A Review of Reverse Osmosis Membrane Materials For Desalination - Development To Date and Future Potential

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A review of reverse osmosis membrane materials for desalination--

Development to date and future potential
Article in Journal of Membrane Science · March 2011

DOI: 10.1016/j.memsci.2010.12.036
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Journal of Membrane Science 370 (2011) 1–22
Contents lists available at ScienceDirect
Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci
Review
A review of reverse osmosis membrane materials for desalination—Development

to date and future potential
Kah Peng Lee, Tom C. Arnot, Davide Mattia ∗
Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, UK
a r t i c l e i n f o a b s t r a c t
Article history: Reverse osmosis (RO) is currently the most important desalination technology and it is experiencing
Received 26 July 2010 significant growth. The objective of this paper is to review the historical and current development of RO
Received in revised form membrane materials which are the key determinants of separation performance and water productivity,
13 December 2010
and hence to define performance targets for those who are developing new RO membrane materials. The
Accepted 16 December 2010
chemistry, synthesis mechanism(s) and desalination performance of various RO membranes are discussed
Available online 24 December 2010
from the point of view of membrane materials science. The review starts with the first generation of
asymmetric polymeric membranes and finishes with current proposals for nano-structured membrane
Keywords:
Desalination
materials. The paper provides an overview of RO performance in relation to membrane materials and
Reverse osmosis (RO) methods of synthesis.
Membrane material To date polymeric membranes have dominated the RO desalination industry. From the late 1950s to
Membrane performance the 1980s the research effort focussed on the search for optimum polymeric membrane materials. In
Nano-materials subsequent decades the performance of RO membranes has been optimised via control of membrane
formation reactions, and the use of poly-condensation catalysts and additives. The performance of state-
of-the-art RO membranes has been highlighted. Nevertheless, the advances in membrane permselectivity
in the past decade has been relatively slow, and membrane fouling remains a severe problem.
The emergence of nano-technology in membrane materials science could offer an attractive alternative
to polymeric materials. Hence nano-structured membranes are discussed in this review including zeo-
lite membranes, thin film nano-composite membranes, carbon nano-tube membranes, and biomimetic
membranes. It is proposed that these novel materials represent the most likely opportunities for enhanced
RO desalination performance in the future, but that a number of challenges remain with regard to their
practical implementation.
© 2010 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Current and Projected Needs of Clean Water Resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Current state-of-the-art RO technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3. Challenges and trends in RO desalination technology development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2. Conventional desalination RO membranes – polymeric materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Early membrane chemistry development and asymmetric membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Thin film composite (TFC) membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2.1. Early development of TFC membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2.2. Interfacial polymerisation synthesis of TFC membrane. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3. Membrane post-synthesis modifications and control of interfacial polycondensation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.1. Surface modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.3.2. Optimisation of polymerisation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3. Novel desalination RO membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.1. Polymeric membrane by rigid star amphiphiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
∗ Corresponding author. Tel.: +44 1225 383961; fax: +44 1225 385713.
E-mail address: [email protected] (D. Mattia).
0376-7388/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2010.12.036
2 K.P. Lee et al. / Journal of Membrane Science 370 (2011) 1–22
3.2. Ceramic/Inorganic membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

3.3. Mixed matrix membranes (MMM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.3.1. Nano-particle/polymeric membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.3.2. Carbon nano-tube/polymeric membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.4. Biomimetic RO membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4. Conclusions and future developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1. Introduction lems [10]. As shown in Fig. 1, the amount of contracted capacity

in desalination plants grew by 43% in 2007 to 6.8 million m3 per
Today reverse osmosis (RO) is the most widely used desalina- day, up from 4.7 million m3 per day in 2006. In the first half
tion technology globally. Over the past few decades remarkable of 2008 growth in contracted capacity was 39%, and the total
advances have been made in the preparation of RO membranes global desalination capacity was about 50 million m3 in 2009
from different materials. Despite this, reviews of RO membrane [11–13].
materials have been rare, probably due to the fact that RO mem-
branes of current practical importance are mainly based on patents 1.2. Current state-of-the-art RO technology
rather than conventional research journal papers. The last pub-
lished comprehensive review on RO membrane materials was by RO is today the leading desalination technology. It has overtaken
Petersen more than 17 years ago [1] and, naturally, this only focused conventional thermal technology such as multi-stage flash (MSF)
on the thin film composite membranes which existed at the time. [14] and is expected to maintain its leadership in the near future,
Recently, Li and Wang published a review of research on surface though new technologies such as membrane distillation [15], elec-
modification of RO membranes [2]. In addition to ongoing research trodialysis [16], capacitive deionization [17] and forward osmosis
into conventional polymeric RO membrane materials, nanotech- [18] that have been proposed. Commercial interest in RO technol-
nology has opened the way to incorporating nanomaterials into RO ogy is increasing globally due to continuous process improvements,
processes. It therefore seems timely to comprehensively review which in turn lead to significant cost reductions. These advances
the historical development of commercially successful RO mem- include developments in membrane materials and module design,
brane materials and to look forward to the novel nano-structured process design, feed pre-treatment, and energy recovery, or reduc-
materials that will shape future trends in membrane materials tion in energy consumption. The beneficial outcomes are shown
research. quantitatively in Fig. 2(a), (b) and (c). The seven-fold decrease in
salt passage over 30 years has greatly expanded the range of saline
1.1. Current and Projected Needs of Clean Water Resources feeds that can be treated to meet the stringent potable water stan-
dards. The enhanced mechanical, biological and chemical strength
The famous Malthusian doctrine states that “population of RO membranes, as well as the increased permeability, have
increases in a geometric ratio, whilst the means of subsistence reduced the membrane cost per unit volume of water produced by
increase in an arithmetic ratio” [3]. This is illustrated by the fact more than 10 times since 1978. The combined effort to minimis-
that global fresh water demand increased by a factor of six between ing fouling and concentration polarization, in addition to maximise
1900 and 1995, an increase of more than double compared to the permeate flux and energy recovery, has decreased the energy con-
concurrent increase in population [4]. Since 1995 this trend has sumption from 12 kWh m−3 in the 1970s to less than 2 kWh m−3 in
further accelerated, due to simultaneous increases in water use 2006 [19,20].
in emerging economies and reduction in fresh water availability Nevertheless, the greatest efficiency gains have arisen from
due to pollution and the effects of climate change. The lack of the improvement of the membranes. The structure, material,
access to potable water and sanitation is a major source of dis- and morphology of RO membranes have been modified to
ease and an obstacle to sustainable growth for a large part of the improve functionality (permeability and selectivity) and applica-
global population [5,6]. Many developing countries are undergoing bility (mechanical, chemical and biological stability). The current
rapid industrialization without appropriate wastewater manage-
ment systems, and are now facing increasing water pollution issues
whilst still struggling with poor water supply and sanitation prob-
lems [7]. According to the World Health Organization, there are
more than 2.5 billion people (about 40% of the world’s popula-
tion) that do not have access to sewer sanitation systems [8]. At the
same time sustainable provision of clean water resources is impor-
tant to all economies irrespective of their size. The shift to biofuels
may add further significant demands for water for crop irrigation
and product manufacturing and refining [9]. In many cases, natural
water supplies are decreasing as a result of climate change and over
exploitation, and solutions such as water conservation and water
transport, or construction of new dams, are insufficient to cope with
increasing demand. Therefore the most pressing challenges today
include the recovery of clean drinking water from salty or sea water,
by far the most abundant global water resource, and the treatment
and recycle of wastewater.
Desalination, a technology that converts saline water into clean
water, offers one of the most important solutions to these prob- Fig. 1. Cumulative desalination capacity from 1960 to 2016 [12,13].
K.P. Lee et al. / Journal of Membrane Science 370 (2011) 1–22 3
Fig. 2. (a) Improvement in salt rejection. Data from [19]; (b) Reduction in membrane cost. Data from [19]; (c) Reduction in energy consumption of RO. Data from [20].
RO membrane market is dominated by thin film composite (TFC) of spacers, feed channels and vessels, as well as the materials of
polyamide membranes consisting of three layers: A polyester construction, have optimised the inter-connection between mod-
web acting as structural support (120–150 ␮m thick), a micro- ule design and fluidic transport characteristics, thereby decreasing
porous interlayer (about 40 ␮m), and an ultra-thin barrier layer both fouling and pressure losses.
on the upper surface (0.2 ␮m) [21]. The polyester support web Polyamide spiral wound membranes dominate RO/Nano-
cannot provide direct support for the barrier layer because it is filtration (NF) market sales with a 91% share. Asymmetric cellu-
too irregular and porous. Therefore, between the barrier layer lose acetate (CA) hollow fibre membranes hold a distant second
and the support layer, a micro-porous interlayer of polysul- spot [27]. Although the latter has superior chlorine resistance,
fonic polymer is added to enable the ultra-thin barrier layer to thereby allowing prevention of the growth of microorganisms
withstand high pressure compression. The thickness of the bar- and algae via chlorine injection, the former has higher salt rejec-
rier layer is reduced to minimize resistance to the permeate tion and net pressure driving force [28]. There are four major
transport. Membrane pore size is normally less than 0.6 nm to membrane module suppliers which provide RO membranes for
achieve salt rejection consistently higher than 99%. The selec- large scale desalination plants, namely DOW, Toray, Hydranau-
tive barrier layer is most often made of aromatic polyamide, for tics and Toyobo. Hence, state-of-the-art seawater desalination RO
example via interfacial polymerization of 1,3-phenylenediamine membrane modules from each supplier are tabulated in Table 1
(also known as 1,3-benzenediamine) and the tri-acid chloride of in order to provide a benchmark of current SWRO performance.
benzene (trimesoyl chloride) [22]. With improved chemical resis- A specific comparison of the various products is not attempted
tance and structural robustness, it offers reasonable tolerance to as the data corresponds to different test or operating conditions
impurities, enhanced durability and easy cleaning characteristics [29–36].
[1,23,24]. Research on the design of modular elements is currently
The spiral wound membrane module configuration is the most focusing on optimization of hydrodynamics in order to minimise
extensively used design in RO desalination. This configuration the concentration polarization effect. In addition, larger modu-
offers high specific membrane surface area, easy scale up operation, lar elements are desirable for increased desalination capacity.
inter-changeability, low replacement costs and, most importantly, Recently, Koch Membrane Systems have released 18-in. spiral
it is the least expensive module configuration to produce from flat wound modules with the MegaMagnum® trade name. Hydra-
sheet TFC membrane [25,26]. Although the spiral wound configura- nautics and DOW (FILMTECTM ) have 16-in. modules which are
tion was developed decades ago, improvements in the dimensions being piloted in cooperation with the national water agency in
Table 1
Some of the state-of-the-art SWRO membrane modules in application.
Membrane module brand Material & module Permeate flux (m3 day−1 ) Salt rejection (%) Specific energy consumption
name (kWh m−3 )
[d]
DOW FILMTECTM 8-in. TFC cross linked fully aromatic 28.0 [a] 99.60–99.75 [a] 3.40 (2.32) [e] at Perth SWRO
SW30HRLE polyamide spiral wound Plant, Australia [30]
Hydranautics 8-in. TFC cross linked fully aromatic 24.6[b] 99.70–99.80 [b] 4.17 (2.88) [e] at Llobregat
SWC4+ polyamide spiral wound SWRO Plant, Spain [30,33]
Toray 8-in. TFC cross linked fully aromatic 19.7–24.6 [a] 99.50–99.75 [a] 4.35 at Tuas SWRO Plant,
TM820C polyamide spiral wound Singapore [31]
Toyobo 16-in. Asymmetric cellulose 60.0–67.0[c] 99.40–99.60[c] 5.00 at Fukuoka SWRO Plant,
HB10255 tri-acetate hollow fibre Japan [32]
Note: [a] Test condition: 32 g L−1 NaCl solution, 55 bar, 25 ◦ C, pH 8 and 8% recovery [29,35]; [b] Test condition: 32 g L−1 NaCl solution, 55 bar, 25 ◦ C, pH 7 and 10% recovery [34];
[c] Test condition: 35 g L−1 NaCl solution, 54 bar, 25 ◦ C and 30% recovery [36]; [d] These numbers should not be compared explicitly because of different operating parameters
(e.g. feed water quality, recovery, pre-treatment processes, process design, etc.) at different desalination plants. [e] The number in brackets is the energy consumption for
the RO membrane unit.
Singapore, PUB. Studies have shown that such module designs can 2. Conventional desalination RO membranes – polymeric
further decrease the cost of desalination by approximately 20% materials
[37,38].
Polymeric RO membranes have dominated commercial appli-
1.3. Challenges and trends in RO desalination technology cations since the very first RO desalination plant. Due to their
development technological maturity they offer low-cost fabrication, ease of han-
dling and improved performance in selectivity and permeability.
Sheikholeslami recently concluded that the future challenges One of the earliest review studies on polymeric RO membrane
in the desalination industry include feed water characterization, materials was reported by Cadotte [43]. It focused on composite RO
process development, materials development, renewable energy membranes, covering activity from the inception of composite RO
source, stringent water standard and brine management [39]. membranes up to approximately 1985. In 1993 Petersen [1] offered
Currently the largest SWRO plant in the world is in Ashkelon, a comprehensive review of the same subject, focusing on the chem-
Israel, and it has a production rate of about 110 million m3 year−1 . istry of the membrane materials. This section will briefly highlight
Considering the global average water consumption per capita of the early development of membrane chemistry and graphical illus-
1243 m3 year−1 (5% for domestic use, 85% for agricultural irrigation, trations are used to visualize the performance improvement of RO
and 10% for industrial use) [40], this plant can supply fresh water membranes. This chronological description provides the readers
to less than 100,000 people. Hence mega-sized desalination plants with a quick overview of RO membranes formed by different mech-
must be developed if we are to provide new clean water supplies anisms and their impact on the desalination industry over the years.
to billions of people. For a complete study of early RO membrane development, readers
In this context, the biggest challenge would be making RO are however advised to refer to Petersen [1].
desalination affordable for poorer countries. Unarguably, the cap- Generally the development of membrane materials can be
ital investment and operating costs of RO plants must be further divided into two periods according to research activity: (i) the
reduced to achieve this. Electricity (energy), labour and chemi- search for a suitable material (chemical composition) and mem-
cals make up about 87% of the total RO cost [14]. Developments brane formation mechanism (1960s to late 1980s), and (ii) the
in membrane material and module optimization can significantly evolution of more controlled conditions for membrane formula-
contribute to the reduction of all three aspects. tion to enhance membrane functionality and durability (late 1980s
Additionally, significant improvement in the rejection of low to date) [44].
molecular weight compounds, especially boron species, is neces-
sary. The highest boron rejection membrane offered in the market 2.1. Early membrane chemistry development and asymmetric
can only achieve 93% boron rejection at optimum conditions, and membranes
it has been reported that 99% of boron rejection is required in the
Middle East region for one-pass RO process to comply with the In 1949 a report entitled The Sea as a Source of Fresh Water initi-
WHO water drinking standard [41]. Furthermore, higher salt rejec- ated research activities on salt-rejecting membranes [45], although
tion can possibly reduce the number of RO passes necessary to initial work on the narrow gap membrane project was not fruit-
achieve appropriate product water quality. Reduction in fouling, ful. In the late 1950s, Reid and Breton reported that a hand-cast
particularly via the development of chlorine-tolerant membranes, thin symmetrical cellulose acetate (CA) membrane could retain salt
is important because it directly reduces the costs of membrane effectively, achieving 98% rejection, but that the permeate flux was
replacement, backwashing chemicals, and energy to overcome the very disappointing, of the order of <10 mL m−2 h−1 [46]. Next, the
additional osmotic pressure. announcement of the Loeb-Sourirajan CA membrane was of histor-
Although the operating pressure in current systems is already ical importance as it first made RO possible in practice [47]. A CA
close to the thermodynamic limit and a further reduction would asymmetric membrane was formed with a dense 200 nm thin layer
have a modest impact on performance [42], the reduction in energy over a thick micro-porous body. This new morphology produced a
consumption would be considerable, as the energy cost represents water flux of at least an order of magnitude higher than the initial
half of the total water production cost. Moreover higher permeabil- symmetric membrane [48]. The material molecular composition of
ity would lead to a reduction in membrane area, and consequently these membranes is shown in Table 2.
a reduction in membrane replacement costs, a smaller plant foot Fig. 3 highlights the major development of asymmetric RO mem-
print and a reduced use of cleaning chemicals. To be of commercial branes up to the 1980s. In the decade after the announcement
interest, any novel membrane must outperform the materials and of the Loeb-Sourirajan membrane, further research on CA mate-
modules listed in Table 1. rials was focused on the improvement of the membrane transport
Table 2
Notable asymmetric RO membranes.
Chemical type & description Chemical structure
1. Cellulose Acetate - Loeb-Sourirajan CA [48]

Flux: 0.35 m3 m−2 day−1
Salt rejection: 99%
Test: > 100 bar, 4% NaCl solution
2. Aromatic Polyamide - Polyamide-hydrazide [49]

Flux: 0.67 m3 m−2 day−1
Salt rejection: 99.5%
Test: 30 ◦ C, > 100 bar, 3.5% NaCl solution
3. Polypiperzine-amide - [50]
Flux: 0.67 m3 m−2 day−1
Salt rejection: 97.2%
Test: > 80 bar, 0.36% NaCl solution
4. Polybenzimidazoline - [51]
Flux: 0.13 m3 m−2 day−1
Salt Rejection: 95%
5. Polyoxadiazole - [52]
Flux: 0.07 m3 m−2 day−1
Salt Rejection: 92%
Note: The chemical structures listed represent segments of these membranes. It does not show all possible forms of the structure, e.g. the CA structure shown is CDA, rather
than CTA or mixed-CA.
properties and simplification of manufacturing to bring the tech- resistance to compaction [55]. More studies have been performed,
nology to industrial application [53]. The cellulose triacetate (CTA) such as control degree of mixed ester substitution for the hydroxyl
membrane was developed for its stability in a wider range of tem- groups found in cellulose to monitor the performance of the CA
peratures and pH, as well as having higher resistance to chemical membranes [56].
and biological attack compared to the initial cellulose diacetate Although there was an intensive search for alternative mem-
(CDA) material. However, CTA is prone to compaction resulting in brane polymers, CA remained the best membrane material for RO
severe loss of flux even at moderate operating pressures of 30 bar or until 1969. However, the susceptibility of the acetate group to
less [54]. A blend of CDA and CTA finally offered higher permeabil- hydrolysis in both acidic and alkaline conditions, as well as sensi-
ity and selectivity than CA membranes, as well as offering greater tivity to microbial contamination, limited the durability and range
Fig. 3. The development of asymmetric RO membrane.
of applications [57]. Thus, a stronger material with higher chemi- superior mechanical and temperature stability but its salt rejection
cal stability was obviously needed and although many alternative and permeability is not commercially attractive for RO applications
polymers were tested in the 1960s the resulting improvements [52,60].
were insignificant.
The first non-cellulosic asymmetric membrane to gain attention 2.2. Thin film composite (TFC) membrane
was developed by Richter and Hoehn and consisted of an aromatic
polyamide (PA) asymmetric hollow-fibre membrane [58]. This was Only a few soluble polymers can form asymmetric structures
subsequently commercialised by Du Pont under the trade name in one-step casting, and even less are commercially attractive in
of B-9 Permasep® , for application in brackish water desalination. terms of the right combination of permeability and salt rejection.
Though it has relatively low flux and salt rejection, the durability, In addition, densification in the middle transition layer of the CA
stability and versatility are greater than CA or aromatic polyhy- asymmetric membrane occurs under pressure [70]. This led to two-
drazides [59]. Despite the low flux, its commercial success can be step casting methods that enabled individual optimization of the
attributed to the highly effective packing of the hollow fibres, which materials used for the micro-porous support film and for the barrier
outperformed the CA spiral wound elements in terms of flux per layer, the former for mechanical support and the latter for optimal
unit module volume. For detailed discussion about the variation in salt rejection and permeate flux. Furthermore, a wide variety of
reactants for PA asymmetric membranes, readers are referred to polymers can be tested for the barrier layer and support layer sepa-
[60]. rately. These anisotropic membrane morphologies are now referred
However the susceptibility of polyamides to attack by disinfec- to as composite membranes.
tants such as chlorine (halogens) and ozone was observed after
the prolonged use of the B-9 Permasep® membrane. Chlorine- 2.2.1. Early development of TFC membrane
resistant asymmetric membranes based on polypiperazine-amides As shown in Fig. 4, Francis cast the first TFC membrane by
have subsequently been developed (Table 6) [50,61,62]. They float-casting a CA ultra-thin film on the water surface followed
have comparable permselectivity to the asymmetric CA mem- by annealing and lamination onto a pre-formed CA microporous
brane. The reduced presence of amidic hydrogen also improves support [71]. Membranes produced with this technique never
the resistance to chlorine attack [63]. However, this membrane gained commercial interest because their asymmetric counterparts
was not commercialised due to its relatively low salt rejection offered a better flux for lower manufacturing costs. After an exten-
(≤95%) [64]. The presence of the sulphonic and phenyl groups sive empirical study, polysulfone was found to be the optimum
in sulfonated polysulfone was expected to enhance permeabil- material for the support layer due to its resistance to compaction,
ity, mechanical, chemical and biological stability however the salt reasonable flux and most importantly, its stability in an acidic envi-
rejection was below the acceptable level necessary for commer- ronment which enables further development of the TFC membrane
cialisation [65]. Similarly, carboxylated polysulfone which gives by acid polycondensation and interfacial polymerisation [72].
a promising flux also suffers from uncompetitive salt rejection A dip-coating method involving acid polycondensation of low-
[66,67]. Whilst polybenzimidazoline (PBIL) membranes developed molecular-weight hydroxyl-containing compounds was proposed
by Teijin show excellent permselectivity even in harsh operating to overcome scaling up problems in float-casting technology
conditions, they are susceptible to pressure compaction and chlo- [60,73]. The first patented product based on this concept was
rine attack [51,68,69]. In contrast, polyoxadiazole is found to have named NS-200, a product of the reaction of furfuryl alcohol,
Fig. 4. The development of thin film composite RO membrane.
sulphuric acid and polyoxyethylene (Table 3) [74]. It showed 2.2.2. Interfacial polymerisation synthesis of TFC membrane
excellent salt rejection but suffered from irreversible swelling The use of polysulfone as a support layer opened the way
and hydrolysis of the sulphate linkage. Another membrane pre- to interfacial polymerisation to produce RO membranes, as it
pared by acid polycondensation was the PEC-1000 TFC RO could withstand the alkaline conditions created by the use of
membrane produced by Toray Industries, Inc., [75]. It used 1,3,5- caustic as an acid acceptor in the interfacial polymerisation pro-
tris(hydroxyethyl)isocyannuric acid instead of polyoxyethylene. cess. The development of NS-100, polythylenimine reacted with
Despite its extremely high salt and organic compound rejection toluene di-isocyanate (Table 3) by Cadotte was a major techno-
with adequate flux, it was susceptible to chlorine attack. Sulfonated logical milestone in the history of RO processes [22]. It was the
polysulfone membranes have since been developed due to their first successful non-cellulosic membrane with comparable flux and
stability in oxidizing environments [65]. Nevertheless, strong Don- monovalent salt rejection. It also demonstrated superior rejection
nan effects were observed, implying the shielding effect of divalent of organic compounds, and good stability in high temperature,
cations can significantly decrease the monovalent ion rejection. A acidic and alkaline environments [93,94]. However NS-100 mem-
summary of notable TFC RO membranes is shown in Table 3. branes have virtually no resistance to chlorine, and they have a
The barrier layer can be formed by plasma polymerization, pronounced surface brittleness as a result of a highly cross-linked
where fragmentation of monomer vapour is induced by the energy structure. Another commercialised product formed by interfacial
of the gas plasma, and atomic polymerization where the monomer polymerization of polymeric amines is polyepiamine with 2 ver-
is propagated onto a cool surface, often a polysulfone support. sions designated as PA-300 and RC-100 (Table 3) [85,95,96]. The
A range of polymers have been tested and good permselec- PA-300 material showed improved flux of about 1 m3 m−2 day−1
tivity have be obtained from vinylene carbonate/acrylonitirile, and an improved salt rejection 99.4% at 70 bar, as compared to NS-
vinyl acetate/acrylonitrile, allylamine, acetylene/water / nitrogen, 100. This enhancement has led to PA-300 spiral wound modular
acetylene/water/carbon monoxide combinations [76–82]. Yasuda’s elements being installed in the TFC SWRO plant at Jeddah [97].
group was particularly active in plasma polymerization and a On the other hand, RC-100 has a high resistance to bio-fouling
membrane formed by acetylene, water and nitrogen performed which has resulted in the successful installation at Umm Lujj II
particularly well in sea water desalination test, with 99% salt and other desalination plants [98]. There are two other noteworthy
rejection for a flux of 1.5 m3 m−2 day−1 at 100 bar operation. interfacially polymerised TFC membranes, namely polyvinylamine
Despite research into plasma-polymerized films and applica- which that offers high flux, and polypyrrolidine where the amino-
tion in gas separation [83], only one commercial RO membrane /carboxy-groups can be controlled to vary amphotericity and
has been commercialized using this technique, namely the Sol- selectivity.
rox membrane. Plasma polymerized RO membranes mostly have Initial attempts at interfacial polymerization of monomeric
low chlorine resistance due to their nitrogen-enriched chemical amines, including both aliphatic and aromatic diamines, with
structure. terephthaloyl chloride, did not produce membranes with attractive
Table 3
Notable TFC RO membranes.
1. Polyfurane - Name: NS-200 - [74]

Flux: 0.8 m3 m−2 day−1
Salt Rejection: 99.8%
2. Polyether-Polyfurane - Name:
PEC-1000 - [75]
-Excellent organic rejection
3. Sulfonated Polysulfone - Name:

Hi-Flux CP - [84]
Flux: 0.06 m3 m−2 day−1
Salt Rejection: 98%
-Excellent chlorine resistance
4. Polyamide via polyethylenimine -

Name: NS-100 - [22]
Salt Rejection: 99%
Table 3 (Continued )
5. Polyamide via polyepiamine - Name:

PA-300 or RC-100 - [85]
6. Polyvinylamine - Name: WFX-X006

- [86]
Test: > 40 bar, Conductivity =
5000 ␮S cm−1
7. Polypyrrolidine - [87]
8. Polypiperazine-amide - Name:
NS-300 - [88]
Salt Rejection: 68%
Table 3 (Continued )
9. Cross linked Fully Aromatic

Polyamide - 1 - Name: FT-30 -[89]
Salt Rejection: 99%

Polyamide - 2 - Name: UTC series
-[90]
11. Cross linked Aralkyl Polyamide -

Name: A-15 -[91]
Flux: 0.26 m3 m−2 day−1
Salt Rejection: > 98%

Polyamide – 3 - Name: X-20 -[92]
Flux: 1 m3 m−2 day−1
Note: The chemical structures listed represent segments of these membranes. It does not show all possible forms of the structure, e.g. the NS-100 structure shown is the
polyamide version, rather than the polyurea equivalent.
salt rejection performance [1]. Cadotte revisited this case and opti-
mised the polymerisation conditions [61,62,99]. Nevertheless, this
polypiperazine-amide membrane exhibited strong Donnan exclu-
sion effects due to the anionic charged surface via the presence
of carboxylic groups, i.e. it can achieve excellent rejection of diva-
lent anions such as sulphate at high flux. This makes it sufficiently
attractive for practical usage in nanofiltration (NF) and the mem-
brane has been designated as NS-300 (Table 3). A range of NF
membranes based on similar chemistry have been commercialised,
e.g. NF-40 series by DOW FILMTECTM [88], NTR-7250 by Nitto Denko
[100], UTC-20 by Toray Industries [101].
Cadotte discovered that membranes with excellent perms-
electivity can be produced using monomeric aromatic amines
and aromatic acyl halides containing at least three carbonyl
halide groups, with trimesoyl chloride giving the best results
[89,102,103]. Unlike other interfacial polymerization methods,
heat curing was avoided, and acid acceptor and surfactants were
not required because polymerisation and crosslinking were both
rapid even when acyl halide was supplied at lower concentra-
tions. Membrane FT-30 (Table 3) was prepared by the interfacial
reaction between 1,3-benzenediamine with trimesoyl chloride,
producing a very unique surface characteristic, which has been
described as a ‘ridge and valley’ structure, rather than the smooth
or slightly grainy surface obtained from aliphatic amines [21].
Studies have shown that this rough ‘ridge and valley’ surface fea-
ture is closely related to the increased effective surface area for
water transport and thus water flux [104]. In seawater desali-
nation tests, FT-30 yielded fluxes of nearly 1 m3 m−2 day−1 , with
Fig. 5. The development of RO membrane by reaction optimisation and post-
99.2% salt rejection operating at 55 bar. The aromatic polyamide synthesis surface modifications: (a) Dow Filmtec seawater series and (b) Toray
structure of FT-30 provides a high degree of resistance to com- brackish water series.
pression, thermal and chemical resistance, as well as a wide
pH operating range. Although not completely resistant to chlo-
rine attack, FT-30 shows a degree of tolerance to chlorine which The biggest manufacturers of desalination membranes, DOW
is sufficient to withstand accidental exposure to this chemical FILMTECTM , currently sells products based on FT-30; membranes
[105], and a series of products based on this membrane have supplied by Toray are based on UTC-70; Hydranautics mem-
been commercialised by DOW FILMTECTM [106]. Crowdus has branes are based on NCM1, which is identical to CPA2; and Trisep
concluded that this membrane has significant impact on the membranes are based on X-20. On the other hand, asymmetric
design and cost of RO desalination [107]. It was the first spiral membrane products are still based on the conventional CA materi-
wound membrane element capable of competing with the Du als, for example the Toyobo HollosepTM range of products is based
Pont asymmetric hollow fibre polyamide B-9 Permasep® mem- on CTA and is the dominant asymmetric RO membrane.
branes, originally released in 1972. The success of FT-30 led Despite the fact that no new polymeric membranes has been
to the release of a number of similar products [108], e.g. the commercialized recently, the performance of RO membranes has
CPA2 membrane produced by Hydranautics [109], and the UTC- still improved dramatically (Fig. 5), i.e. water permeability has
70 by Toray Industries [110]. The Permasep A-15 TFC membrane been at least doubled, and the recovery of fresh water can be
(Table 3) was prepared by reacting 1,3-benzenediamine with a over 60%. These improvements are the results of surface modifica-
saturated cross-linking agent, cyclohexane-1,3,5-tricarbonyl chlo- tion, and closer monitoring of interfacial polymerization reaction
ride, resulting in an aralkyl polyamide membrane giving better parameters, as well as more effective design of the module struc-
flux [91,111]. Sundet also patented the use of isocyanato aromatic ture [41,113,114]. In addition, better understanding of, and insight
acyl halides (e.g. 1-isocyanato-3,5-benzenedicarbonyl chloride) as into, the membrane structure, associated with advancements in
cross-linking agents for 1,3-benzenediamine, in order to produce a membrane characterization techniques, has undoubtedly played an
membrane containing both amide and urea linkages that excels important role [115]. For example, Atomic Force Microscopy (AFM)
in both flux and salt rejection (Table 8) [92]. This latter mem- has been a useful tool which has confirmed that surface rough-
brane, designated X-20, showed superior resistance to fouling and ness of a membrane can greatly enhance permeability, whilst at
chlorine due to its relatively neutral surface charge and stronger the same time maintaining high salt rejection due to the increase
polyamide-urea bond linkage [112]. in effective membrane area [116].
It has been difficult to track post-1990 development of commer-
2.3. Membrane post-synthesis modifications and control of cially important RO membranes due to greatly reduced patenting
interfacial polycondensation reactions activity by membrane manufacturers. To reveal the chemical
composition and post-treatment that has been performed on com-
After the revolutionary success of the introduction of cross- mercial RO membranes, researchers have been combining the use
linked fully aromatic polyamide TFC RO membranes into the of various analytical techniques. Rutherford back scattering spec-
market, research and development towards new polymeric materi- trometry is a powerful tool for elemental composition analysis at
als for RO membranes has declined dramatically. Current products different layers and physicochemical characterisation [117–120]. A
from major manufacturers of RO desalination membranes are still combination of various analytical techniques, XPS, ATR-FTIR, TEM,
based on the original chemistry discovered during the 1980s, and streaming potential measurement has also been used to gain
i.e. interfacial polymerisation of monomeric aromatic amines. a better understanding of both physical and chemical structure of
the membrane and how it relates to the membrane performance grafting, are currently used to covalently attach some useful
[121–123]. Cahill et al. has reviewed the use of various analytical monomers onto the membrane surface which has been covered in
tools for membrane characterisation [124]. [2]. Gas plasma treatment is also used to induce surface modifica-
Whilst there are proactive academic research activities in this tion: water permeability is improved by oxygen plasma treatment
field, this review has focused on the most influential engineering due to the introduction of hydrophilic carboxylate groups, whereas
developments that have been adapted into commercial products. argon plasma treatment can greatly enhance chlorine resistance
For a more complete review of academic research activities on sur- by increasing the extent of cross-linking at the nitrogen sites
face modification of TFC membranes readers are directed to [2]. [143,144]. Recently, Lin et al. reported that the use of atmo-
spheric gas plasma surface activation and graft polymerisation
2.3.1. Surface modification on the surface of conventional polyamide TFC membranes can
A major area of membrane post-treatment research involves greatly enhance anti-fouling properties [145]. After gas plasma
hydrophilization, which can give an increase in permeability and surface activation, a polymeric brush layer is formed by free rad-
chlorine resistance. Although there has been some success in syn- ical graft polymerisation using methacrylic acid or acrylamide
thesizing membranes using monomer reactants with incorporated monomers. This brush layer can effectively reduce the ability of
hydrophilic groups (such as carboxylate) and eliminated amidic foulants to adhere to the surface, as proven in various fouling
hydrogen, the monomer reactants used are not readily available tests where this membrane has outperformed the commercial
and the preparation method is complex [125–128]. Therefore post- low-fouling membrane LFC1, particularly in mineral fouling test.
treatment to chemically modify the membrane surface properties In addition, both atmospheric gas plasma treatment and graft
is preferred, and various chemical and physical techniques have polymerisation are readily adaptable to large scale membrane
been developed. Various water soluble solvents such as acids and manufacture.
alcohols have been used to treat the membrane surface. Mixtures
of alcohol (ethanol and iso-propanol) and acid (hydrofluoric and 2.3.2. Optimisation of polymerisation reactions
hydrochloric acid) in water have also been used to improve flux Another area of intense research study is the optimization of
and rejection due to the partial hydrolysis and skin modification interfacial polymerisation reaction mechanisms, including kinet-
initiated by the alcohol and acid [129]. The presence of hydro- ics, reactant diffusion coefficients, reaction time, solvent solubility,
gen bonding is claimed to encourage interaction between the acid solution composition, nucleation rate, curing time, polymer molec-
and water, which produces more surface charge and eventually ular weight range, and characteristics of the micro-porous support
enhances the hydrophilicity and water flux remarkably. Mickols [146–150]. The early success of Tomaschke [109] and Chau [151] in
patented post-treatment of a membrane surface with ammonia or using additives in the casting solution (amine reactants) has led to
alkyl compounds, particularly ethylenediamene and ethanolamine, intensive research in using different species of additives. The use
achieved both enhanced flux and salt rejection [130]. A 70% flux of amine salts such as the triethylamine salt of camphorsulfonic
improvement is attained by soaking composite membranes in acid, as an additive in the aqueous amine reaction solution enabled
solutions containing various organic species, e.g. glycerol, sodium post-reaction drying at temperatures higher than 100 ◦ C. As a result
lauryl sulphate, and the triethylamine salt of camphorsulfonic acid a more cross-linked membrane was formed with an improve-
[131,132]. Post-treatment of membranes using an aqueous solution ment of the salt rejection without compromising the flux. Chau
of poly (vinyl alcohol) and a buffer solution can effectively improve added polar aprotic solvents, especially N,N-dimethylformamide,
the abrasion resistance as well as the flux stability of the membrane into the casting solutions which eventually gave higher
[133,134]. residues of carboxylate content and thus increased the water
Hydrophilization has also been achieved by coating the mem- permeability.
brane surface with more hydrophilic compounds. As mentioned The inclusion of additives into the casting solution plays a major
in reference [2], coatings have been the preferred method to role in alteration of monomer solubility, diffusivity, hydrolysis,
tackle fouling issues. One important example was the launching protonation, and they can also act to scavenge inhibitory reac-
of Hydranautics LFC series in 1996 [135], and the introduction tion byproducts [149]. Many patents disclose that the addition
of the LFC3-LD in 2005 [136] targeting applications in wastewa- of alcohols, ethers, sulphur-containing compounds, water soluble
ter treatment/reclamation. Neutrally charged, these membranes polymers, or polyhydric alcohol to the amine solution can improve
are designed to minimise the adsorption of organic foulants. The membrane permeability without significant change in salt rejection
reported stable performance over time has been [137] attributed [152–156]. For example, the miscibility of water and hexane has
to a poly(vinyl alcohol) (PVA) coating on the surface of conven- been improved by the addition of dimethyl sulfoxide into the cast-
tional fully aromatic polyamide membranes [122]. Coatings of PVA ing solution. Diffusion of the monomer amine reactants has been
and poly(N,N-dimethylaminoethyl methacrylate) have also shown enhanced resulting in the formation of a thinner barrier layer and
superior resistance against chlorine attack [123,138]. Recently improved water flux [157]. Fig. 6 shows micrographs of RO mem-
hydrophilic dendritic polymers have been reported to have suc- branes produced using different additives which result in different
cessfully modified a membrane surface to reduce fouling effects permselectivities, from Kwak et al. [158].
[139,140]. Instead of mixing additives into the amine reactant solutions,
Dramatic flow enhancement was achieved via chemical treat- Mickols patented the addition of a ‘complexing agent’ into the
ment of a FT-30 membrane. The membrane was soaked in a 15% acyl chloride (normally trimesoyl chloride) solution. Most widely
solution of hydrofluoric acid for seven days and exhibited about a used are phosphate-containing compounds such as triphenyl phos-
4-fold improvement in flux and slightly higher salt rejection. Mem- phate, which can modify and eliminate the repulsive interaction
brane surface analysis showed that the fluorine ratio was increased of acyl chloride with other compounds by removing the halides
as a result of the treatment. In addition, etching of the surface formed during amide bond formation. This minimises the concur-
resulted in a thinner barrier layer [141]. Whilst increasing the flux rent hydrolysis and allows sufficient reaction between the acyl
without altering the chemical structure, this method however suf- halide and amines to take place for enhanced membrane formation,
fers from leaching of the hydrophilizing components over time in particular permeate flux is increased [159,160].
causing the loss of any flux enhancement [142]. Recently the introduction of active additives, more specifically
Other surface modification techniques including the use of free surface-modifying macromolecules, into the reactants has been
radical-, photochemical-, radiation-, redox- and plasma-induced reported. In this method the additive can move toward the active
Fig. 6. FE-SEM micrographs of RO membranes surface of various permselectivity. (a) Flux: 1.15 m3 m−2 day−1 , Salt rejection: > 96%. (b) Flux: 1.16 m3 m−2 day−1 , Salt rejection:
> 99.1%. (c) Flux: 1.52 m3 m−2 day−1 , Salt rejection: > 98.7%. (d) Flux: 1.85 m3 m−2 day−1 , Salt rejection: > 98.4%. (Reprinted with permission from Kwak et al., 1999) [158].
Note: Tested at 20 ◦ C, > 15 bar for 0.2% NaCl solution. Scale bar is 600 nm for all figures.
surface during the polymerization, and hence alter the surface 3.1. Polymeric membrane by rigid star amphiphiles
chemistry to obtain desirable properties. For example, the par-
ticipation of hydrophilic surface-modifying macromolecules, such A nanofiltration membrane based on rigid star amphiphiles
as poly(ethylene glycol) end-capped oligomers, in the interfacial (RSA) has been reported recently [162,163]. As illustrated in
polycondensation reaction has improved the membrane flux and Fig. 7(a), the membranes were prepared by direct percola-
stability of salt rejection over time [23]. tion of methanol solutions of the RSAs, through an asymmetric
polyethersulfone support that had been previously conditioned
with methanol and a cross-linked poly-vinyl alcohol. Fig. 7(b)
3. Novel desalination RO membranes shows one of the RSA molecules that were synthesized by vari-
ous cyclization approaches as membrane building block materials.
Since the operation of the first RO desalination plant, only poly- In SEM and AFM analysis, this membrane exhibited an extremely
meric membranes have been employed for industrial use. As shown smooth surface, with an average roughness in the range of 1–2 nm
in Fig. 5, the advances in conventional polymeric RO membrane as compared with the higher values of roughness for commercial NF
has been rather limited since the late 1990s, especially the mem- membranes (20–70 nm). The RSA membrane barrier layer is ultra-
brane permeability. Though more membrane modules have been thin, with a thickness of about 20 nm. The composite multi-layer
released, most of them are improved by increasing membrane area dendrimer structure allows the control of narrower pore size distri-
per module. Recently, advances in nanotechnology have led to the bution. In respect to commercial NF membranes, these membranes
development of nano-structured materials which may form the have shown comparable contaminants rejection performance with
basis for new RO membranes. Li and Wang have included inorganic double the flux. Considering the similarity of polymeric NF and RO
membranes and thin film nano-composite membranes in a recent membrane morphology, this new route of polymeric membrane
review whereas Mauter and Elimelech have discussed the perspec- synthesis may offer a better alternative in tuning the membrane
tive of carbon nanotube membranes as high flux filters [2,161]. In structure. However, further investigation is needed to verify the
this section, the development of membranes that have been dis- suitability for RO process; in particular its salt rejection is still
cussed in the previous two reviews will be briefly highlighted with unknown.
a focus on their possibility to be engineered into commercial RO
membranes. At the same time, discussion about structured poly- 3.2. Ceramic/Inorganic membranes
meric membranes synthesized via a new route, carbon-derived
nanoporous membranes and biomimetic membrane are included. Ceramic membranes are mostly made from alumina, silica, tita-
The coverage of all proposed novel desalination RO membranes in nia, zirconia, or any mixture of these materials. Due to the high
this section is aimed to provide a general overview of these materi- manufacturing cost, use is currently limited to applications where
als and to draw a fair comparison to their possibility to be developed polymeric membranes cannot be used, i.e. high operating tempera-
into commercial RO membranes. tures, radioactive/heavily contaminated feeds, and highly reactive
Fig. 8. Micro-porous ceramic membrane structure: micro-porous channel in the

crystalline structure (a) Type A Zeolite; and (b) MFI Zeolite. (Reprinted with permis-
sion from Baerlocher et al., 2007) [171].
being motivated by molecular dynamic simulation results show-

ing 100% of ion rejection by perfect all-Si ZK-4 zeolite membranes
[170], this group has experimentally investigated the RO separation
mechanism and the feasibility of application of ceramic mem-
branes. Fig. 8 shows the sub-nm inter-crystalline pores within the
zeolite structure that allow the passage of water molecules and
rejects the salt [171].
Fig. 7. (a) RSA membrane synthesis process (Adapted from Lu et al., 2007) [162] and
(b) one of the RSA molecules tested in [162]. Theoretical calculations have shown that ions can be completely
excluded by zeolite membranes with pore sizes smaller than the
size of the hydrated ion. A-type zeolite membranes Exhibit 0.4 nm
environments [164]. Generally ceramic membranes are made up of pores and MFI-type membranes 0.56 nm. The first experimental
a macro-porous support layer and a meso- or micro-porous active attempt at RO of a NaCl solution using a MFI silicalite-1 zeolite
layer. The state of the art ceramic membrane preparation tech- membrane showed 77% salt rejection and a water flux as low as
niques include paste extrusion for supports, and slip-casting of 0.003 m3 m−2 day−1 at 21 bar. It is also reported that rejection of
powder suspensions or sol–gel processing of colloidal suspensions bivalent cations was higher than for monovalent ions, in a test using
for deposition of the active layer. Membrane elements have been a feed containing mixed ion species. In other words the rejection of
developed from simple tubular modules to monolithic honeycomb- sodium ions in a mixed ion solution was lower than that for a pure
type structures which offer higher packing efficiency. Currently solution of NaCl. These results show that the filtration mechanism is
commercial ceramic membranes are widely used in micro- and not only dependent on size exclusion, but also on Donnan exclusion
ultra-filtration applications whereas ceramic membranes for nano- due to the charged double layer induced by adsorbed ions on the
filtration are under development [165]. pore or the intercrystalline walls [172].
The industrial use of ceramic membranes in domestic water Although the first RO test with a zeolite membrane was unsuc-
production is rare but their process robustness has attracted the cessful, i.e. both salt rejection and water flux were too low to be
attention of researchers for both membrane distillation [166,167] of practical use, subsequent work has been conducted to improve
and pervaporation [168]. Early results on the use of ceramic mem- both by modifying the zeolite structure. The Si / Al ratio, which
branes for RO desalination have recently been reported by a group dominates the wettability and membrane surface charge, has been
of researchers from the New Mexico Institute of Mining and Tech- optimised to give improved flux and salt rejection. The Al content
nology [169]. Given the potential of desalting oil field water, and in the membrane can alter the surface hydrophilicity and therefore
Fig. 10. Schematic cross-section of zeolite nanocomposite membrane (Reprinted

with permission from Jeong et al., 2007) [186].
3.3. Mixed matrix membranes (MMM)
Fig. 9. Differential pore size distribution for CDC synthesized membrane at different
The concept of MMM, the combination of organic and inorganic
chlorination temperature measured by methyl chloride adsorption. (Reprinted with material, is not new. UOP developed a silicalite-cellulose acetate
permission from Gogotsi et al., 2003) [178]. MMM for gas separation in 1980, showing superior selectivity to
conventional polymeric membranes [180]. Despite the fact that
affinity with water [173]. Defects in the crystal structure are min- MMMs were developed for water / ethanol separation via perva-
imised by secondary growth of a zeolite layer on zeolite seeded poration in the 1990s, the incorporation of inorganic materials into
onto a porous ␣-alumina substrate [174]. This combined effort organic RO TFC membranes only started in the early 2000s [181].
generated a remarkable improvement, with a 2 ␮m thick zeolite The main objective of MMM is to combine the benefits offered by
membrane with 50:50 Si/Al ratio rejecting 92.9% of sodium ions each material, i.e. the high packing density, good permselectivity,
with a water flux of 1.129 kg m−2 h−1 at 28 bar [175]. In a recent and long operational experience of polymeric membranes, cou-
report from the same group, the thickness of the membrane has pled with the superior chemical, biological and thermal stability
been further reduced to 0.7 ␮m, providing excellent organic (>99%) of inorganic membranes [182].
and salt rejection (97.3%) as well as nearly 4 times improvement in
water flux [176,177]. 3.3.1. Nano-particle/polymeric membranes
Though the improvement of zeolite membranes has been Titanium oxide (TiO2 ) is a well known photocatalytic mate-
tremendous in the past 10 years, their performance and economics rial, widely used for disinfection and decomposition of organic
are still no match for polymeric membranes. The zeolite mem- compounds [183], and these properties make it interesting as
brane thickness is still at least 3 times higher than the current an anti-fouling coating. Anatase TiO2 nano-particles (<10 nm)
state of the art polymeric RO membranes, causing higher resistance have been prepared by the controlled hydrolysis of titanium
to water flux. Consequently ceramic membranes require at least tetra-isopropoxide. These were subsequently dip-coated onto an
50 times higher membrane area than polymeric ones to achieve interfacially polymerized fully cross-linked polyamide TFC mem-
an equivalent production capacity. This value can be even higher brane with a surface layer functionalised with carboxylate groups
when the higher density and lower packing effectiveness are con- [184]. The carboxylate groups are necessary for the self-assembly of
sidered. Moreover, whilst zeolite membranes are claimed to have TiO2 within the barrier layer via an adsorption mechanism. Testing
high organic rejection, organic fouling has caused almost 25% loss with E. coli-containing feed water has shown superior anti-bio-
in flux after only 2 h of operation, though full recovery of flux was fouling properties, especially with the aid of UV excitation, without
achieved after chemical washing [177]. compromising the flux and salt rejection performance of the orig-
Feeds of higher salinity are expected to cause shrinkage of the inal membrane. No significant loss of TiO2 nano-particles from
double layer due to the screening effect of counter ions on the the membrane was observed after a continuous 7-day RO trial
surface charge. Hence, an undesirable increase in effective inter- [184,185].
crystalline pore size would facilitate ion transport and therefore Zeolite nano-particles have also been used to prepare MMMs
reduce rejection efficiency. These tests were carried out with a low (Fig. 10). First zeolite nano-particles are synthesized via a templated
NaCl concentration (0.1%) and standard seawater desalination tests hydrothermal reaction. This is followed by a series of com-
at 3.5% NaCl should be investigated to evaluate potential usage for plex processes involving template removal, carbonization, sodium
desalting oil field seawater. exchange and calcination [186]. The resultant NaA-type zeolite par-
Carbon is another candidate for formation of sub-nm porous ticles are in the size range of 50–150 nm with a Si/Al ratio of 1.5.
material. Controlled pore size distribution of carbide derived car- These particles have been reported to be very hydrophilic (contact
bon (CDC) materials has been reported [178]. CDC offers good angle < 5◦ ), with negatively charged 0.4 nm pores which are highly
control of pore size, shape and uniformity, for example via manipu- repulsive to anions. The zeolite nano-particles are dissolved into a
lation of chlorination temperature as shown in Fig. 9. The synthesis cross-linking agent solution (trimesoyl chloride dissolved in hex-
of CDC membranes by formation of a thin CDC film on top of a ane) before the interfacial polycondensation reaction takes place.
porous ceramic support has been reported [179]. This preliminary This is different to dipping the previously formed membrane into
study introduces a route to producing asymmetric CDC membranes a nano-particle-containing solution, as with the TiO2 nanocom-
with average pore sizes of about 0.7 nm, showing a potential for posite membrane. A homogeneous dispersion of zeolite particles
monovalent salt exclusion. Nevertheless, further research is neces- is achieved using ultrasonication before the standard interfacial
sary to test the feasibility and practicality of CDC membranes for polymerization is carried out. RO membranes with various zeo-
RO desalination. lite loadings were prepared and consequent changes in membrane
Fig. 11. Effect of zeolite loading dosage on (a) surface properties, and (b) separation performance (Reprinted with permission from Jeong et al., 2007) [186].
characteristics were observed, i.e. the membranes were smoother, formation of a vapour layer between the surface and the bulk flow
more hydrophilic and more negatively charged with increasing that facilitates the water transport in a slug flow manner [198,199].
nano-particle loading. The MMM membrane exhibited 90% of flux On the other hand, it also has been argued that the frictionless water
and a slight improvement in salt rejection relative to the hand cast flow is due to the formation of a layer of liquid water molecules
TFC membrane without zeolite nano-particles. The authors suggest on the CNT walls, which provides ‘shielding’ of the bulk water
that this could be a result of enhanced Donnan exclusion by the molecules such that they flow faster [200].
zeolite particles and changes of membrane morphology [186,187]. Ion transport through the CNT channels has been investigated
Fig. 11 illustrates the changed surface properties and membrane both experimentally and computationally. Transport of ions of var-
separation performance as a result of variation in zeolite nano- ious valences has been studied in double walled CNTs of 1–2 nm
particle loading. diameter, functionalized with negatively charged groups. Although
the ion rejection is not sufficiently high for desalination, this study
3.3.2. Carbon nano-tube/polymeric membranes suggests that the ion exclusion mechanism in CNTs is dominated
Carbon nano-tubes (CNTs) have caught the attention of many by electrostatic interactions (Donnan exclusion) rather than steric
researchers due to the similarity between their fluid transport effects. This conclusion is based on the observation that solution pH
properties and those of water transport channels in biological and electrostatic screening length significantly influences ion rejec-
membranes [188]. Experimental results of fluid flow in a CNT mem- tion [191,201]. Majumder’s group also demonstrated two methods
brane was first reported in 2004 [189]. Well aligned multi-wall
CNTs were grown by catalytic chemical vapour deposition (cCVD)
on the surface of quartz substrates. These were spin coated with
polystyrene to seal the inter-tube gaps and plasma etching was
used to open the tips of the CNTs. Shortly after this, experimental
analysis of water transport in a solid polystyrene film mem-
brane incorporating 7 nm diameter multi-wall CNTs was published.
The observed flow velocity was four to five orders of magnitude
higher than the value expected from the Haagen–Poiseuille equa-
tion, which governs macroscale hydrodynamics [190]. Another
fluid flow experiment with a CNT membrane synthesized using
nanofabrication techniques has been reported (Fig. 12(a)). This
membrane contained double wall CNTs with <2 nm diameter,
and showed flow velocities of three to four orders of magnitude
higher than the theoretical calculation [191]. Recently, water trans-
port through template-grown carbon nanopipes (CNPs) of about
44 nm in diameter was investigated. These CNPs were synthesized
using non-catalytic CVD, yielding an amorphous (or turbostratic)
graphitic structure (Fig. 12(b)). The presence of the template
eliminates structural imperfections such as tortuosity, pore mis-
alignment, and branching. The factor of flow enhancement over
the predicted value is about 20, much smaller than in previous
cases [192]. The authors suggest that this might be due to the dif-
ferent surface chemistry and structure compared to the CNTs in the
previously cited articles, prepared by cCVD.
The fast water transport observed has led to many ongoing sci-
entific discussions [188,193,194]. The origin of this extremely fast
water transport in CNTs is not completely clear, and seemingly con-
tradictory explanations have been reported by simulation studies
on this topic [195–197]. It has been suggested that the develop-
ment of a strong hydrogen-bonding network between the water
molecules and the atomically smooth hydrophobic inner nanotube Fig. 12. (a) Schematic of CNT membrane reported in [191]; (b) SEM micrograph
wall causes spontaneous imhibition. This subsequently leads to the showing cross-section of CNP membrane [192].
Fig. 14. Schematic cross-section of Aquaporin embedded membrane (Adapted from

Fig. 13. Schematic cross-section of CNTs embedded TFC membrane (Adapted from
Jensen et al., 2010) [212].
Ratto et al., 2010) [206].
to alter the selectivity of different ion species, namely alteration 26 L m−2 day−1 bar−1 ) was obtained. However as the membrane
of pore size by CNT tip-functionalization, and voltage based gate disc that was synthesized was only 47 mm in diameter, studies on
control [202,203]. Although monovalent salt rejection is not tested much larger surface area membranes are needed before large scale
in either case, these studies have demonstrated the potential of manufacturing methods can be developed.
altering pore properties to enhance selectivity.
A molecular dynamic simulation of RO using CNTs has been per- 3.4. Biomimetic RO membranes
formed depending solely on physical size exclusion mechanisms.
This has shown that 0.8 nm CNTs can completely reject the salt The excellent water transport properties of biological mem-
whilst giving at least a 4 fold flux improvement over current state branes has led to the study of membranes incorporating
of the art TFC RO membranes, depending on the assumed packing aquaporins, which are proteins functioning as water-selective
density of the CNTs [204,205]. Effects of charged functionalities, channels in biological cell membranes [207]. Membranes incor-
which are often present at both ends of CNTs, were not considered porating bacterial Aquaporin Z proteins have been reported
in this simulation. The effect of their presence would probably be to show superior water transport efficiency relative to con-
able to expand the CNT size regime, as the formation of charged ventional RO membranes [208]. Aquaporins were incorporated
double layer can improve the salt rejection [193]. into the walls of self-assembled polymer vesicles consti-
Mauter and Elimelech summarize previous research efforts tuted of tri-block co-polymer, poly(2-methyl-2-oxazoline)-block-
into the development of CNT membranes for desalination, and poly(dimethylsiloxane)-block-poly(2-methyl-2-oxazoline). An ini-
forecast the necessary work on the next generation of CNT mem- tial permeability test was carried out on the aquaporin-triblock
branes [161]. The study concludes that whilst CNT membranes polymer vesicles by stopped-flow light-scattering experiments.
are promising for flux enhancement, more work is needed in The results reported at least an order of magnitude improvement
the development of efficient synthesis methods to align arrays of in permeability compared to commercially available TFC RO mem-
single-walled CNTs, with sub-nanometre diameters, and also the branes [208]. Although a salt separation test has yet to be reported,
development of tip-functionalization for more efficient salt rejec- extremely high salt rejection is expected from aquaporins since
tion. their functional biological performance is to only allow the passage
The fabrication of the CNT/polymeric membrane in the experi- of water molecules. Hence, they represent an ideal opportunity for
mental studies described above [189–191], and in many other gas the production of ultra pure water [208–210]. These studies have
separation studies, involves multiple complex steps, such as cat- so far been limited to investigating water permeability properties
alytic growth of CNTs onto expensive substrates, polymer filling across a barrier layer composed of aquaporins and triblock poly-
of the inter-tube spaces, substrate removal, and CNT tip open- mers. Many practical issues, such as identification of appropriate
ing via etching. Furthermore, the size distribution of the CNT support materials, understanding of the resistance to membrane
diameters is still not small enough to complement the simulation fouling, and even identification of an appropriate range of operat-
studies performed. To overcome this problem, a patent has dis- ing conditions must be carried out to develop this membrane for
closed the blending of CNTs into solutions, preferably cross-linking practical use.
agent solutions (trimesoyl of isophthalic chlorides), for formula- The use of an NF membrane as a biomimetic membrane sup-
tion of composite polymeric membranes (Fig. 13). In this way port has been reported [211]. A continuous phospholipid bilayer
CNTs can be effectively embedded onto the barrier layer formed was successfully formed on a, and fully covered a NTR-7450, using
by conventional interfacial polymerization on a micro-porous the vesicle fusion approach. Further study is needed to incorpo-
polyethersulfone support [206]. The CNTs need to be functionalized rate aquaporins into the phospholipid bilayer for practical use in
to obtain better solubility in organic solvents, and in this patent the water purification. A company named Aquaporin was founded in
CNTs are functionalized with octadecylamine. The resulting mem- Denmark in 2005 in order to develop these membranes for practi-
brane can be easily adapted into current filtration and RO systems, cal industrial use. The company has recently been awarded a patent
with the CNTs used being 0.8 nm in diameter. The water permeates on the method of fabricating membranes incorporating aquaporins
through the membrane via both the conventional polymeric barrier (Fig. 14) [212]. Rather than using triblock polymers the aquaporins
layer and the embedded CNT pathways. A test is disclosed in the are reconstituted into lipid bilayers fabricated using the Langmuir-
patent which compares membranes fabricated with and without Blodgett method, a vesicle fusion method, or they are spin-coated.
embedded CNTs, to demonstrate the enhanced flow generated by The patent also discloses the two different orientations of the mem-
the CNT pathways. With CNTs present a slightly higher salt rejec- brane: (i) a lipid bilayer incorporating the aquaporins is sandwiched
tion was achieved (97.69% as compared with 96.19%) and a near between two hydrophilic porous support layers such as mica, poly-
doubling of water flux (44 L m−2 day−1 bar−1 as compared with sulfone or cellulose; or (ii) a lipid bilayer incorporating aquaporins
is assembled over a hydrophobic porous support membrane such Polymeric membrane fabricated via rigid star-shaped
as a porous PTFE film. In either case the patent does not disclose any amphiphilic molecules is one of the first real breakthroughs
numerical data regarding the flux and salt rejection performance of since the interfacially polymerised RO/NF membrane, which has
the membranes, whereas severe fouling and concentration polar- been dominating for more than 30 years. Although it offers the pos-
ization are reported. sibility of engineering membrane structure in the nano-scale, there
is no report of an RO membrane fabricated by this means so far.
4. Conclusions and future developments Although the increased permeability of zeolite thin film
nano-composite membranes is the lowest when compared with
RO desalination has more than half a century of industrial opera- membranes incorporating CNTs and aquaporins, they appear to
tion. Coupling this with the ability to handle a wide range of water be more readily adaptable to commercial use due to their sim-
sources makes it a strong candidate to tackle current and future ilarity to current commercial RO membranes. Nonetheless, their
water shortage problems. It is so far the most efficient technology cost effectiveness needs to be investigated because significant addi-
for wastewater reclamation (tertiary treatment), and is one of the tional expense is expected to arise from the complex synthesis of
best performing technologies for desalting brackish water and sea nano-particles, and the extra energy required to effectively disperse
water. The former is obviously a highly desirable solution in densely the nano-particles into the barrier layer. Further technical studies
populated regions since it solves two problems simultaneously, such as optimisation of nano-particle size and dosage, elimination
namely wastewater treatment and enhancement of fresh water of crystalline defects, and simplification of nano-particle synthesis
supply. Alongside the advancements in other aspects of RO tech- procedures are also needed.
nology, the development of membrane materials has undeniably As with zeolite nano-composite membranes, the incorpora-
made RO desalination more economic by increasing performance tion of CNTs into membranes, disclosed in the patent granted to
and efficiency. Nevertheless, the search for multifunctional mem- NanOasis, shows a promising and scalable production technique
brane materials that offer higher permeability, high ion and organic that is almost identical to conventional RO membrane production
contaminant rejection, and operational robustness is still ongoing. [206]. However the manufacturing cost of the suggested 0.8 nm
This research is expected to benefit the desalination industry by single walled CNTs for RO membranes can range from US$1,800
lowering the energy cost and membrane area required; simplifying per gram and upwards [213]. The cost of CNT tip functionaliza-
pre-treatment processes; providing lower membrane mainte- tion and the energy required to homogeneously disperse the CNTs
nance costs; potentially achieving single pass RO desalination; and also have to be added. Unless combined savings from the enhanced
increasing plant capacity. In summary it promises to make signifi- permeability and superior membrane properties are proven, the
cant reductions in both capital investment and operating costs. incorporation of CNTs into membranes for water production
The development of polymeric membrane materials has gone appears economically unfavourable. However, the potential perfor-
through three main stages: (i) empirical trial-and-error testing of mance can be further improved by more dense and ordered packing
polymers; (ii) selecting suitable polymerisation reactants based of the CNTs. Instead of incorporation of CNTs into polymer solu-
on a better understanding of polymer chemistry; and (iii) closely tions, in situ growth of CNTs via ceramic templating could offer a
monitoring membrane morphology with the aid of advanced char- better method of engineering these novel membranes.
acterization tools. Despite major earlier breakthroughs such as the Theoretically, biomimetic membranes offer the highest perme-
Loeb-Sourirajan asymmetric membrane (1960s), fully cross linked ability, but this conclusion is solely derived from transport velocity
aromatic TFC membrane (1970s to 1980s), and controlling morpho- measurements of water molecules through individual aquaporin
logical changes by monitoring polymerisation reactions (1990s), channels rather than conventional membrane permeability tests.
the evolutionary improvement of a commercial RO membrane has In addition, the packing density of aquaporins in a membrane can
been rather slow during the first decade of this century. Another significantly affect the overall permeability performance. Identifi-
key limitation of commercial RO membranes is the degradation cation of a suitable membrane support is another technical problem
by chlorine, which requires de-chlorination of the RO feed and re- preventing practical implementation. Despite the almost absolute
chlorination of the RO permeate. Furthermore, excessive pressure salt rejection, these bio-materials are relatively unstable, with par-
is required to overcome the resistance arising when membranes ticularly severe fouling having been observed. The durability of the
become fouled. The evolutionary improvement of membranes membrane is therefore expected to be relatively low. Most impor-
solely prepared from polymeric materials seems to be approaching tantly, the fabrication process for these membranes are amongst
saturation. the most complex of all the systems analyzed in this review, and
Various nano-structured RO membranes have been proposed to are also possibly the most expensive.
offer attractive permeability characteristics, and many scientists Whilst nanotechnology is leading the way in the development of
believe that nanotechnology could possibly bring revolutionary novel RO membranes for desalination, there are many fundamental
advancements to the desalination industry. However, the devel- scientific and technical aspects that have to be addressed before
opment of such membranes is only in the initial stages and many the potential benefits may be realized. An example target is the
problems are yet to be overcome. The two major practical chal- development of single-pass RO using multifunctional membranes,
lenges are the high cost of nano-structured materials, and the eliminating the need for pre-treatment. At this stage these novel
difficulty in scaling up nano-membrane manufacturing processes technologies are still too expensive for practical application, and
for commercial use. In addition, health and safety issues around the hence the development of novel RO membranes with improved
use of nano-materials have to be addressed in the domestic water salt rejection and permeability at a reasonable cost is still the key
industry, particularly with respect to the use of nano-particles. Cur- focus of RO desalination technology.
rently, nano-structured RO membranes appear to be in the same
position as the initial development phase of polymer RO mem- Acknowledgement
branes, albeit with the latter now being a successful competitor
in the market. The novel membrane materials are expected to out- The authors would like to acknowledge the University of Bath
perform current RO membranes especially those listed in Table 1, for supporting this work via the award of an Overseas Research
however strong competition is foreseen, particularly via the intro- Student Excellence Scholarship to Kah Peng Lee. Additionally we
duction of 16 and 18-in. RO membrane elements. In addition, more acknowledge the UK EPSRC (grant EP/G045798/1) and the EU
resistance to biological and chemical attack is also very desirable. (grant PIRG03-GA-2008-230876) for funding support. The contents
reflect only the authors’ views and not the views of the European [38] H.Y. Ng, K.G. Tay, S.C. Chua, H. Seah, Novel 16-inch spiral-wound RO systems
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Journal of Membrane Science

A review of reverse osmosis membrane materials for desalination—Development

3.2. Ceramic/Inorganic membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

1. Introduction lems [10]. As shown in Fig. 1, the amount of contracted capacity

Chemical type & description Chemical structure

1. Cellulose Acetate - Loeb-Sourirajan CA [48]

2. Aromatic Polyamide - Polyamide-hydrazide [49]

Fig. 3. The development of asymmetric RO membrane.

Fig. 4. The development of thin ﬁlm composite RO membrane.

Chemical type & description Chemical structure

1. Polyfurane - Name: NS-200 - [74]

3. Sulfonated Polysulfone - Name:

4. Polyamide via polyethylenimine -

Chemical type & description Chemical structure

5. Polyamide via polyepiamine - Name:

6. Polyvinylamine - Name: WFX-X006

Chemical type & description Chemical structure

9. Cross linked Fully Aromatic

10. Cross linked Fully Aromatic

11. Cross linked Aralkyl Polyamide -

12. Cross linked Fully Aromatic

Fig. 8. Micro-porous ceramic membrane structure: micro-porous channel in the

being motivated by molecular dynamic simulation results show-

Fig. 10. Schematic cross-section of zeolite nanocomposite membrane (Reprinted

3.3. Mixed matrix membranes (MMM)

Fig. 14. Schematic cross-section of Aquaporin embedded membrane (Adapted from

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