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Separation Science and Technology

ISSN: 0149-6395 (Print) 1520-5754 (Online) Journal homepage: https://www.tandfonline.com/loi/lsst20

Hollow fiber nanofiltration membranes: A


comparative review of interfacial polymerization
and phase inversion fabrication methods

Gulsum Melike Urper, Reyhan Sengur-Tasdemir, Turker Turken, Esra Ates


Genceli, Volodymyr V. Tarabara & Ismail Koyuncu

To cite this article: Gulsum Melike Urper, Reyhan Sengur-Tasdemir, Turker Turken, Esra Ates
Genceli, Volodymyr V. Tarabara & Ismail Koyuncu (2017) Hollow fiber nanofiltration membranes:
A comparative review of interfacial polymerization and phase inversion fabrication methods,
Separation Science and Technology, 52:13, 2120-2136, DOI: 10.1080/01496395.2017.1321668

To link to this article: https://doi.org/10.1080/01496395.2017.1321668

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Published online: 26 May 2017.

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SEPARATION SCIENCE AND TECHNOLOGY
2017, VOL. 52, NO. 13, 2120–2136
https://doi.org/10.1080/01496395.2017.1321668

Hollow fiber nanofiltration membranes: A comparative review of interfacial


polymerization and phase inversion fabrication methods
Gulsum Melike Urpera,b, Reyhan Sengur-Tasdemirb,c, Turker Turkena,b, Esra Ates Gencelia,
Volodymyr V. Tarabarad, and Ismail Koyuncua,b,c
a
Department of Environmental Engineering, Istanbul Technical University, Istanbul, Turkey; bNational Research Center on Membrane
Technologies, Istanbul Technical University, Istanbul, Turkey; cDepartment of Nanoscience and Nanoengineering, Istanbul Technical
University, Istanbul, Turkey; dDepartment of Civil and Environmental Engineering, Michigan State University, East Lansing, Michigan, USA

ABSTRACT ARTICLE HISTORY


Membrane-based separation is now established as one of staple technologies used in water Received 20 September 2016
treatment and reuse applications. Nanofiltration, in particular, can be a cost-effective solution Accepted 18 April 2017
for removing large ions and low-molecular-weight compounds from water. Nanofiltration mem- KEYWORDS
branes have been manufactured mostly as flat sheets and used in spiral wound modules. Hollow Dual layer membrane;
fiber geometry, however, offers several advantages over flat sheet and other configurations. This hollow fiber; interfacial
paper overviews recent developments in the design of hollow fiber nanofiltration membranes and polymerization;
provides a comparative analysis of two main methods of their fabrication: interfacial polymeriza- nanofiltration; phase
tion and phase inversion. inversion

Introduction (400–800 m2/m3)[4] similar to that of spiral wound


membranes (300–1000 m2/m3).[5] In contrast, HF
Nanofiltration (NF) is a pressure-driven process that
membranes require less pretreatment and mainte-
employs membranes capable of selective removal of
nance while having relatively high packing density
multivalent cations and larger dissolved species while
(750–1700 m2/m3).[4]
having limited rejection of monovalent ions. Due to its
Methods that have been employed to fabricate hol-
relatively high water permeability and smaller osmotic
low fiber nanofiltration (HF NF) membranes fall into
pressures, NF consumes significantly less energy than
one of five broad categories (Fig. 1). Direct phase
reverse osmosis (RO) process. NF membranes are made
inversion (direct PI) and interfacial polymerization
in various geometries (flat sheet, tubular or hollow
(IP) on phase-inverted membranes methods are used
fiber) and are packed into modules of different config-
most often. Direct PI method is commonly used to
urations (e.g., spiral wound module for flat sheet
prepare integrally skinned NF membranes where the
membranes).[1,2] NF membranes are now broadly
porous sublayer and the separation layer (i.e., the mem-
used for water softening, municipal and industrial was-
brane skin) are made of the same polymer.[6] IP on
tewater reclamation, as well as for various separation
phase-inverted membranes is used to prepare thin film
applications in chemical and pharmaceutical industries.
composite (TFC) membranes where the porous support
Hollow fiber (HF) membranes have several advan-
is made of a different material (typically polysulfone)
tages with respect to both flat sheet membranes in
than the skin (typically aromatic polyamide (PA)).
spiral wound modules and tubular membranes.
Direct PI dual layer (DL) casting enables one-step pre-
Spiral wound modules require higher energy input
paration of DL NF membranes where inner layer can
due to headloss in the spacer-filled channels. They
be made from a different material (such as polyether-
do not permit backflushing,[3] and they are susceptible
sulfone or polyamide-imide) than the outer layer (such
to fouling which is caused by suspended solids.[3]
as polybenzimidazole (PBI) or polyacrylonitrile
Because of that, they require extensive feed water
(PAN)).[7,8] Recently, the concept of thin film nano-
pretreatment. Tubular membranes are less susceptible
composite (TFN) membrane was proposed[9] wherein
to fouling by particulate matter and afford facile
nanoparticles are included as components of the
cleaning approaches but have low packing density

CONTACT Esra Ates Genceli gencelies@itu.edu.tr Department of Environmental Engineering, Istanbul Technical University, 34469 Istanbul, Turkey.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsst.
Supplemental data for this article can be accessed on the publisher’s website.
© 2017 Taylor & Francis Group, LLC
SEPARATION SCIENCE AND TECHNOLOGY 2121

Figure 1. Methods of fabrication of hollow fiber nanofiltration


membranes [6, 8, 12–15, 20–27].

Figure 2. Number of papers published on the fabrication of


separation layer of an NF membrane. Nanoparticles hollow fiber nanofiltration membranes grouped by the year of
publication and the method of fabrication [7, 11, 21–25, 27, 32–
such as zeolite,[9] TiO2,[10] and SAPO-34 (synthesized 52]. Source: Google Scholar. Retrieved: July, 22, 2016.
from SiO2, Al2O3, and phosphoric acid)[11] have been
incorporated into membrane by IP method on phase-
inverted membranes to achieve improvements in water inverted membranes and direct PI strategies. To date,
permeability and selectivity. the total of 39 papers have been published where fab-
In addition to IP on phase-inverted membranes and rication of HF NF membranes by one of these methods
direct PI methods, grafting, coating, and self-assembly was reported (Fig. 2). This review offers a discussion of
have also been used to make HF NF membranes. A variety the challenges associated with each method as well as
of grafting methods can be employed. In the e-beam graft future prospects for HF NF membranes.
polymerization method high-energy electron beam is used
to create active sites on polymers and no contamination
occurs since no catalyst or additives are used.[12] Another Nanofiltration membrane fabrication methods
grafting method is plasma-induced graft polymerization
Thin film composite membranes
where the separation and support layer are chemically
bonded.[13] In contrast, UV photo surface grafting creates IP on phase-inverted membranes as a method of fabricat-
a new layer of polymer at a membrane surface; the method ing high-performance thin film composite (TFC) mem-
is inexpensive and easy to implement.[14] Dip-coating branes was first implemented by J. E. Cadotte in
method is perhaps the simplest.[15] Dip coating enables 1970s.[25,26] Consisting of an ultrathin (20–200 nm) separa-
tailoring of the final thin films, since the method serves as tion layer[27] and a porous support layer, TFC membranes
one important link between the structure of the solution have a major advantage over integrally skinned membranes
and the microstructure of the deposited thin film.[16] An in that it is possible to optimize each layer in the TFC
alternative approach to creating a thin polymer layer with membrane separately to achieve superior selectivity, per-
NF separation properties is based on the self-assembly of meability, and mechanical strength.[21] In the IP on phase-
oppositely charged polyelectrolytes[17]; the method has inverted membranes process, two highly reactive mono-
gained attention as a facile way of creating removable mers – a diamine (in an aqueous solution) and acyl chlor-
skins with controlled properties.[18,19] With this method, ide (in an organic solvent) – are brought into contact to
it is possible to control multilayer thickness and prepare irreversibly polymerize the monomers near the interface of
membraned with higher resistance to fouling.[20] It should the two non-miscible solvents and form a thin polymeric
be kept in mind that all these methods can be applied as a film – the separation layer of the resulting membrane[28]
modification of phase-inverted membranes. (Fig. 3). IP process on phase-inverted membranes can be
Four recent papers[21–24] provide a broad overview explained by diffusion-controlled models. According to
of the recent advances in the fabrication of NF mem- this model, IP of monomers in aqueous and organic sol-
branes. The present paper is of smaller scope and vent phase is believed to involve in incipient fast stage that
complements these earlier publications by focusing on forms a dense core barrier layer followed by a slow growth
HF NF membranes and comparing three methods of stage which is monomer diffusion limited. At the interface,
their fabrication: (1) IP on phase-inverted membranes, fast reaction upon contact leads to dense core layer which is
(2) direct PI for DL and single layer (SL) membranes, significantly thinner than the extended loose layer formed
and (3) a hybrid method that combines IP on phase- later as the monomer diffuses through the layer. Thickness
2122 G. M. URPER ET AL.

Figure 3. Schematic illustration of interfacial polymerization applied to hollow fiber membranes.

of the dense core layer can be determined by concentration concentrations, and other parameters on the IP on phase-
of monomers.[29] To improve IP addition of surfactants to inverted membranes process.[35,39,41–43] Monomer concen-
the acyl chloride, solution can assist the monomer in water tration affects the morphology and the structure of the thin
phase moving into organic phase, thus improving poly- film. For example, lower monomer concentration prolongs
merization efficiency and consequently properties of the polymerization process leading to the formation of a
formed TFC membranes.[30] Variables affecting the IP “thin and loose” PA skin with low rejection and high
process are the reactivity of the monomers, the partitioning permeability.[44]
coefficients of amine and acyl chloride monomers, diffu- Since IP occurs in the organic phase, the importance of
sion rate of the amine into the organic solvent, absolute and acyl chloride monomers can be higher than that of dia-
reactive concentrations of reactants, the polymer film mines. The choice of the organic solvent can also be critical
growth rate, the acyl chloride hydrolysis rate, the polymer as the amine monomer diffusivity in the organic phase has
film permeability, the interfacial tension of the solvent,[31] an impact on the reaction rate. Hexane has often been used
the acid acceptor type, surfactant type,[28] and lag time as the organic solvent. The addition of dimethylformamide,
(defined as time spent for removing the excess aqueous propanol, and other solvents to amine solution affects the
monomer solution from the surface of the support layer miscibility of water and the organic solvent as well as the
prior to its immersion to acyl chloride solution). diffusivity of the amine monomer in the aqueous phase.
The structure (pore size, thickness, roughness) and che- High diffusion rate and solubility of monomers in the
mical properties (degree of crosslinking, hydrophilicity, organic phase could increase the amount of monomer
functional groups) of the separation layer are the main reacting with acyl chloride monomers and produce PA
determinants of membrane performance. Monomers typi- layers having more terminal amine groups.[45] Organic
cally used in TFC membrane fabrication are aliphatic or solvent choice affects film structure, morphology, film
aromatic diamines such as m-phenylenediamine (MPD), thickness, and crosslinking degree of TFC membranes
p-phenylenediamine (PPD), and piperazine (PIP); and acyl due to enabling the control over the protonation of
chloride monomers such as trimesoyl chloride (TMC), amine monomer and hydrolysis of acyl chloride monomer
isophthaloyl chloride (IPC), and 5-isocyanatoisophthaloyl during IP on phase-inverted membranes.[46] Surfactants
chloride (ICIC)[21] (Table S1). Of these monomers, MPD employed in the IP reaction [30,47] can help move the
and TMC[29] have been applied the most. Only hyper- monomer from the aqueous phase into the organic phase
branched poly-ethyleneimine (HPEI), TMC, IPC, MPD, and improve performance of the resulting TFC membrane.
PIP, poly(amidoamine) dendrimer (PAMAM), ethylene Surfactants can also facilitate wetting of the support layer
diamine (EDA), terephthaloyl chloride (TPC), cyclic esters, surface to improve efficiency of polymerization.
and dihydric esters have been used to date to make TFC HF Other than the choice of monomers and the pre-
NF membranes. Several of the studies involving HF NF sence and properties of surfactants, the following vari-
explored the effects of the monomer choice, monomer ables may have an impact on the IP on phase-inverted
SEPARATION SCIENCE AND TECHNOLOGY 2123

Table S1. Amine and acyl chloride monomers commonly used to prepare TFC membranes.[32].
Amine monomer and its chemical structure Acyl chloride monomer and its chemical structure
Ethylene diamine (EDA) Terephthaloyl chloride (TPC)
NH2 Cl
O
H2N

O Cl

Triethanolamine (TEOA) Trimesoyl chloride


HO (TMC)[33,34,35,36,37]* O Cl

N
HO OH O O

Cl Cl

Polyethyleneimine (PEI)[18,33,38]* Isophtaloyl chloride (IPC)[6,21]*


NH2 O Cl
NH2 NH

N NH N NH
H2N NH2
N n

O
N
NH2 Cl
H2N

[34,36,37,39,40]
Piperazine (PIP) * 5-Isocyanato-isophtaloyl
chloride (ICIC) NCO
HN NH

O O

Cl Cl

m-Phenylene diamine (MPD) Cyclohexane-1,3,5-tricarbonyl


[35,39] * NH2 chloride (HTC) O Cl

NH2 O O

Cl Cl

p-Phenylene diamine (PPD) 2,3,4,5,6,-Biphenyl pentaacyl


chloride (BPAC) O O
H2N NH2 Cl
Cl
Cl

O
Cl Cl
O O

m-Phenylene-4-methyl (MMPD) 2,3,4,5,6,-Biphenyl hexaacyl


NH2 O O
chloride (BHAC)
Cl Cl

Cl O

NH2 O Cl
Cl Cl
CH3
O O

(Continued )
2124 G. M. URPER ET AL.

Table S1. (Continued).


Amine monomer and its chemical structure Acyl chloride monomer and its chemical structure
Bis[4-(3-amino-phenoxy)phenyl] mm-Biphenyl tetraacyl
O O
sulfone (S-BAPS) chloride (BTEC)
O
O O Cl Cl
NH2
H2N S

Cl Cl
O O

*HF NF studies where these monomers are used.

membranes process: support layer properties, lag time,


and post treatment. The influence of the support layer
on TFC membrane’s properties has been recognized
recently,[48–50] although none of the published studies
on HF NF addressed this issue. Ghosh and Hoek[48]
studied the effect of different polysulfone supports on
TFC membrane performance. It was found that large,
hydrophobic support layer pores translate into higher
skin roughness and higher permeability of the compo-
site membranes because of the lower amount of PA
forming within these pores. Fathizadeh et al.[51]
explored the effect of the IP lag time on the separation
performance and surface properties of PA TFC mem-
branes having different support layer. It was found that
surface properties and film thickness can be varied as a
function of hydrophilicity and pore size of support
layer as well as lag time. When support layer has large
pore size and low hydrophilicity, at the lowest lag time,
highly water- and salt-permeable TFC membranes were
fabricated. As lag time increases, water and salt perme-
ability decreases. Besides, as lag time increases, rough-
ness of TFC PA membranes decreases. Another
important factor identified was the post-treatment pro-
cess. Improved salt rejection could be obtained by
Figure 4. SEM images of a typical thin film composite hollow
increasing the degree of crosslinking, achievable at
fiber nanofiltration membrane: A) top view of the selective
higher curing temperatures. However, too high a tem- layer, B) cross section of the selective layer and the adjacent
perature can compromise the integrity of PA layer and support layer. The support layer is made of polysulfone whereas
decrease rejection.[52] the polyamide selective layer is prepared by the interfacial
polymerization of m-phylenediamine and trimesoyl chloride.
(Images recorded by personnel of the MEM-TEK Center.)
Hollow fiber thin film composite nanofiltration
membranes: Applications
TFC HF membranes, illustrated in Fig. 4, have been applied
to NF,[35,39,42] forward osmosis,[53] pressure-retarded to remove dyes (e.g., Reference [33]), heavy metals (e.g.,
osmosis,[54–56] and ethanol dehydration.[57] In Fig. 4, as Reference [42]), trace phthalate esters,[72] treatment of tex-
support polysulfone was used, whereas IP was made with tile plant effluents,[74] organic matter removal from surface
MPD and TMC monomers. Table 1 summarizes prior water,[77] extraction of sericin protein,[73] and organic sol-
studies on TFC HF NF membranes. Observed rejections vent nanofiltration.[50,75] Wei et al.[33] used three different
of NaCl and MgSO4 only are included in Table 1, although dyes (chromotrope FB, cationic red X-GTL, and cationic
some studies also reported rejection values for other salts: gold yellow X-GL) in testing TFC HF NF membranes and
MgCl2,[61,62,76] Na2SO4.[35,61,62,76] MgSO4 removal was as reported removals of 98.8%, 99.8%, and 96.4%, respectively;
high as 99%.[40] HF NF membranes have also been applied the authors concluded that dye concentration and
Table 1. Summary of published research on hollow fiber thin film composite nanofiltration membranes.
Observed salt
rejection (%) Operational conditions
Specific pure water Salt
permeate flux Flow rate concentration
Objective Monomers (L/(m2∙h∙bar)) MgSO4 NaCl (L/min) (mg/L) Main conclusions References
To develop HF TFC membranes that PEI and TMC 8.5 ~80 ~40 n.a. 1000 A proper PEI molecular weight is needed. A –[24]
can operate at pressures <2 bar highly hydrophilic selective layer is obtained. It
has a potential to be used in water softening.
[8,58]
To combine dual layer HF support Hyperbranched poly 0.982 ~84 ~87 1.5 200 High molecular weight of HPEI tends to decrease
layer and IP selective layer ethyleneimine (HPEI) and IPC pore size with increased rejection at a cost of
decreased flux. Membranes show superior
rejection properties for charged dyes. NF
membranes have potential for recycling valuable
products, water reuse in textile and
pharmaceutical industries.
[41]
To optimize IP process by varying MPD and TMC n.a. n.a. 99.5 n.a. 3000 Decreased imperfections lead to superior
monomer concentration rejection properties. Further formic acid
treatment increases both water permeability and
rejection.
[42]
To fabricate TFC NF membranes for PIP and TMC 7.91 96.2 n.a. 1.1 n.a. Operating pressure and pH affect permeate flux
heavy metal removal and heavy metal removal.
[59]
To form a TFC membrane by dip CMCNa and PP n.a. n.a. 99.8 n.a. 500 Relatively dense thin skin layer formation.
coating; target application is dye Negative surface charge increased removal of
removal anionic dye solutions.
Membranes show long-term stable performance
and anti-fouling capacity.
[39]
To form dual layer TFC HF PIP, DOX, THF, TOX, and ACE n.a. n.a. n.a. 1 n.a. Oxolane (THF), dioxane (DOX), trioxane (TOX), and
membranes using different cyclic acetone (ACE) are used to increase mass transfer
esters of PIP in the organic phase as co-solvents. Cyclic
esters are found desirable since permeability and
separation performance of membranes improved.
[33]
To fabricate positively charged Polyethyleneimine (PEI) and TMC 9.5 85 50 n.a. 1000 Isoelectric point of membranes is found to be pH
composite HF NF membrane for 8.2. Fabricated membranes show a dye retention
dye purification >98 for different dyes. Positively charged TFC HF
NF membranes are promising for dye purification.
[35]
To make membranes using different MPD, PIP, TEA and SDS, TMC 0.33/1.033 88.6/77 86.9/76.4 n.a. 1000 PIP addition increases pure water flux. However,
monomers in aqueous phase to solute rejection is decreased.
react with TMC for dye removal
[43]
To examine the effects of PIP, MPDA, TEA, TMC, and n.a. 96.3 n.a. n.a. 2000 PEG200, PEG300, PEG400, and EG increase water
environmental conditions, dihydric alcohols flux of NF membranes. Temperature and humidity
reaction time, and different affected rejection and water flux. Optimized NF
dihydric alcohols on TFC membrane is produced at 22°C, in 60% humidity,
membrane performance reaction time is 55 s when PEG 200 and EG are
used.
[60]
To investigate the effects of reaction PIP an TMC n.a. 72.1 26.8 n.a. 1000 Water flux decreases with an increase in reaction
time, flushing time of N2 gas on time. Effective flushing time is 3 min at 5 L(N2)/
SEPARATION SCIENCE AND TECHNOLOGY

TFC membrane performance min. Membrane is negatively charged due to


partial hydrolysis of acyl chloride group.
(Continued )
2125
Table 1. (Continued).
2126

Observed salt
rejection (%) Operational conditions
Specific pure water Salt
permeate flux Flow rate concentration
Objective Monomers (L/(m2∙h∙bar)) MgSO4 NaCl (L/min) (mg/L) Main conclusions References
[61]
To investigate the effects of PIP, TEA, and TMC n.a. 7 14.2 0.25 2000 Membranes fabricated with conventional IP have
monomer concentration TFC better performance. With improved IP process,
membranes rejections by PA/PVDF hollow fiber composite NF
membranes of Na2SO4, MgCl2, KCl, NaCl, PEG600,
G. M. URPER ET AL.

and PEG1000 are found as 92.3%, 7.0%, 9.5%,


14.2%, 88.4%, and 89.3%, respectively.
[62]
To investigate the effects of PIP, TEA, and TMC 15.46 72.1 26.8 n.a. 1000 Fabricated membranes show good long-term
monomer concentration and stability. Addition of TEA increases water
residence time of monomer permeability with an accompanying modest
solutions decrease in salt rejection. High permeability is
attributed to higher surface roughness.
[63]
To investigate the effects of PIP and TMC n.a. 98.02 12.95 n.a. 1000 As concentrations of PIP and TMC increase,
monomer concentration and heat rejection increases while permeate flux decreases.
treatment Surface roughness and structure of the polyamide
layer affect flux and rejection.
[64]
To investigate the parameters that PIP and TMC n.a. 98.13 18.6 n.a. 1000 The optimal aqueous phase coating pressure is 1
affect IP process bar. Membrane performance is affected by PIP
and TMC concentration, PIP solution coating
pressure, air blowing rate, and time after aqueous
coating, TMC solution flowing rate, and heat
treatment time.
[65]
To fabricate positively charged HF NF PEI and TMC 9 85 48 n.a. 1000 Isoelectric point of HF NF membranes is 8.2. If
composite membranes reactive monomers have many alkalinity reactive
groups, then heat treatment and addition of acid
acceptor can be omitted.
[66]
To develop TFC HF NF membranes Poly(amidoamine) dendrimer 0.26 n.a. n.a. 0.3 200 Amine groups in PAMAM increase hydrophilicity
with graftable monomer for heavy (PAMAM) as well as water permeability. Membranes have
metal removal improved long-term stability and anti-fouling
properties.
[67]
To develop TFC HF NF membranes PIP and TMC 11.88 96.2 39.8 1.1 1000 Membranes are hydrophilic with an isoelectric
for dye rejection and point of 6.6 which affected rejection performance.
concentration Membranes can effectively separate dye/salt
mixtures of acid red b, cationic red X-GTL,
reactive brilliant blue X-BR, and NaCl.
[68]
To investigate the performance of Tetramethyl-tetrakis- 22 98 40 80 n.a. Flux performance of capillary membranes is
capillary HF NF membranes aminomethyl-methane (TTAM) superior to that of spiral wound membranes.
and polyacylhalide
[69]
To investigate the effects of reaction PIP, TMC, and 2,2′-bis(1-hydroxyl- 5.2 ~95 ~45 n.a. 2000 Ratio for PIP/BHTTM is 1:1. Membranes are stable
conditions on NF membranes in 1-trifluoromethyl-2,2,2- for 7 days and rejection of ferric ion and oxyanion
terms of removal of oxyanions triflutoethyl)-4,4′- is above 95% and 90%, respectively. Membranes
and ferric ions methylenedianiline (BHTTM) have high tolerance with respect to chlorine.
[40]
To develop greener TFC membranes PEI, TMC, glutaraldehyde (GA), 1.74 99 90 n.a. 1000 Membranes crosslinked with glutaraldehyde have
by crosslinking for cadmium and epichlorohydrin (ECH) stable separation performance during the 72 h
removal continuous run. Also membranes can be used for
a wide range of operation temperature from 5°C
to 60°C.
(Continued )
Table 1. (Continued).
Observed salt
rejection (%) Operational conditions
Specific pure water Salt
permeate flux Flow rate concentration
Objective Monomers (L/(m2∙h∙bar)) MgSO4 NaCl (L/min) (mg/L) Main conclusions References
[70]
To investigate the effects of PIP, Na3PO4, and TMC 6.9 98 30 0.5 2000 Poly(vinyl chloride) is used as a substrate for IP.
substrate properties on NF HF Differences in membrane pore size, porosity, and
membrane characteristics surface hydrophilicity of different substrate
contribute to changes in the thickness and
degree of crosslinking.
[71]
To improve water permeability and PIP, TMC, and TEOA 17.01 n.a. 49.9 n.a. 500 TEOA modification improves membrane’s water
anti-fouling properties of TFC permeability. TEOA reduces hydrophobic
membranes by modifying the interactions and decreases membrane fouling.
active layer with triethanolamine TEOA-modified membranes feature improved NF
separation performance in tertiary treatment of
industrial effluent.
[72]
To investigate rejection properties of PIP and TMC 11.9 96.2 n.a. n.a. 1000 Operation pressure, ionic strength, and
TFC HF NF membranes with temperature affect permeate flux. Phthalates of
respect to phthalate esters higher molecular weight have longer equilibrium
adsorption time and higher rejection.
[73]
To recover sericin protein from silk PIP and TMC 36.2 95 13.5 n.a. 1000 Feed temperature has great impact on NF
reeling wastewater by TFC HF NF membranes. According to sericin protein
membranes accumulation on NF membranes, membrane
surface showed cauliflower-like structures.
[74]
To treat textile wastewater effluent MPD and TMC 20 n.a. n.a. n.a. n.a. HF NF membranes were able to reject reactive
with TFC HF NF membranes black, red, and yellow dye by 99.9% and blue dye
by 98.8%.
[75]
To fabricate TFC membranes for PEI and isophthaoyl dichloride n.a n.a n.a n.a n.a. Membranes were characterized by brilliant blue R
solvent-resistant nanofiltration (IPD) and Safranin O in methanol with rejection values
of 88% and 43%, respectively. Study proved that
polyamide coating on propylene has solvent
resistance to alcohols and aromatic hydrocarbons.
n.a., not available.
SEPARATION SCIENCE AND TECHNOLOGY
2127
2128 G. M. URPER ET AL.

molecular weight, pH of the solution, Donnan exclusion, seen in Fig. 7. In contrast to SL HF membranes, DL HF
and steric hindrance had effects on dye removal. Wei et al.- membranes can be made using two different polymer
[42]
studied heavy metal removal from wastewater using solutions that are extruded simultaneously using a triple
TFC HF NF membranes and reported rejection values for orifice spinneret (Fig. 8). By varying the choice of the two
chromium, copper, and nickel ions as 95.76%, 95.33%, and polymers, one can optimize characteristics of the resulting
94.99%, respectively. Results of the study revealed that DL membrane.[7,84,85]
heavy metal removal was affected by feed temperature, The DL method inherits many benefits of the SL HF
pH, and operating pressure. fabrication process (i.e., high surface to volume ratio,
self-supporting structure) while minimizing the
amount of the relatively more expensive material used
Single-layer hollow fiber nanofiltration membranes
to fabricate the salt rejecting layer.
Another method to fabricate HF NF membranes is the For example, block copolymers can be employed to
single-layer (SL) direct PI process. It is possible to fabricate make the outer “thin” layer, while cheaper polymer mate-
integrally skinned asymmetric HF membrane by the direct rial can be used as to prepare the thick support layer.[86]
PI method (Table 2). The resulting membranes have ultra- Further, the separation layer can be co-extruded from a
thin selective layer on a highly porous substrate. The com- material with improved resistance to chlorine (e.g., poly-
plexity and long production time of IP on phase-inverted benzimidazole (PBI))[87] giving the DL HF method
membranes process can be avoided.[6] SEM images of a SL increased chlorine resistance, an important advantage
HF are given in Fig. 5. over IP TFC phase-inverted membranes. To date, DL
Direct phase separation is described by phase diagram HF membranes have been applied to gas separation,[88,89]
(Fig. 6). In this diagram, triangle is divided into two regions NF,[38] pervaporation,[90,91] pressure-retarded osmosis,[87]
by binodal curve which are a single-phase region where all membrane distillation,[92,93] protein separation,[94] organic
components are miscible and a two-phase region where solvent nanofiltration,[95,96] and forward osmosis.[85]
system separates into a solid (polymer rich) and a liquid Table 3 summarizes prior studies on DL HF NF
(polymer lean phase). Between initial casting composition membranes.
and final membrane composition, solvent is exchanged by Jiang et al.[98] studied the effects of draw ratio and
the nonsolvent. Precipitation point is described as the point air gap on zeolite-added SL HF and DL HF mem-
where the polymer precipitation occurs. At this point, branes. It was found that particle distribution in the
viscosity of polymer is sufficiently high to be regarded as cross section is determined by draw ratio, shear rate
solid. When a tie is drawn at this point, composition of in the spinneret, and the air gap. Early studies
polymer-rich and -lean phases can represent polymer focused on the integrity and adhesion of two layers
matrix and pores, respectively. Initial casting composition, to each other in DL HF membranes. With the
binodal curve position, and precipitation path are related to increased viscosity of the outer layer dope solution,
the final morphology of membranes. When polymeric better adhesion could be obtained. In recent studies,
systems are considered, phase inversion is assumed to be high polymer concentrations in the outer layer are
mainly governed by kinetic parameters. However, kinetics used for nanofiltration.[46,53]
only affects precipitation path line, whereas thermody-
namics governs the position of binodal points.[81] For
Prospects of fabrication methods of the hollow
hollow fiber membranes, polymer solution is extruded
fiber nanofiltration technology
through a spinneret and a fiber starts to form after entering
coagulation bath where solvent and nonsolvent is Recent developments in the fabrication of HF NF
exchanged. Spinning parameters also have effect on phase membranes target improvements in permeate flux,
inversion process. Spinning parameters include dope solu- selectivity, long-term durability, and resistance to
tion viscosity, dope and bore solution compositions, air fouling. One shortcoming of TFC HF NF membranes
gap, dope and bore extrusion rates, and take-up speed.[82] is the vulnerability of amide nitrogen and aromatic
To date, only the removal of chromate[78] and removal of rings in the PA structure to chlorine, a disinfectant
perfluorooctane sulfonate from water[34] have been studied commonly applied in water and wastewater
with membranes prepared by this method. treatment.[21,32,62,76,99] To address this concern,
novel monomers have been employed including
cyclohexane-1; 3,5-tricarbonyl chloride; 5-chlorofor-
Dual-layer hollow fiber nanofiltration membranes
myloxy-isophthaloyl chloride; isomeric biphenyl
The first DL asymmetric HF membranes were fabricated tetraacyl chloride; m-phenylene-diamine-4-
by Dupont.[83] SEM images of a DL HF membrane can be methyl; hexafluoroalcohol-mphenylenediamine; 3,5-
SEPARATION SCIENCE AND TECHNOLOGY 2129

Table 2. Summary of prior studies on the fabrication of single-layer hollow fiber nanofiltration membranes.
Salt rejections
(%) Operational conditions
Specific pure Salt
water Flow concentration
permeate flux rate in the feed
Objective Dope composition (L/(m2∙h∙bar)) MgSO4 NaCl (L/min) (mg/L) Major conclusions References
[78]
To fabricate SL HF Heterocyclic poly 1.86 ~85 ~38 0.8 m/s 409.2 MgSO4 Due to surface charge
membranes for the benzimidazole 198.7 for NaCl characteristic of PBI membranes,
removal of chromate (PBI) rejection of NaCl show V-shape
trend. It is possible to remove
chromate from solution effectively.
[34]
To fabricate SL Poly (m-phenylene ~5.7 ~50 ~15 1.5 200 Increase in the concentration PFOS
membranes for the isophthalamide) and solution pH increased
removal of (PMIA) rejection of PFOS. Rigid aramid
perfluorooctanate groups and 3D hydrogen bonding
sulfonate (PFOS) networks of PMIA polymer
increased mechanical stability.
[6]
To investigate the PMIA 0.937 46.57 8.80 1.5 0.41 for Increasing dope viscosity is the
effects of additives MgSO4 main cause for MWCO and pore
on the morphology 0.19 for NaCl size decrease. Optimal values of
and separation MWCO and pore size are found to
performance of SL be 911 Da and 0.556, respectively.
HF membranes
[37]]
To investigate the PES 0.204 n.a. 18.64 n.a. 1000 Dope extrusion rate as a spinning
effects of spinning parameter affects salt
parameters on the permeability, pure water
properties of SL HF permeability, and salt rejection
membranes properties of the fabricated
membranes. Increasing the rate
resulted in a better rejection and
lower water permeability.
[79]
To prepare defect-free Poly 70.33 n.a. n.a. n.a n.a. Using ethylene glycol methyl ether
skinned (phthalazinone (EGME) or acetic acid (AA) as
nanofiltration ether sulfone additive changes membrane
membranes ketone) (PPESK) morphology from finger-like to
sponge-like. Fabricated
membranes have higher pure
water permeability and high
solute rejections.
[80]
To prepare solvent- Polyphenylsulfone n.a. n.a. n.a n.a. n.a. Fabricated membranes found
resistant (PPSU) promising for the nanofiltration of
nanofiltration mild organic solvents. However,
membranes solvent fluxes should be
optimized.
n.a., not available.

Figure 5. Morphology of a single layer HF nanofiltration membrane [41].

diaminobenzoic acid; 2,5-bis(4-amino-2-trifluoro- aminophenoxy) phenyl] sulfone.[100] These novel


methyl-phenoxy)benzenesulfonic acid; 4,4-bis(4- monomers showed good chlorine tolerance and are
amino-2-trifluoro-methylphenoxy)biphenyl-4; 4-dis- likely candidates for the fabrication of TFC HF NF
ulfonic acid; and disulfonated bis[4-(3- membranes.
2130 G. M. URPER ET AL.

TFN membranes are organic–inorganic nanocompo-


sites that may include a diverse range of nanomaterials.
Silica,[101] titania,[102–104] carbon nanotubes,[105,106] and
zeolite[107] have been used to prepare TFN flat sheet
membranes; however, only titania and SAPO-34 nanopar-
ticles have been studied for the fabrication of TFN HF
membranes.[10,11] Recently, Rajaeian et al.[102] fabricated
TiO2 impregnated TFN HF membrane by using ceramic
HF support. The presence of nanoparticles within PA
matrix can be a concern as aggregation or poor interac-
tion of nanoparticles with monomers or PA matrix itself
may lead to membrane surface defects. These defects are
considered as a flux enhancement mechanism for TFN
membranes but may also compromise salt rejection.
Figure 6. Phase diagram [81]. Coating nanoparticles on the membrane surface would

Figure 7. Morphology of DL HF nanofiltration membrane [37].

Figure 8. Schematic of the dual layer hollow fiber spinning system.


Table 3. Summary of dual layer HF NF membrane studies.
Salt
rejections
(%) Operational parameters
Specific pure Salt
water concentration
permeate flux Flow rate in the feed
Objectives Dope composition (L/(m2∙h∙bar)) MgSO4 NaCl (L/min) (mg/L) Major conclusions References
[38]
To fabricate dual layer HF membranes for Torlon poly(amide-imide)a 6.45 94.2 92.3 0.08 1000 NF selective layer has a positive charge. Compared
water softening and PESb with NF membranes, operating pressure of the
fabricated dual-layer membranes is at least five times
lower and salt rejection is higher.
[7]
To fabricate dual layer HF NF membranes for Poly benzimidazole (PBI)a and n.a. 98 95 n.a. 200 Newly developed membranes exhibit superior heavy
the removal of heavy metal ions from PESb metal removal. PBI material decreases transport
wastewater resistance across the membranes and lowers material
cost.
[8]
To control the effects of inner dope Torlon poly(amide-imide)a 11.93 ~45 ~30 1.41 200 Thermodynamic and kinetic properties of both
additives and outer dope additives and cellulose acetateb spinning dopes are important. NF membrane
performance is affected by the addition of different
non-solvents. An increase in spinneret temperature
can increase solute rejection.
[36]
To use immiscibility induced phase P84 copolyimidea and PANb 3.2 95 40 n.a 1000 Selective layer has narrow pore size. Protection layer
separation for co-spinning dual layer increases PWP and prevent compaction problems in
membranes for dye removal NF. Also, fabricated dual layer HF NF membranes has
found effective for dye removal.
[97]
To simultaneously spin membranes with PVDF and PVP, lithium 560 n.a. n.a. n.a n.a. Optimizing the composition PVP, LiCl and glycerol
thermally induced phase separation (TIPS) chloride (LiCl), ethylene glycol mixtures helps tune the dimensions of pores as
and non-solvent induced phase (EG), and glycerol (Gly) micro-sized pores in the spherulite structure.
separation (NIPS)
[11]
To fabricate DL HF TFN nanofiltration PES, PVDF, PIP, TMC, TEA and 20 n.a 15 1 n.a. Modified TFN membranes have improved pure water
membranes by adding SAPO-34 SAPO-34 nanoparticles permeability and smaller pore size with high porosity
nanoparticles and dense thin film layer. Compared to NF-90,
fabricated membranes have superior hydrophilicity,
water flux, and rejection of micropollutants.
[96]
To fabricate DL HF TFC membranes for Matrimid polyimide, 1.97 n.a. 64 0.15 200 Fabricated membranes could withstand high
organic solvent nanofiltration by slow– diethylene glycol, PVP, pressures (16 bar). SFPS process improved membrane
fast phase separation (SFPS) process tetrahydrofuran, 1,6- defective structure. Fabricated membranes showed
hexadiamine, MPD and TMC 99.3% rejection against ramazol brilliant blue with
methanol flux of 14.4 L/m2.h at 16 bar.
[95]
To fabricate DL HF membranes for organic PBI and P84 polyimide n.a. n.a n.a. n.a n.a Fabricated membranes offered high rejections to low-
solvent nanofiltration molecular-weight compounds in various solvents.
Also, these membranes decreased solvent
consumption during fabrication process.
n.a: not available.
a
Outer layer.
SEPARATION SCIENCE AND TECHNOLOGY

b
Porous support layer.
2131
2132 G. M. URPER ET AL.

Table 4. Comparison of interfacial polymerization and phase inversion methods for NF HF applications.
Interfacial polymerization on phase inverted membranes Phase inversion membranes
Advantages Disadvantages Advantages Disadvantages
High water permeability and good Complex and time-consuming Easy to fabricate Poor adhesion between layers
separation properties fabrication process Cost-effective large-scale in DL membranes
production and operation
Method is well established Material susceptible to degradation Usage of cheap polymers for Hard to find compatible
by chlorine support layer polymers for DL membranes
Good adhesion between support and Hard to obtain homogeneous thin Functional materials for separation Selective layer can be the outer
separation layer film layer in HF membranes layer in DL membranes HF membrane surface
Available commercially
Selective layer can be at either inner or outer
HF membrane surface or both

avoid defect formation but potential detachment and loss direct PI method can produce composite HF mem-
of nanoparticles may defeat this strategy. Another possible branes in one step. SL direct PI produces an ultra-
approach is to incorporate nanoparticles into a separate, thin selective layer and highly porous substrate, so
additional layer under the PA layer.[108] that complexity and long production time of IP on
The most important problem with DL membranes is phase-inverted membrane process can be avoided.
the poor adhesion of the two layers. To improve adhesion, Each method has its own limitations. DL membranes
spinning parameters (e.g., concentration of the dope can be fabricated to have higher tolerance to chlorine
solution[109]) should be optimized. Another strategy could but would have relatively low water permeability. In
be the use of nanoparticles. Dzinun et al.[110] have fabri- contrast, TFC membranes can have higher water per-
cated DL membranes by incorporating TiO2 into the selec- meability, yet their ability to resist chlorine is worse.
tive layer and achieved good interfacial adhesion between For each method, different strategies can be used to
layers with no delamination. Also, mussel-inspired surface minimize respective limitations and achieve optimal
chemistry agents such as norephirephrine, polydopamine, tradeoffs. In the case of DL membranes, adhesion pro-
and heparin can be a solution to this adhesion problem.- blem can be solved by using compatible dope solutions.
[111–113]
They have not been used in DL membranes yet; For TFC membranes, use of nanomaterials that can
these agents can be used as a filler, skin layer, pre-decorator make membranes to resist chlorine or other harsh
of other polymers, and interface layer for TFC membranes. conditions can be solution.
They can also help to enhance the compatibility between
two layers.[113]
Funding
In Table 4, advantages and drawbacks of membranes
prepared by phase inversion and by IP are presented. The authors are grateful to TUBITAK (The Scientific and
The use of reactive materials, layer-by-layer assembly of Technological Research Council of Turkey) for providing
financial support under project number 113Y359.
polyelectrolytes, and biomimetic approaches are promising
and can be adapted to benefit the HF NF technology. For
example, layer-by-layer assembly method uses different
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