Advances in Polymeric Nano-filtration Membrane: A Review

Sedra Tul Muntha1, Ayesha Kausar2 , Muhammad Siddiq1

1
Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan,
2
Nanosciences Division, National Center For Physics, Quaid-i-Azam University Campus,
Islamabad, Pakistan

Corresponding author Ayesha Kausar, E-mail: dr.ayeshakausar@yahoo.com

Abstract

Nanofiltration membrane (NF) was first introduced during late 1980’s possessing

properties between reverse osmosis (RO) and ultrafiltration membrane (UF). NF

membranes have been employed for applications including food industry,

pharmaceutical, waste water treatment, and desalination. This review presents an

inclusive outlook of recent research and advances in polymeric NF membrane

technology. Various methods were reported for NF membrane preparation particularly

through electron-beam irradiation, UV/photo-grafting, layer by layer, plasma-treatment,

interfacial polymerization, and nanoparticle incorporation. NF membranes were reported

to remove microorganisms, turbidity, dissolved salts, and hardness. Major problem in

application is NF membrane fouling, thus efforts regarding fouling mitigation are

discussed.

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GRAPHICAL ABSTRACT

KEYWORDS: Nanofiltration membrane; polymer; layer by layer; nanoparticle; fouling.

1. INTRODUCTION

The progress of synthetic/artificial membranes, which opponent biological membranes

in permeability, is an important aim in environmental and bio organic chemistry. There

are varieties of artificial membranes capable of selective solute transport [1]. In some

cases, reversible complex formation is cause of selectivity between solute and membrane

bound carrier, and immediate shuttling of solute in between membrane carrier sites. Wide

range of proteins and neutral molecules are selectively transported through artificial

polymer membranes [2]. The incorporation of specific receptors is a challenge in the

transport of molecules. Molecular imprinting is the phenomena in which recognition sites

are generated in synthetic polymeric networks. A synthetic membrane is an interface,

which acts as selective barrier between two adjacent phases. In this way, the transport of

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substances can be regulated between two compartments [3-5]. The unique separation

principle is the basic application of membrane technology, in which additives are not

required. The separations can be performed at low temperature isothermally. Moreover,

downscaling and upscaling of membrane procedures and their integration into other

reaction or separation processes are feasible. The progress of artificial membranes has

been inspired by selective transport through membrane. The highly specialized

supramolecular and macromolecular assemblies involved in the recognition of molecules

enable the transport through membrane. The general characteristics of pressure driven

membranes are reported in Table 1. Nanofiltration membranes (NF) were first recognized

in 1980’s. Their properties were determined to be in between reverse osmosis (RO) and

ultrafiltration (UF). The pore size of NF membrane is typically 1 nm corresponding to

300-500 Da molecular weight cut off. The slight charge on NF membranes in aqueous

solution is due to charge solute adsorption or surface functional groups [6]. For example,

ionisable groups in polymeric nanofiltration membranes (sulfonic acid groups and

carboxylic groups) result in charge surface generation in the presence of feed solution.

NF membranes can efficiently remove small organic molecules and inorganic salt just

like RO membranes. However more rejection of divalent ions, less rejection of

monovalent ions, and high flux are the key features of distinction in NF and RO

membranes. These properties enable NF membrane to be employed in range of

applications such as waste water treatment, biotechnology, pharmaceutical, and food

engineering [7]. Dissociation of ionisable groups generates charges on membrane surface

and in membrane pores. Such groups may be basic or acidic or certainly combination of

both depending on the specific material employed during synthetic process [8]. The

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surface group dissociation is greatly influenced by contacting solution’s pH, as surface

chemistry of membrane is amphoteric. However, at certain pH isoelectric point may be

exhibited by the membrane [9]. Electrostatic attraction or repulsion may occur in

accordance with the fix charges and valance ions of the membrane. The nature of

interaction is explained by two competing hypothesis i.e. (i) solvation energy barrier

mechanism, and (ii) image forces phenomena [10]. The nanofiltration membrane can be

categorized as pressure driven membrane having properties between ultrafiltration and

reverse osmosis membrane [11]. Several advantages have been offered by NF membranes

such as high flux, low maintenance, low operation cost, low operation pressure, and high

retention of anion salts. These advantages have increased the worldwide applications of

nanofiltration membranes [12]. In 1970’s, RO membranes operating at low pressure and

having reasonable water flux were developed. Considerable energy cost may result for

high pressure in RO membranes. Thus, membranes with greater water permeability but

less rejection of mixed components could improve the separation technology [13]. These

low pressure reverse osmosis membranes are called nanofiltration membranes. Various

NF membranes have been used and developed in different separation techniques.

Companies in Japan and US are successful in commercialization of NF membranes [14].

The most effective method to fabricate NF membrane is the composite membrane

technique. On the porous substrate, ultra thin dense layer is formed to obtain a composite

membrane. However, several other methods could be employed to fabricate NF

composite membrane [15]. The interfacial polymerization (IP) has been frequently

employed, which occur at the interface of two immiscible phases. The key of IP is to

select appropriate diffusion speed of reactant and to set reactant’s right partition

4
coefficient in two phases to attain ideal degree of densification. Membrane fouling limits

the utilization of membrane technology successfully. The maintenance and operation cost

could be increased by fouling due to shortening of membrane life and ultimate

deterioration of membrane performance [16]. In recent years, numerous studies have

determined the control and cause of membrane fouling. However, membrane fouling has

become serious problem in several applications. Thus, the chemical and physical

mechanisms governing fouling need to be explored. Recent studies indicated that the

structure and surface morphology of membrane influences the characteristic membrane

performance [17]. Membrane surface properties such as roughness, pore size distribution,

electrokinetic characteristics, structure, and chemical properties have been investigated to

effect membrane fouling. Specific chemical and physical membrane properties can be

elucidated by employing analytical techniques including contact angle, electro spin

resonance (ESR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy,

streaming potential, and nuclear magnetic resonance spectroscopy (NMR). However, the

roughness of membrane surface significantly influences the extent and rate of fouling

[18]. The purpose of this article is to critically review the research based on nanofiltration

membranes [19]. The initial portion of review includes synthesis and results reported by

various researchers in the field of NF membranes followed by fundamentals of NF

membranes such as fabrication procedures and separation techniques. Applications of NF

membranes in several fields, such as biotechnological, pharmaceutical, food industry, and

water purification, have been discussed. Finally the phenomena and effect of NF

membrane fouling have been discussed [20].

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 2. TYPES OF NANOFILTRATION MEMBRANE

Obaid et al., fabricated polysulfone-silica (Psf-SiO2) and polysulfone-grapheneoxide

(Psf-GO) nanofiber membrane and investigated high flux water/oil separation [21]. The

polysulfone membranes were synthesized by dissolving polysulfone (Psf) in

dimethylformamide (DMF). Hexane-water separation system was used for electrospun

membranes (Psf, Psf-SiO2, Psf-GO) and properties are reported in Table 2. The solution

was electrospun without pumping system. The copper pin was inserted into the solution

and inclination angle was adjusted. For batch separation process, special setup was

designed as represented in Fig. 1. Particularly, the system constitutes a feed tank having

mechanical stirrer. The main cell constitutes a vertical cylinder having a cone and product

tank. The perforated surface of main cell was covered by membrane. The mixture was

transferred from feed tank by the use of pump to the cylinder. Through the membrane,

petroleum fractions were passed. Water molecules were sedated under gravity through

annular space between cylinder and cone to the feed tank. The process was continued

until the product tank became filled with petroleum fraction and feed tank filled with pure

water. The obtained daily fluxes are displayed in Fig. 2. Gupta et al. synthesized

polyaniline-based nano-membranes through aniline polymerization in acidic aqueous

solution and were studied for gas separation applications [22]. Oxidative attack on aniline

monomer produced radical cation species. By reducing the thickness of polyaniline

membrane, increase in gas transport rate was reported. Separation membranes were

exposed to gas mixtures, which may be contaminated with liquid or solid particles.

Polyvinylidene difluoride (PVDF) has excellent chemical and mechanical stability and it

has good support porosity, so it can be used as a support polymer. The fabricated

6
polyaniline nanomembranes with thickness of 300 nm were reported. Scanning electron

microscopy (SEM) images of nanomembranes is represented in Fig. 3. The transport of

gases were explained through solution diffusion model. Gas permeation set-up is

represented in Fig. 4. For these membranes, high gas transport rates were reported. The

gas transport rate was reported to be 105 times higher for polyaniline nano-membranes

supported on PVDF than for self-supported polyaniline films. Yurekli et al. studied

filtration and adsorption processes by impregnation of zeolite nanoparticles in Psf

membranes for removal of nickel and lead cations [23]. SEM image of the prepared

membrane is represented in Fig. 5 [23]. The membrane filtration performance is mainly

affected by two parameters i.e. (i) amount of nanoparticles added, and (ii) pore size.

Under dynamic conditions, the performance of composite membranes was measured.

During filtration period, water fluxes remained constant at each pressure indicating a

stable membrane structure. The membrane’s ion exchange performance occurred under

dynamic conditions through reduction of metal in permeate. It was reported that the lead

ions were possessed by neat Psf membranes. However during filtration of nickel ions

through similar membrane, no rejection was revealed. Lead possesses an ionic of radius

1.19 nm, while nickel ion has radius of 0.69 nm. The electronegativity of nickel and lead

were reported as 1.99 and 2.33 respectively. At high metal concentration, the rate of

reaction was smaller during coupling process than mass transfer rate revealing the

adsorption capacity of membrane. Thus, it was concluded that the Psf membranes can be

used effectively for the removal of nickel and lead ions from water especially at low

pressure and temperature. Vrijenhoek et al. investigated that the membrane structure and

surface morphology influence the colloidal fouling, and rejection and permeability

7
behaviour of nanofiltration membranes and reverse osmosis membrane [24]. The RO and

NF membranes were kept in deionized (DI) water. The membranes were characterized

for chemical and physical properties such as contact angle, zeta potential, chemical

composition (XPS), roughness and performance (salt rejection and pure water flux).

Characterization of membranes for chemical and physical surface properties was

performed, and these properties were associated with fouling data demonstrated in Table

3. Despite of chemical and physical operating conditions, the roughness of membrane

surface significantly influenced the extent and rate of colloidal fouling. Atomic force

microscope (AFM) analysis reported the deposition of more particles on rough membrane

than smooth membranes at constant test conditions. Preferential accumulation of particles

in rough membranes was studied by AFM. Shape analysis of fabricated membrane is

represented in Fig. 6. Lu et al. synthesized high performance nanofiltration membranes

through interfacial polymerization [25]. Ultrafiltration membrane was used as substrate

and water flux performance was studied. Fig. 7 represents the effect of pressure on flux

through membrane. Atomic-force microscopy (AFM) image of surface layer of NF

membrane is exhibited in Fig. 8. The electrolytes were highly rejected including divalent

ions through NF membranes, however high water flux was observed through the

membrane. The morphology and composition of NF membrane were studied by AFM

and Infra Red (IR) spectroscopy. The composition was detected as polyamide,

polyarylate, polypiperazine amide respectively. Good prospects of NF membranes in

dyeing industry were reported. Gopal et al. examined the development of fibrous

membrane through electrospun nanofibrous web for liquid separation. PVDF nanofibers

were electrospun into membrane and its structural properties were related to membrane

8
separation performance and properties [26]. Fig. 9 represents the scanning electron

microscopy image of electrospun membrane. Nanofibers were employed for pre-filters

applications to reduce contamination and fouling prior to nano or ultra filtration. Bubble

point method was used to determine the pore size of electrospun nanofibrous membrane

(ENMs). The basic principal of bubble point method is to calculate the pressure essential

to blow air via liquid filled membrane. The setup for determination of pore size is

represented in Fig. 10. At the end of permeation experiment, wet membrane was located

in the cell having 5 cm3 of distilled water in contact with bubble flow meter. To the

membrane base, pressure was applied and the respective bubble flow rate was

determined. Young-Laplace equation gives the relationship between corresponding

pressure and pore size (Eq. 1)

R 2 / Pcos (1)

∆P = differential pressure, = surface tension, Θ = wetting angle

3. FABRICATION PROCEDURE

Nnanofiltration membrane technology is one of the desirable filtration techniques for

the separation of organic and inorganic substances from liquid solution. The fabrication

of better membranes resulted in great advances in nanofiltration technology through

techniques such as UV treatment, nanoparticle (NP) incorporation, interfacial

polymerization (IP), and many others. All these techniques developed membranes with

rejection tendency, higher selectivity, and overwhelming the fouling issues.

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3.1. Electron Beam (EB) Irradiation

EB irradiation is good and easy method in piercing into polymer layer. Effective

active sites could be formed on the polymer without requirement of special additives

during irradiation process. Fig. 11 represents the mechanism of electron beam radiation,

where the three dimensional network has been formed by cross-linking reaction

decreasing the pore size of membrane [27]. Xu et al. reported the fabrication of

nanofilteration membrane through grafting of 2-acrylamido-2-methylpropane sulfonic

acid on the polysulfone substrate. Variation of irradiation dose from 20 to 100 kGy was

applied. High efficiency was demonstrated for the removal of hexavalent chromium (VI)

ions, which were carcinogenic and mutagenic [28]. High negative charge density was

reported due to degree of grafting, which improved the nanofiltration membrane

performance.

3.2. UV/Photo-Grafting

The chemical bonding between the active layer and membrane substrate could

result in grafting polymerization without affecting the polymer bulk. At different

functionalization conditions, the performance of NF membranes was investigated. Qiu et

al. reported that the NF membranes were prepared through photo-grafting method having

polyelectrolyte hydrogel as selective layer. In order to obtain NF membranes, the surface

of polyether ketone ultrafiltration membrane was modified. The UV irradiation and graft

co-polymerization combination method was performed using water (H2O) soluble

monomers [29].

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3.3. Layer by Layer

Lajimi et al. investigated the effects of layer by layer (LBL) surface modification

on performance and characteristics of cellulose acetate nanofiltration membranes. The

membrane was fabricated by adsorption of alternate layers of chitosan and sodium

alginate. For best membrane performance, the optimal condition was 15 bilayers [30].

Saeki et al., introduced two crosslinking methods namely silane coupling and amine

coupling in nanofiltration membranes [31]. The reaction between oppositely charged

polyelectrolytes on silane group was performed by silane coupling, while the crosslinking

between carboxyl groups on anionic polyelectrolytes and amino groups on cationic

polyelectrolytes was performed by amine coupling. Ng et al. reported the progress of

nanofiltration membranes with performance stability and salt selectivity using layer by

layer method. The multilayer polyelectrolyte membrane provided a substitute way in

fine-tuning the membrane performance [32].

3.4. Plasma Treatment

In order to increase wettability and surface hydrophilicity, plasma treatment is an

effective technique in which polar groups are introduced to the surface. It is a beneficial

technique because chemical and physical properties of polymer surface can be modified

while bulk properties remain same. Plasma treatment involves the application of nitrogen

containing plasma to the polymer membrane. In this way, nitrogen functional groups can

be generated, which may have more hydrophilicity and low membrane fouling [33].

Buonomenna et al. investigated the modification of polymer membrane through plasma

technique for nanofiltration of solution containing having organic compounds [34]. Wang

11
et al. grafted 2-acrylamido-2-methylpropane sulfonic acid (AMPS) on PSF membranes to

fabricate novel negatively charged nanofiltration membrane by employing 2 step plasma

technique [35]. The polymer surfaces were permanently modified due to plasma induced

graft polymerization, as the monomers were grafted to the plasma treated polymer.

Scheme for plasma treatment is represented in Fig. 12.

3.5. Interfacial Polymerization

Interfacial polymerization (IP) has become very useful and practical technique for

the generation of reverse osmosis and nanofilteration membranes. On the membrane

surface, thin layer is formed due to copolymerization and reaction of two reactive

monomers. Much attention has been gained by thin film composite membrane fabricated

through IP due to significant improvement in membrane characteristics such as fouling

resistance and selectivity. IP is self inhibiting reaction which is easily applied and thin

film is fabricated with in nanometer range. The overall permeability, efficiency, and

solute retention of particular membrane were determined by thin active layer. Various

types of monomers have been applied in IP technique such as trimesoyl chloride,

bisphenol A, isophthaloyl chloride, m-phenylene diaamine, and tannic acid to fabricate

active thin film layer. New types of monomers such as tetra-ethylene pentamine,

diethylenetriamine, piperazidine and triethylene tetramine have also been studied. Fan et

al. reported the introduction of calcium chloride as an additive during interfacial

polymerization reaction [36]. The complexation ability of calcium ions with carbonyl

groups led to the generation of loose polyamide layer. The significant increase in pure

12
water fluxes through composite nanofiltration membrane was reported with the increase

in CaCl2 concentration.

3.6. Nanomaterials

Much attention has been received by nanoparticle due to unique properties such as

antimicrobial activity, photoemission, and catalytic activity. Membranes incorporated

with nanoparticles have gained much attention as they have capability to increase

mechanical properties, selectivity, permeability, and hydrophilicity in some cases.

Commonly reported nanoparticles in the fabrication of nanofiltration membrane are silica

(SiO2), zinc oxide (ZnO), silver, and titanium dioxide (TiO2). Daraei et al. reported in-

situ oxidative polymerization of iron oxide nanoparticle and polyaniline [PANI/Fe3O4].

The essential properties of Fe3O4 and PANI revealed great enhancement for the removal

of Cu (II) from water. PANI/Fe3O4 core shell structure is represented in Fig. 13 [37].

4. SEPARATION PROCEDURE

Various interfacial and microhydrodynamic events occur in the membrane nanopores

and at the membrane surface. These are very important for nanofiltration as it is a

complex process [38-40]. Combination of dielectric, Donnan, and transport effects are the

processes, which can cause rejection through nanofiltration membrnes. Neutral solute can

be transported through steric mechanisms. The potential interaction of membrane

between the interface and charged species and equilibria are described by the Donnan

effects. The ionizable groups dissociate at the surface of membrane and within the pore

structure of membrane, as a result the membrane charge may develop [41, 42]. Such

13
groups may be basic or acidic in nature or certainly the combination of both depending

on the materials used in synthesis process. The surface group dissociation is influenced

strongly by pH of solution. If the membrane surface chemistry is amphoteric in nature, an

isoelectric point may be exhibited at specific pH. Besides, low ion exchange capacity

may be exhibited by nanofiltration membranes due to ionizable surface groups.

Sometimes, ions may be adsorbed by the membrane surface from contacting solution

resulting in a slight alteration of membrane charge [43]. Electrostatic attraction or

repulsion occur according to fix charge and valance ion of the membrane. The alteration

depends on the localized ionic environment. The dielectric exclusion phenomena are less

understood and the nature of interaction is explained by two competing hypothesis of

solvation energy barrier phenomena and image force mechanism [44-48]. Exclusion

mechanism originates as a consequence of nano-length scales and spatial confinements

that exist in nanofiltration membrane. The solvent, while flowing through the pore

structure of membrane, exert drag forces to solutes in free solution. Obstructed transport

can be represented as diffusive and convective elements, which are the parameters of

overall transport effects [49, 50]. As the dimensions of active layer of nanofiltration

membrane are on atomic scale, it has postponed a comprehensive knowledge of electrical

and physical properties of existent nanofiltration membranes [51-53]. It resulted in

significant debate and uncertainty over the role of dielectric exclusion and nature of

separation mechanism. In various nanofiltration membranes, the active porous layer is

eminently present and these nanopores are characterized in terms of distribution and pore

size. Variety of methodologies such as SEM, AFM, transmission electron microscopy

14
(TEM), Brunauer-Emmet-Teller method (BET), and pore size indirect measurement have

been employed to achieve NF membrane characterization [54-56].

5. APPLICATION OF NANOFILTRATION MEMBRANE

5.1. Biotechnological and Pharmaceutical Application

Purification of pharmaceutical additives from genotoxic impurities (GTI) have

been reported through membranes. Szekely et al. reported various mechanisms for the

elimination of 1,3-diisopropyl urea (IPU), which is a potential impurity from

pharmaceutical additive [57]. The dilution ratio of 3 was reported for diafiltration with

the implication of organic solvent to attain 90% removal of 1,3-diisopropyl urea. The loss

of pharmaceutical additive was estimated to be 2.5%. The final polishing was done with

molecularly imprinted polymer for the removal of remaining 1,3-diisopropyl urea. In

single stage, 83 % of 1,3-diisopropyl urea was removed below 100 ppm. It was

concluded that the reduction of 1,3-diisopropyl urea contaminated from 100 to 2mg

IPU/g with loss of pharmaceutical additive occur mostly at 3% organic solvent stage.

Martinez et al. fabricated nanofiltration membranes of polyether sulfone (PES) and

investigated the recovery of 1-(5-bromo-fur-2-il)-2-bromo-2-nitroethane, a

pharmaceutical additive, by employing cross-flow configuration. Greater than 80%

retention was achieved for PES NF membranes [58]. Kim et al., explained the cascade

process that works through high pressure pump and did not require a buffer tank in

between membrane [59]. This configuration was approved on the purification of

roxithromycin macrolide antibiotic from ethyltosylate and 4-dimethylaminopyridine. By

applying the cascade configuration for difiltration membrane, an increase in process yield

15
from 58% to 95% was reported. However, genotoxic impurity was maintained less than 5

ppm in the final solution. Siew et al. studied recovery of organic solvent and enrichment

of pharmaceutical additive in a multi-stage cascade [60]. The dilute pharmaceutical

additive product was concentrated with simultaneous downstream recovery of solvent.

The 80% rejection was reported by 3 stage cascade in comparison to 55% single pass

rejection.

5.2. Food Industry

Beverage industry, vegetable oil processing, sugar industry, and dairy industries are

the conventional methods for food processing. An important alternative to such processes

is nanofiltration. The membrane technology applications to vegetable oil involve

deacidification and separation of compound such as antioxidant from oil. Soto ft et al.,

studied the recovery of aroma and multistep evaporators through concentrate production

of blackcurrant juice by integrated membrane processes [61]. The operation cost was

43% lower than the cost of traditional operation. Thus, the conventional evaporators

could be superseded by integrated membrane process. Sereewatthanawut et al. reported

the enrichment and refining of rice bran oil through nanofiltration processing [62].

Various solvent resistant membranes were successfully screened and applied. The fluxes

were adjusted in between 39 and 53 L/m2 h. The overall enrichment of 0.95-4.1 wt.% was

recorded, which revealed an increase of two fold in the antioxidant capacity of oil.

Prudencio et al. investigated nanofiltration followed by diafiltration technique through

which a new mechanism for production of ricotta cheese with similar rheological,

physicochemical, microstructural, and color properties were reported [63].

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5.3. Water Purification

Nanofiltration membranes are capable for generation of pure water. Oily waste

water components are listed in Table 4. Low energy consumption, enhanced capacity for

removal of contaminants, the excellent life time, and cost effectiveness have led to great

popularity and wide acceptance of NF membranes worldwide. Recent studies have shown

that apart from removal of small organic and divalent salts, NF membranes are being

used increasingly for the removal of hormones and pharmaceutical active compounds

such as diclofenac (DIC), carbamazepine (CBZ) and ibuprofen (IBU). Waste water

treatment plant may hardly remove personal care products and pharmaceuticals. However

nanofiltration membranes are proved to be eminent for the removal of such products from

water as represented in Fig. 14. Rohricht et al. investigated the removal of

pharmaceuticals from municipal water through nanofiltration membranes at low pressure

[64]. Approximately, 65% of DIC was possessed by membrane, however CBZ was

slightly retained. Ren et al. determined the viability of utilizing poly(m-phenylene

isophthalamide) NF membranes (PMIA) for chromium ion removal from waste water

[65]. Different rejections were exhibited by membranes to the electrolytes. Sequence was

reported to be Na2SO4 > MgSO4 > NaCl > MgCl2, which indicated Donnan exclusion

mechanism. Separation experiments of PMIA membranes for Cr(VI) can be employed

effectively on the basis of interaction between Cr(VI) and negatively charged NF

membrane. Zaviska et al. fabricated ceramic nanofiltration membrane and studied for

treating the adapted sludge [66]. The pharmaceutical compounds (ciprofloxacin and

cyclophosphamide) were used to dope the system. The potential of bioreactor membranes

were confirmed by high color removal and chemical oxygen demand (COD). Andrade et

17
al. studied the application of nanofiltration membranes as tertiary treatment effluvium

from dairy industry. High removal was shown by membrane bio-reactor (MBR) for

nutrients (86%) and COD (98%). However, its reuse was prevented by dissolved solids in

permeate.

5.4. Organic Solvent Nanofiltration (OSN) Application

Polymers having intrinsic microporosity are considered to have high stability as

they are soluble in few solvents, thus they are suitable for OSN applications.

Darvishmanesh et al. [67] characterized range of membranes from reverse osmosis to

ultrafiltration. Binary mixture of n-hexane and ethanol was used. The role of surface

tension, solubility parameter, viscosity, and couple diffusion between solvents and

membranes were highlighted. Valtcheva et al. fabricated novel category of OSN

synthesized from crosslinked polybenzimidazole (PBI) [68]. Different types of bases and

acids were employed to critically assess the chemical stability of membranes. It was

determined from filtration experiments that the synthesized membranes were stable and

could be implemented in harsh conditions in range of processes from petrochemical to

pharmaceutical industries. Micovic et al. designed a four step technique for combination

of distillation and OSN in a separation of hydroformylation mixture having 70% decane,

25% dodecanal, and minor amount of aldol condensation product [69]. Sairam et al.

reported spiral wound asymmetric nanofiltration membranes of PANI through both

chemical and thermal methods. Good separation performances and stable permeate fluxes

were observed in NF range upto 65 °C [70].

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 6. MEMBRANE FOULING

The fast commercialization of polymer membranes could be hindered by membrane

fouling. The membrane fouling can be assigned to both clogging of membrane pores and

deposition of sludge cake on membrane [71-75]. Due membrane fouling, trans membrane

pressure increases and permeate flux reduces depending on mode of operation [76-82].

The mechanisms responsible for membrane fouling are (i) sludge flocs desorption onto

the membrane surface; (ii) foulant detachment mainly attributed to shear forces; (iii)

colloids or solutes adsorption within membrane; (iv) temporal and spatial changes of

composition of foulant during operation; and (v) cake layer formation on the surface of

membrane [83]. Thus, the phenomena can be defined as undesirable accumulation and

deposition of solutes, microorganisms, cell debris, and colloids on/within the membrane

[84, 85]. The measurement or prediction of fouling resistance is remarkable for the

understanding of fouling extent for operating optimization conditions. Common foulants

and phenomena of fouling are described in Table 5. In order to avoid fouling,

understanding of filtration mechanism can be helpful to determine convenient methods.

Schematic representation of membrane fouling is represented in Fig. 15.

7. CLASSIFICATION OF MEMBRANE FOULING

7.1. Organic Fouling

The biopolymers (polysaccharides and proteins) deposition on membrane is referred

to as organic fouling. Due to permeate flow and small size, it is easy to deposit

biopolymers onto the membrane, however due to lift forces the back transport velocity is

lowered. Metzger et al. characterized the biopolymers deposited on the membrane [86].

19
The membrane filtration was followed by backwashing, rinsing, and chemical cleaning to

fractionate the fouling layers into lower, intermediate, and upper layer. The results

exhibited loosely bound, porous cake layer composition for upper fouling layer. High

concentration of polysaccharides and bacteria aggregates was reported for intermediate

layer. Irremovable fouling fraction and highly concentrated bound proteins was

represented by lower fouling layer. The study exhibited spatial distributed biopolymers

on the surface of membrane. Rosenberger et al. reported that the molecular weight of

polysaccharides and organic matter greater than 120,000 Da can impact membrane

fouling [87]. Additionally, fouling rates were determined to be higher for high

polysaccharides concentrations.

7.2. Bio-Fouling

Biofouling corresponds to deposition, metabolism, and growth of flocs or bacteria

cells on the membrane. Biofouling initiates with precipitation of individual or cluster of

cells on the membrane surface, after which multiplication of cells result in the generation

of biocake. Yun et al. investigated the structure of biofilm and analysed membrane

permeability for waste water treatment [88]. It was evaluated that the filterability of

membrane was associated closely with biovolume and porosity of the biofilms. These

techniques were used to visualize the biofouling and was helpful to understand the

process of cell deposition and architecture/microstructure of the cake layer. The cell’s

affinity to membrane effects the cell deposition to membrane.

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7.3. Inorganic Fouling

Ognier et al. investigated CaCO3 fouling for ceramic ultrafiltration membrane. The

study reported the preparation of synthetic waste water with hard tap water

(concentrations of Mg+2 and Ca+2 were 8 mg/L and 120 mg/L) [89]. Precipitation of

CaCO3 was attributed to increase alkalinity of activated sludge. Lyko et al. determined

the contribution of metal substances to membrane fouling [90]. Sometimes, it is not easy

to eliminate inorganic fouling even through chemical cleaning. There are two ways to

form inorganic fouling i.e. (i) biological precipitation and (ii) chemical precipitation. A

large number of anions and cations such as Al+3, Ca+2, PO4-3, Fe+3, Mg+2, OH-, CO3-2 are

present. Chemical precipitation takes place, if the chemical specie concentration is

stipulated by saturation concentration due to concentration polarization. The surface layer

of membranes can be protected by fouling layer from shear stress as biocake or biofilm

leading to greater precipitation and concentration polarization of inorganics. Biological

precipitation contains ionisable groups such as PO4-3, COO-, OH-, SO4-2, CO3-2. These

negative ions can easily capture metal ions. In some cases, acidic functional groups and

calcium can built complexes, and may form gel layer or dense bio-cake layer which may

aggravate flux decline [91].

7.4. Irremovable and Removable Fouling

Irremovable fouling is the phenomena in which it is impossible to remove fouling

using any method (such as chemical cleaning) [92-95]. The control and investigation of

irremovable membrane fouling is beneficial for sustainable and long term operation of

membranes. Instant precipitation of inorganic substances may occur on the membrane.

21
Solutes, colloids, and microbial cells pass through membrane pores and precipitate inside

[96-98]. Removable fouling can be eliminated easily by enactment of physical cleaning.

The phenomena of reversible fouling and removable fouling are same. Loosely attached

foulants are the main reason to cause removable fouling. In general, irremovable fouling

are assigned to pore blocking while removable fouling is assigned to cake layer formation

[99]. Membrane fouling is an ineluctable phenomena during membrane filtration.

Different strategies such as appropriate membrane selection, cleaning, and operating

conditions have been employed [100]. Membranes can be cleaned biologically,

chemically or physically. In biological cleaning, viable microorganisms are removed by

using biocides. Physical cleaning involves water jets, sponges or back flushing by

employing permeate [101]. However, chemical cleaning include bases and acids to

remove impurities and foulants. During membrane filtration, operating conditions are

also requisite as fouling conditions may be effected during filtration [102].

8. CONCLUSION

Nanofiltration membranes are the category of pressure driven membranes and have

applied successfully in various industries. The transport of solute in nanofiltration

membrane is controlled generally by Donnan, steric, transport, and dielectric effects.

Different methods were reported to be quite successful for membrane fabrication such as

electron beam irradiation through which active sites could be generated on polymers

without adding additives. The chemical bonding in between membrane substrate and

active layer may result in grafting polymerization without effecting polymer bulk. Plasma

treatment is an effective technique to increase the surface hydrophilicity and wettability

22
for the introduction of polar groups to the surface. It is beneficial technique as physical

and chemical properties of polymer surface can be altered, whereas bulk properties

remain constant. Nanofiltration and reverse osmosis membranes can be fabricated

successfully through interfacial polymerization. Nanoparticles have gained much

attention for NF fabrication due to unique properties such as photoemission,

antimicrobial, and catalytic activity. Various microhydrodynamic and interfacial events

occur in the membrane nanopores, which are very important for nanofiltration. Donnan

effect describes the potential interaction of membrane between charged specie, interface,

and equilibria. Due to varied permeability and selectivity, NF membranes have explored

application in various industries such as pharmaceutical, biotechnological, waste water,

OSN, and food industry applications. However, membrane fouling may hinder fast

commercialization of polymer membranes, and so problems exist in mitigation and

control of fouling.

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36
Table 1. General characteristics of pressure driven membrane.

Pressure driven Pressure Permeability Pore size Application

membranes (bar) (1/h.m2.bar) (nm)

Microfiltration 0.1-2 >1000 100- Bacteria removal

10,000

Ultrafiltration 0.1-5 10-1000 2-100 Bacteria, viruses

removal

Nanofiltration 3-20 1.5-30 0.5-2 Organics and ion

removal

Reverse osmosis 5-120 0.05-1.5 <0.5 Desalination

37
Table 2. Properties of polysulfone membrane and electrospun solution [21].

Membrane Membrane Solution Porosity Solution viscosity (cP)

thickness conductivity (%)

(µm) (µS/m)

Polysulfone 131 0.285 20 256

Polysulfone- 154 1.045 18 239

1%GO

Polysulfone- 121 0.46 25 290

1% SiO2

38
Table 3. Correlation of chemical and physical membrane properties with flux decline

[24].

Membrane Average Contact Salt Flux Zeta Water

type roughness angle ( ) rejection decline potential permeability

(nm) (%)

NF-70 43.3 51.7 83.0 7.97 -25.0 31.9

HL 10.1 51.9 35.0 0.00 -18.0 30.7

LFC 52.0 52.5 98.0 9.32 -13.0 11.0

X-20 33.4 54.1 98.0 5.32 -20.0 8.8

Correlation 1 0.07 0.87 - 0.05 -0.41

Coefficient

39
Table 4. Components of waste water.

Inorganic components Organic components Production chemicals

K+1, Na+1, Mg+2, Ca+2, Cl-1, Aromatic, aliphatic, polar Corrosion inhibitors,

CO3-2, SO4-2, borates compounds eg Grease, oil, improved oil and water

(H3BO3), silicates (H4SiO2) fatty acid, benzene, phenol separation through emulsion

beakers

40
Table 5. Common pollutants and phenomena of fouling.

Fouling Definition Pollutant

categories

Biofouling Growth and adhesion of micro-organisms Fungi, bacteria

along with extracellular cluster on

membrane surface

Colloidal Accumulation of particulate and retained Metal oxides, silica,

fouling colloidal matter on the membrane surface suspended matter, clay

minerals and salt

precipitates.

Organic Adsorption or deposition of colloidal or Effluent organic matter,

fouling dissolved organic matter on the membrane polysaccharide, proteins

surface

Scaling On the membrane surface, sparingly soluble Calcium sulphate, barium

salt’s ionic product go beyond equilibrium sulphate, calcium carbonate,

solubility product and form scaling layer silica

due to precipitation.

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Figure 1. Representation of separation cell.

42
Figure 2. Hexane flux of Psf membranes [21].

43
Figure 3. SEM micrograph of polyaniline nanomembrane supporte on PVDF [22].

44
Figure 4. Gas separation set-up.

45
Figure 5. SEM cross sectional images of the (a) PSf10-0, (b) PSf10-30 and (c) PSf10-

300 membranes. [23].

46
Figure 6. Shape analysis of polyamide membrane [24].

47
Figure 7. Pressure effects on flux through NF composite membrane [25].

48
Figure 8. AFM image of nano-filteration composite membrane [25].

49
Figure 9. FESEM micrographs of electrospun PVDF membrane (a) before and (b) after

heat treatment. [26].

50
Figure 10. Pore size measurement setup.

51
Figure 11. Radicals of EB irradiated nylon-66 combine intramolecularly to form

crosslinks [27].

52
Figure12. Schematic representation of plasma treatment.

53
Figure 13. Core shell structure of PANI/Fe3O4 nanoparticles [37].

54
Figure 14. Water purification setup for NF membrane

55
Figure 15. Membrane fouling.

56