repeating unit. Some bonding of the PVA via the
crosslinker to –OH groups introduced to the membrane sur-
face must take place. The membranes were used for osmotic
distillation of oily feeds.
Grafting of proteins onto crosslinked PVA surfaces by
the use of oxidised starch has been explored [109]. The
coupling is based on Schiff base formation between the
amino groups of proteins and the aldehyde groups of oxi-
dised starches that have been grafted onto the substrate
membrane through acetalisation of the aldehyde of starch
with the –OH groups of the substrate polymer. Another
way of doing this would be to react the substrate polymer,
PVA as the prime example, with sufficient dialdehyde to
leave a pendant –CHO group at each site. The reverse situa-
tion would be the reaction of the dialdehyde with terminal
amino groups in a polyamide membrane to produce pen-
dant –CHO groups, which in turn would be reacted with
PVA in a grafting process.
Commercial RO and NF membranes that have been
coated with PVA are less fouled in the treatment of dye
house wastewater than uncoated membranes [110]. This
was ascribed to the reduction of both the surface nega-
tive charge and the surface roughness that accompanied
the coating: a neutral and smoother surface was signifi-
cantly beneficial. Passage of NaCl and CaCl2 was slightly
reduced for the NF membrane, and slightly increased for
the RO membrane.
A membrane has been made from PVA blended with
poly(ethylene glycol) or PEG, and crosslinked with a
dialdehyde [111]. It was investigated as a modified com-
posite membrane for membrane distillation (MD), where
normally water vapor is transported through a porous
hydrophobic membrane. A PVDF membrane of 0.2 ␮m pore
size was used as a substrate, pretreating one side of it
with a potassium dichromate/sulphuric acid solution and
casting a PVA (MW 2 kDa)/PEG (MW 10 kDa) solution that
was then crosslinked with the dialdehyde, which would
bond the PVA to the treated membrane. The hydrophilic
layer obtained was placed in contact with the salt solu-
tion. In desalting 3.5% NaCl, 91% of the flux obtained with
a purely hydrophobic membrane was achieved with a sep-
aration efficiency above 99% when the temperature of the
feed was 70 ◦ C. The lower the cooling temperature, which
varied from 12 to 25 ◦ C, the higher the flux, with a range
977
of 26–23.5 L/m2 h, which was 91% of that from the totally
hydrophobic membrane. The wetting problem facing tra-
ditional MD with the hydrophobic membrane was avoided
by incorporating the hydrophilic layer. There can be serious
problems with membrane wetting of hydrophobic mem-
branes, causing MD to slow down and, in the worst cases,
being brought to a halt.
4. Commercial PVA membranes
There is limited information on commercial membranes
in the open literature. NF composite membranes have
been prepared by coating a mixture of PVA and a reactive
dye onto a porous polypropylene membrane, followed by
crosslinking by heating [112,113]. Stable to pH 12 at 60 ◦ C,
the membranes give 98% rejection of ionic dyes with MWCO
of ≥700 Da at 2–3 MPa. They have been used industrially in
the desalting of dye liquors.
To overcome slow fluxes, porous supporting membranes
have been coated with thin PVA films crosslinked with a
dialdehyde, using phosphoric acid as catalyst and pore for-
mer at 110 ◦ C [113,114]. The resulting NF membranes have
found application in copper recovery from alkaline plating
baths. The membrane was stable to pH 13. Rejection of NaCl
was 20% and MgSO4 , 85%.
Low pressure RO membranes with high salt rejection
have been made from polysulphone UF substrates by form-
ing a thin skin of PVA on the surface [115]. No preparative
details are given, but the PVA must be crosslinked to ensure
insolubility. Two such membranes made by the Nitto Elec-
tric Industrial Company (now Nitto Denko, Kusatsu, Japan),
used in spiral wound mode, have been designated NTR-
739HF and NTR-729HF. They can desalt brackish water at
1 MPa pressure to give salt rejections of 95.5 and 91.5%
respectively, at fluxes of 33 and 54 L/m2 h. An important
feature is their resistance to chlorine attack.
These commercial PVA membranes have been used to
separate the constituents of a lipase hydrolysate of high-
oleic sunflower oil after dilution with organic solvents
[116]. The pressure used was 4 MPa at 40 ◦ C, when the mem-
branes performed as well as a polyamide RO membrane in
terms of rejection or selectivity, but not as well as cellulose
acetate membranes. The RO performance of the two PVA
systems was quoted as 93 and 60% salt rejection respec-
tively by the supplier. Under the same conditions the salt
rejections of a cellulose acetate and a polyamide membrane
were 98 and 99.5% respectively.
A similar product has been reported that has an aro-
matic polyamide RO membrane as the substrate [117]. After
coating with the PVA, the composite membrane was heat
treated at 130 ◦ C for 5 min, resulting in a 0.1 ␮m thick
layer being formed on the original membrane. For both the
coated and uncoated membranes the salt rejection from a
1500 mg/L NaCl solution was 99.5–99.7% at an operating
pressure of 150 kPa and a flux of 4–25 L/m2 h, showing that
the main salt barrier was provided by the supporting aro-
matic polyamide membrane. High anti-fouling properties
were claimed for the coated product.
Low fluxes are claimed to be the reason why PVA mem-
branes are not in large-scale commercial use [118].
978 B. Bolto et al. / Progress in Polymer Science 34 (2009) 969–981

Table 2 Table 4
Attributes of PVA membranes. RO results for PVA membranes crosslinked by different means.

Positive Negative Crosslinker Pressure NaCl Rejn. Flux Reference

(MPa) (%) (L/m2 h)
Excellent hydrophilicity High degree of swelling
Permeability to water Permeability to ions Heat treatment 5.2 26 – [15]
Good mechanical properties Compaction under pressure Heat treatmenta 8 93 28 [16]
Thermal resistance Low flux when highly crosslinked ␥-Irradiation 10 20–50 – [20]
Resistance to chemicals Acid-catalysed dehydration 2 70–85 29–33 [4]
Anti-fouling potential Persulphate 2 45 42 [22]
Low operating pressure Formaldehyde 4 93–97 – [23]
Film forming ability Formaldehyde 10 90 – [24]
Formaldehyde 5 25–28 35-54 [25]
Formaldehyde 1.7 67 – [56]
5. Conclusions Glutaraldehyde 4 85 – [26]
Glutaraldehyde 1.7 99 <5 [56]
Glyoxal 1.7 46 – [56]
The main characteristics of PVA membranes are sum- Oxalic acid 4 95 – [26]
marised in Table 2, and the types of crosslinking agents Malic acid 1.7 60–99 – [65]
that have been used on PVA are listed in Table 3. A fur- Trimesic acid 1.7 88 8 [56]
Maleic anhydride 40 98 – [75]
ther point worth considering is the toxicity of the reagents
copolymer
or the by-products formed during the crosslinking. This Maleic anhydride 2 >60% – [76]
applies particularly to formaldehyde, which in the presence copolymer
of hydrochloric acid can form chloromethyl ether, the use Toluene diisocyanate 10 98 21 [92]
of which is highly restricted as it poses a significant hazard. Acrolein 10 97 – [24]
Methacrolein 1.7 55 – [56]
Other crosslinkers such as toluene diisocyanate are unlikely
Divinyl sulphone 0.7 15 14 [98]
to be approved for potable water production. Nitti Denko NTR-739HFb 1.0 95.5 33 [115]
The beneficial properties relevant to membrane opera- Nitto Denko productc 0.15 99.7 4–25 [117]
tion are many, outweighing the detrimental ones. Arising a
A 3:2 PVA/poly(styrene sulphonic acid) composite.
from the superior hydrophilicity, the disadvantages can be b
PVA on polysulphone support, crosslinker unknown.
overcome by crosslinking reactions through some of the OH c
PVA on aromatic polyamide support.
groups responsible for the hydrophilicity. However, this is
really counterproductive: what is really needed is a net-
water permeability and permeate flux rate. This arises
work that provides a tight restraining without serious loss
because of the tighter network, but there is a decrease in
of hydrophilic behaviour.
hydrophilicity as some of the OH groups are consumed by
PVA membranes crosslinked by a variety of means have
reaction with the crosslinking agent. There is hence an opti-
been tested for RO salt rejection as detailed in Table 4.
mum degree of crosslinking for each bridging system. To
GA is a more effective crosslinking agent than formalde-
overcome the possible low fluxes associated with a high
hyde or glycidyl acrylate, which in turn gives a less swollen
degree of crosslinking, thin film composite structures are
product than that obtained by increasing the crystallinity
appropriate, as have been developed in early commercial
by heating. TDI and acrolein give similar results, but at an
PVA membranes.
extremely high applied pressure. Crosslinking with maleic
The high swelling behaviour can be countered also by
anhydride/vinyl methyl ether copolymers gives as good a
forming the active PVA component inside the pores of an
result, but at even higher pressure.
MF membrane. Crosslinked PVA inside such membranes
The degree of crosslinking is not always specified. Good
would have its swelling suppressed, and could function as
crosslinking is crucial for performance as highly crosslinked
the active RO material; by merely coating the pore walls,
membranes will have a higher salt rejection, but a lower
leaving porosity, MF or UF membranes could be prepared. In
both situations some grafting to the host membrane would
Table 3 be beneficial.
Crosslinkers used on PVA.

Freeze–thaw treatment Malic acid References

Heat treatment
Acid-catalysed dehydration
␥-Irradiation
Persulphate treatment
Formaldehyde
Glutaraldehyde
Glyoxal
Terephthaldehyde
Acrolein & methacrolein
Urea formaldehyde/H2 SO4
Citric acid
Maleic acid & anhydride
Maleic anhydride
copolymers with vinyl
methyl ether
Malonic acid
Fumaric acid
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