10 1016@j Desal 2019 114178

Desalination 478 (2020) 114178
Contents lists available at ScienceDirect
Desalination
journal homepage: www.elsevier.com/locate/desal
Engineering advance
Recent advances in nanofibrous membranes: Production and applications in T

water treatment and desalination
Haleema Saleema, Levent Trabzonb, Ali Kilicc,d, Syed Javaid Zaidia,
⁎
a
Center for Advanced Materials, Qatar University, Doha, Qatar
b
Mechanical Engineering Department, Istanbul Technical University, Turkey
c
Textile Engineering Department, Istanbul Technical University, Turkey
d
Areka LLC, Istanbul, Turkey
GRAPHICAL ABSTRACT
ARTICLE INFO ABSTRACT
Keywords: Desalination of seawater is a promising technique that contributes a reliable and abundant source of clean
Nanofibers potable water. This review investigates the current status and forthcoming advancement in nanofiber tech-
Desalination nology, with a special attention on its production along with its application in seawater desalination and water
Water treatment treatment. Nanofibers are the latest generation of nonwoven filter media, that contribute extraordinary features.
Electrospinning
In this paper, we discuss about the conventional techniques in the nanofiber production, like electrospinning
Membranes
(ES), melt blowing (MB), fibrillated bicomponent fiber extrusion, phase separation, drawing, self-assembly, and
template synthesis, along with its benefits and limitations. We then present the developing nanofiber production
techniques, like centrifugal spinning, plasma-induced synthesis, and solution blow spinning. Here, we also in-
vestigate the developing applications of nanofiber membranes (NFMs) in separation processes like forward os-
mosis (FO), membrane distillation, ultrafiltration (UF), microfiltration (MF), and nanofiltration (NF). This work
also highlights the surface modifications performed in the NFMs for enhancing its efficiency. However, still there
are difficulties to be considered and overpowered for NFM technology to approach further development. We
⁎
Corresponding author.
E-mail address: [email protected] (S.J. Zaidi).
https://doi.org/10.1016/j.desal.2019.114178
Received 4 August 2019; Received in revised form 8 October 2019; Accepted 9 October 2019
0011-9164/ © 2019 Elsevier B.V. All rights reserved.
H. Saleem, et al. Desalination 478 (2020) 114178
believe that with additional advancement in the nanofiber manufacturing procedures and recognition of new
utilization of NFMs, the nanofiber field of technology will develop and cross its present state towards com-
mercialization and utilization.
1. Introduction categorized as electrical, chemical, mechanical, and thermal energy

processes. The desalination innovations are either pressure or thermally
There is a huge requirement for efficient water filtration technolo- driven, and consists of different types of technologies, for example,
gies, because of population growth, global warming and contamination multistage flash (MSF) distillation, membrane distillation, mechanical
of freshwater, and this has prompted increased attention to the devel- vapor compression distillation, multiple-effect distillation, electro-
opment of advanced nanomaterials which can help in the seawater dialysis, reverse osmosis, and nanofiltration processes. Thermally-based
desalination as well as water treatment. The size-dependent filtration is processes are considered to be first-generation technologies, whereas
conceivable by means of nanofiber membranes as they have superior membrane-based techniques are the second generation. A membrane is
porosity and this pore size is adjustable through the manufacturing considered to be a semipermeable medium which just permits specific
procedure. Consequently, it is timely to thoroughly review the different molecules and compounds to go through and restricts the flow of
nanofiber production techniques along with its benefits and drawbacks, others. The membrane-based techniques include membrane distillation
and use of nanofiber membranes in desalination and water treatment; (MD), forward osmosis (FO), reverse osmosis (RO), microfiltration
which will format future trends in the research of nanofiber mem- (MF), nano-filtration (NF), and ultrafiltration (UF).
branes. MD is the most preferable thermally-driven procedure, whereas RO
is noted to be the most favored pressure-driven operation. In this
1.1. Requirement of clean water manner, both MD and RO strategies have been actively explored be-
cause of their great salt-removal performance (especially, > 98% re-
Clean water is considered to be the most fundamental resource for moval of NaCl) and, as a result, are the most utilized seawater desali-
human utilization, and at present, almost 11% of the world's total po- nation methods for generating potable water. Other techniques, for
pulation have no access to pure potable water. In spite of the fact that example, NF, are mostly utilized for removal of lesser NaCl content
water comprises over 70% of the surface of the earth, 97% of this is (about 20 to 80% removal of NaCl) and primarily employed for
unreasonably salty for human consumption. In addition, majority of the brackish water treatment [9,10,11]. Desalination has turned out to be
rest of the 3% is caught in ice caps and glaciers or underground, leaving most convenient and efficient, and studies into membrane-based desa-
lesser than 1% of the world's total supply of water accessible to human lination strategies have progressively increased over the last decade. RO
use [1]. Due to the developing worldwide population and constant and NF membranes are extensively utilized in desalination applications.
economic growth, we have approached a potentially critical situation in The operation efficiency of membrane-based desalination strategies,
adjusting the supply and accessibility of freshwater assets [2]. Because with respect to separation (rejection of salt) and permeability (water
of several factors, such as industrialization, global warming (since en- flux), relies considerably on the membrane characteristics. With con-
vironmental variation influences the hydrologic cycle), and freshwater stant advancements accomplished through the membrane character-
contamination, the current sources of water, for example, recycled istics optimization, the membrane procedures have become more effi-
wastewater, surface water (dams and rivers), and certain underground cient (for example, enhanced permeability) and, as a result, utilize
sources, are getting to be exhausted due to increasing demand as well as lesser energy relative to the thermally-driven operations.
diminishing rainfall for pure water supply. Recycling of wastewater is
further not able to satisfy the need, contingent upon the degree or se- 1.2. Introduction to nanofibers
verity of contamination. The urban populace is anticipated to develop
from around 2.5 billion in 1950 to 9.8 billion in 2050 [3]. Predictions Developments in nanotechnology could extraordinarily assist in
up to 2030 demonstrate an enhancement in worldwide water uptake of overcoming the present problems of satisfying the demand for drinking
almost 40% of the present available and dependable supply sources, water supplies utilizing unique, nanoengineered/nanostructured ma-
which means a heightening of water demand [4]. With pure water as- terials. Nanotechnology, with respect to nanoparticles or nanofiber
sets rapidly running out, the requirement for additional effective as well membranes (NFMs), for desalination or water treatment applications, is
as cheap water treatment strategies is very important to help meet our a relatively latest approach that has developed swiftly in interest as a
constantly developing water needs. Subsequently, the requirement for strategy to enhance efficiency by upgrading the membrane surface
technological advancement to empower innovative desalination and properties. The field of nanomaterials includes a wide scope of inter-
wastewater/water treatment technologies cannot be exaggerated [5,6]. esting materials with extraordinary physical as well as chemical prop-
The conversion of seawater, brackish water, and wastewater into po- erties. The nanomaterials include zero-dimensional (0-D) nanoparticles
table water needs superior water treatment. (all 3 dimensions are in the range of 1 nm–100 nm, for example,
Desalination can be carried out on seawater or inland underground quantum dots), one-dimensional (1-D) (here, one of the dimensions is in
brackish water, of which seawater treatment is more achievable relative nanometer scale, examples include nanofibers, nanorods, nanotubes,
to brackish-water treatment. Desalination of seawater offers a con- nanowires), and two-dimensional (2-D) nanosheets (here dimensions
sistent and abundant supply of water with good quality. The seawater are > 100 nm [12,13,14]. Extensively presented as nanomaterials with
desalination is regularly utilized in deserts as well as in arid regions, incredible application possibilities, the nanofibers distinguish itself
however, because of global water stresses the desalination has turned among the remaining nanomaterials. A standout among the most re-
out to be increasingly prevalent in developing nations over the years. markable characteristics of nanofibers is their significantly higher sur-
Desalination includes the seawater evaporation, by that separating the face-area-to-volume ratio along with greater porosity [15]. The afore-
salts, minerals, as well as different impurities, to produce pure water for stated features turn these fibers a strong and excellent candidate for
household in addition to industrial utilization. The greater salt con- several progressive utilizations in areas like superior performance fil-
centration of seawater makes it an expensive operation. The salt con- tration, composite materials, battery separators, tissue engineering,
tent or salinity of seawater is because of the existence of almost 3.5% wound dressing, electrochemical sensing, blood vessel engineering,
sodium chloride (NaCl). Potable water ought to have a salt concentra- vascular grafts and reinforcements [16,17,18]. As a matter of fact, the
tion below 280 ppm [7,8]. The methods for seawater desalination are significance of nanofibers can be seen from the numerous constituent
2
H. Saleem, et al.
Table 1
Comparison of different conventional nanofiber production techniques.
Nanofiber production Types of material Range of fiber Benefits Drawbacks Ref.
techniques dimension
Electrospinning PA, PU, PEO, PVP, PLA, PP, PCL, Few nanometer to Highly porous, long, continuous, interconnected, 3-D fibrous system, Toxic solvents, Instability of jet [27], [77]
polylactide, PVA, PES, PAN, PVDF, PSf, several microns that contributes an elevated internal surface area and consequently
PANi, PET, Kevlar, PI, PS immense separation ability. Simple instrument, continuous process,
Cost effective.
Melt blowing Polyesters, PE, PP, PA, PU, PVC, PVA, PAN, 250 nm to several High productivity, Continuous and long fibers, No issues of solvent Polymer thermal degradation, Incapability to [77],
PBT, PS microns recovery design adequately smaller orifice in the die
Drawing PMMA, PVB, PEO, PVA, PCL, blend of 2 to 100 nm Process simplicity, accessibility, can be effectively modified, no Process is time-consuming, not suitable for entire [58], [77],
hyaluronic acid (HA), Fish gelatin (FG) requirement for an expert person for handling the system polymers. Gets exceptionally long single fiber [73]
having poor shape.
3
Phase separation PLLA, PLGA, PDLLA, chitosan 50–500 nm Inexpensive, Simple equipment requirement, Generates one by one Hard to retain porosity, time-consuming [61], [77]
continuous nanofiber and large scale manufacturing is likewise procedure, absence of structural stability, and
conceivable not appropriate for all polymers
Template synthesis PCL, PANi 25–400 nm Capability to manufacture nanofibers with various diameter Complicated process. Cannot generate nanofibers [57], [77]
with extended fiber length
Fibrillated bicomponent fiber Polyester, polystyrene, co-polyesters 100–800 nm Long as well as continuous fibers, relative uniformity Solvent recovery along with additional [77]
extrusion (COPET), PVA, thermoplastic starches processing
Self-assembly PA, PVA, PEI Diameter 5–25 nm Considerably lesser diameter of nanofibers in the range of a few No control on fiber dimensions. Complicated and [78], [77]
nanometers low productivity technique.
Not scalable.
Polyamide - PA, Polyurethane - PU, Polyethylene oxide - PEO, Polyvinylpyrrolidone - PVP, Polylactic acid - PLA, Polypropylene - PP, Polycaprolactone - PCL, Polyvinylalcohol - PVA, Polyether sulfone - PES,
Polyacrylonitrile - PAN, Polyvinylidene fluoride - PVDF, Polysulfone - PSf, Polyaniline - PANi, Polyethylene terephthalate - PET, Polyimide - PI, Polystyrene - PS, Polyethylene - PE, Polyvinyl chloride - PVC, Polybutylene
terephthalate - PBT, Polystyrene - PS, Fish gelatin (FG), polymethylmethacrylate – PMMA, polyvinyl butyral –PVB, poly-lactic-co-glycolic acid- PLGA, poly-DL-lactic acid – PDLLA, Poly-L-lactide acid – PLLA.
elements from which they are synthesized to the scope of utilization in frameworks with extensive pore size distributions (pore size in micron
which they have been exhibited to have a critical effect. Nanofibers are range) restrict their capability to separate dissolved salts, like NaCl,
usually produced from a combination of materials, for example, syn- from water. In this manner, they are restricted to MF-separation utili-
thetic polymers [19,20], natural polymers [21], composite nanoma- zation involving microsized particles, or as pre-filters before sensitive
terials [22,23], semiconducting nanomaterials [24,25] and carbon- RO procedures. With proper modification, the water treatment utili-
based nanomaterials [26]. Besides the quick advancement in the pre- zation of these membranes could be additionally extended to the se-
paration as well as characterization of nanofibers during recent years, paration of extra complex colloidal solutions, like oil/water suspen-
considerable efforts have been concentrated on investigating the po- sions, that involves the organic solute separation. Modification of an
tential nanofiber utilization, inclusive of water treatment, environ- electrospun nanofiber membrane surface with a thin selective coating
mental treatment, biomedical engineering, healthcare, energy storage, layer by crosslinking leads to the development of a composite mem-
and generation. brane having small pores which could be utilized for ultrafiltration
It can be noted that nanofibers are attaining great recognition in separation applications. Additional modification using interfacial
their utilization as membranes essentially because of the remarkable polymerization (IP) coating results in nonporous composite membranes
properties of these materials. Membrane filtration system is improved which could be employed in RO and NF utilization. IP develops a
further by integrating the nanofibrous media. It is widely recognized coating of polyamide (PA) as a super-thin top selective layer on the
that a nanomaterial should have minimum one dimension of the order ENFM surface, leading to a thin-film nanofiber composite membrane;
of 100 nm or lesser [27]. On the other hand, many researchers count and this type of membrane could be utilized in MD as well as RO se-
fibers having a diameter up to 1000 nm as nanofibers [28,29]. Nano- parations. The coated layer of a thin-film nanofiber composite mem-
fibers can be prepared utilizing various techniques, for example, bi- brane could be furthermore modified to enhance salt rejection and
component extrusion, electrospinning (ES) [30], melt blowing (MB) permeability through the incorporation of nanoparticles. The inclusion
[31], phase separation [32], centrifugal spinning (CS), drawing [33], of nanoparticles into electrospun nanofiber membranes assist to im-
self-assembly and template synthesis [34]. Out of them, ES is a direct, prove performance (both salt rejection and flux); and hence, the ap-
economical, and flexible strategy that basically utilizes a cost-effective plication of nanotechnology in current desalination technologies can
and simple setup to manufacture nanofibers in different sizes and lead to superior membrane efficiency.
shapes. In the majority of the aforestated operations, the fibers are Despite the fact that a few research works have been published on
assembled as non-woven random fiber mats. nanofiber preparation, it has been acknowledged that a thorough and
Nanofiber membranes manufactured by ES technique form part of efficient review covering all the traditional and emerging strategies for
the nanotechnology-based strategies employed to manufacture unique nanofiber manufacturing must be carried out which is necessary for
separation membranes. The electrospun nanofiber membranes (ENFMs) future improvements in the field. Hence, we will discuss in this article
have remarkable properties, and hence these type of membranes can be all the important conventional and emerging techniques for the nano-
utilized to prepare multi-functional water purification materials. fiber preparation, along with its benefits and drawbacks. Besides, we
Despite that, for desalination utilization, their extremely porous will briefly examine the membrane manufacturing using the ES
Fig. 1. a: Diagrammatic representation of the nanofiber production process by ES technique. Adapted from reference [72]; b: Schematic portrayal of the MB system.
Adapted from reference [48]; c: Portrayal of bicomponent spunbonding process. Adapted from reference [51]; d: Schematic representation of the nanofiber man-
ufacturing process by template synthesis method. Adapted from reference [73]; e: Schematic depiction of the nanofiber fabrication process by phase separation
technique [58] f: Schematic representation of the nanofiber production process by drawing technique. Reference [58]; g: Demonstration of the apparatus utilized for
CLSD. Adapted from reference [70]; h: Schematic representation of the nanofiber fabrication process by self-assembly technique. Adapted from reference [58].
4
technique, with a specific focus on the various ES strategies, factors strategies for nanofiber membrane production, and the recent advances
affecting the ES process and modifications of electrospun membranes. in the nanofiber membranes for microfiltration, ultrafiltration, nano-
This review paper will also inspect the advancement of electrospun filtration, membrane distillation and forward osmosis in desalination
nanofiber membrane for seawater desalination and water treatment and water treatment applications.
processes.
Considering the latest updates in desalination and water treatment 2. Conventional nanofiber fabrication methods
field, we believe that it is important to summarize the latest findings in
this review paper with the cutting-edge research advancements. The various methods capable of manufacturing nanofibers are
Numerous developments are promptly being made in the manu- electrospinning, melt blowing, fibrillated bicomponent fiber extrusion,
facturing as well as modification of nanofiber membranes for desali- template synthesis, phase separation, drawing, and self-assembly. The
nation as well as water/wastewater treatment, particularly in the past required alignment, the amount, the cost, and the fiber material re-
several years. Accordingly, in this review paper, we review the nano- quired are the elements to be considered while selecting the appro-
fiber applications in desalination and water treatment with special priate among these techniques. Distinct nanofiber structures, for ex-
emphasize on the research advancements in the last 5 years. We also ample, porous, hollow, bicomponent, and core-shell structures, could
examine the emerging applications of nanofiber membranes in se- be manufactured by utilizing these methods. Table 1 is the comparison
paration processes like MD, FO, NF, UF, and MF. In combination with of different conventional nanofiber production techniques including its
the differing modifying techniques, we analyze the relation between the advantages, drawbacks, types of material, and range of fiber dimension.
structure of membrane and separation performance. Likewise, we will In the subsequent section, we present a brief review on each of the
present here the industrial scaling-up and future scope of nanofiber conventional nanofiber fabrication techniques.
membranes. We believe that this paper would contribute new insights
and knowledge for the scientific community in this field. This will also
2.1. Electrospinning
contribute to the investigation of more advanced nanofiber membranes
for desalination and water treatment applications. To the best of our
Electrospinning (ES) is a versatile method appropriate to various
knowledge, there are not many studies dealing with nanofiber mem-
inorganic as well as organic systems and this method has a wide scope
brane preparation and application, and discusses about the conven-
of utilization which can give rise to a firmly controlled nanomaterial
tional and emerging nanofiber production techniques, different
size distribution [9,35]. The resultant nano-framework can be
Fig. 1. (continued)
5
portrayed as an exceedingly porous network framework, possessing an be favorable [42]. The major benefits of electrospun nanofiber mem-
enormous surface-area-to-volume ratio, whose dimensions could be branes are the existence of the exceedingly porous, interconnected,
effectively adjusted as well as optimized at the time of manufacturing. three-dimensional (3-D) fibrous system, that contributes an elevated
The ES technique permits for the increased volume production of na- internal surface area and consequently immense separation ability,
noscale, mesh-like, lightweight, extremely functional structures. The ES relative to typical membranes with a two-dimensional (2-D) framework
technique involves the utilization of a superior voltage electric field on [9].
a dope polymer solution (that is, a polymer-solvent system) to generate Electrohydrodynamic (EHD) direct-writing is a prominent strategy
a solution jet [36]. At the point when the jet is being extended and the for the manufacturing of nanofiber because of its high productivity and
solvent is vaporized, specifically subsequent to the whipping procedure, simplicity. EHD direct writing is a highly effective method for satisfying
fibers in the range of several microns to nanometer scale can be at- the growing demands of huge-area nano/micro-manufacturing. It is
tained [37]. The fundamental ES system comprises of three major parts, innovative to direct-write sub-100 nanometer fibers on a flexible/rigid
inclusive of a feeding area, a collector area, and a high voltage power substrate utilizing organic materials. A kinetically regulated mechano-
supply. The aforestated fundamental parts are presented in Fig. 1.a. The electrospinning (MES) procedure for the programmable and continuous
feeding segment consists of feed storage (solution of polymer), a spin- direct writing of hierarchic nanofibers/microfibers in the superior re-
neret (specifically a thin metallic needle), along with an injection pump solution goals was illustrated by Huang e. al. [43]. Also, this technique
for injecting the dope polymer solution at a consistent flow rate. is characterized by its high resolution, noncontact, additive as well as
The fibers with various characteristics (for example, topography and reproducible processing, as well as organic material compatibility. EHD
morphology) can be manufactured by changing the ES conditions [38]. direct-writing technique has numerous benefits: additive process for
For majority of the applications, uniform nanofibers are preferable less-cost, noncontact designing with low imperfections, eco-friendly
[39]. On the other hand, in the field of the superhydrophobic and hy- manufacture, patternability on non-planar surfaces, digital procedure
drophobic materials, beaded fibers as well as particles are regularly for real-time modification, registration over enormous regions, and a
preferred [40]. In the ES technique, fiber morphology, orientation, and lower-temperature process which is compatible with room temperature.
surface topography are to a great extent determined by operating Also, the EHD direct-writing might be integrated with different manu-
conditions along with properties of solution [41]. The polymer solution facturing methods to generate novel functional frameworks. For in-
conductivity is additionally known to alter the properties of the re- stance, on the basis of consolidation of self-assembly and EHD jet
sulting fibers [42]. For enhancing the conductivity of dope solution, a printing, 3-D block-copolymer films with various configurations might
few researchers included various salts, where the results were noted to be manufactured [44]. By means of the contribution of a greater
Fig. 1. (continued)
6
engineering and scientific network, EHD direct-writing will most likely 2.4. Template synthesis
turn out to be a regenerative nano-fabricating procedure for nanos-
tructures as well as devices, not only for nano-materials or nanofibers. Template synthesis is another regularly utilized method mainly to
generate inorganic nanofibers, for example, carbon nanotubes, and
nanofibers [54], polypyrrole (PPy) [55] or conductive polyaniline
2.2. Melt blowing
(PANI) [56], and so forth. In this technique, utilizing electrochemical or
chemical oxidative polymerization, polymeric, ceramics, semi-
Melt blowing (MB) is a standout among the most well-known pro-
conductors, or metallic nanofibers can be produced employing a non-
cedures to prepare superfine fibers on the submicron or micron scale. In
porous membrane consisting of various cylindrical pores (thickness
this technique, a thermoplastic polymer is undergone extrusion using a
from 5 mm to 50 mm). The technique involves the utilization of mold or
die, and attenuation is quickly carried out by the hot air stream to
template to get the required structure or material and generate nano-
prepare fine fibers [45]. Fig. 1.b presents a schematic representation of
fibers. In this technique, the nanofibers are prepared by allowing to
the MB system where high-speed air jets impinge over the polymer as it
pass solution of a polymer through the pores having a diameter in na-
comes from the spinneret. The fibers, which are attenuated, are later
noscale under the water pressure application on one side, that brought
located on a collector screen to generate a self-bonded, fine-fibered
about polymer extrusion and delivering fibers after interacting with
web. Consolidation of fiber-to-fiber bonding and fiber entanglement
solidifying solution. Fig. 1.d is the diagrammatic representation of the
gives proper cohesion of web, that the web could be utilized with no
nanofiber manufacturing process by template synthesis method. This
additional bonding. The fibers, prepared from MB technology, have
strategy cannot manufacture nanofibers with extended fiber length,
diameters from 2 μm to 5 μm. Recently, the researches have focused on
only nanofibers with certain micrometers long can be prepared, and the
achieving nano-sized fiber diameters under the process conditions of
fiber diameter is based on the membrane pore size [57]. The capability
the MB process [46]. Nanofibers could be manufactured by extra-
to manufacture nanofibers with various diameter, utilizing various
ordinary die designs having a smaller orifice, by decreasing the poly-
templates, is one of the benefits of this technique. The system might be
meric melt viscosity and by reasonable modification of the MB setup.
further investigated to produce inorganic membranes for separation
If the MB technique can be utilized to generate the nano-sized fibers,
application.
then this will contribute a lot simpler, quicker, and less expensive
strategy to generate nanofibers, different from the ES procedure. The
MB procedure depends on Wente's unique research published in the
2.5. Phase separation
year 1956, where the nano-sized meltblown fibers with fiber diameters
as reduced size as 500 nm were reported [47]. In recent times, Khan
In the phase separation technique, phases will separate due to the
and his coworkers have analyzed the preparation of melt-blown non-
physical incompatibility. The solvent phase is separated from the so-
woven nanofiber along with their filtration features [48]. They stated
lution whereas the other phases persist. The concentration of polymer
that when the size of fiber was decreased lesser than 1 μm, superior
influences the nanofiber properties. As the concentration of polymer is
filtration properties was accomplished at lesser weights compared to
elevated, the porosity of fiber is diminished, and the fiber mechanical
those of typical melt-blown webs. The results indicated a substantial
properties are enhanced [57]. In phase separation technique, the first
guarantee to utilize melt-blown nanofibers in filtration.
step is the preparation of a homogeneous solution by dissolution of
polymer at elevated/room temperature and after that getting the gel
2.3. Fibrillated bicomponent fibers extrusion from the solution by retaining the solution at the gelation temperature
where nanofibrous frameworks are developed because of phase se-
In this method, the nanofibers are prepared by pulling apart the paration, succeeded by extraction of solvent and matrix drying which
various components or separating one of the segments of bicomponent prompts the generation of nanofibers. The schematic depiction of the
fibers which have two immiscible polymers organized in the cross- nanofiber fabrication process by phase separation technique is pre-
section [49,50]. For generating nanofibers, minimum one of the com- sented in Fig. 1.e [58]. The phase separation technique has a require-
ponents should have a nanosized cross-section. The most widely ob- ment of process minimum equipment. Also, this method can legiti-
served cross-sectional shapes of fibrillated bicomponent fibers are mately manufacture a nanofiber matrix where the mechanical
hollow segmented-pie, segmented-pie, and islands-in-the-sea. The characteristics of the matrix could be adjusted by changing the con-
schematic representation of the fibrillated bicomponent fiber extrusion centration of polymer [59]. Up till now, only certain polymers, for
process is presented in Fig. 1.c [51]. In general, when the islands-in-the- example, polyglycolide and polylactide (PLA), have been manufactured
sea fibers are seen in the cross-section, different individual fibrils (is- into nanofibers utilizing this strategy [60]. By utilizing this technique,
lands) composed of single polymer constituent are in the middle of a no long continuous fibers are prepared, and not all polymers are able to
matrix (sea) composed of the second polymer constituent. Islands-in- experience phase separation and manufacture nanofibers as it needs
the-sea nanofibers might have a non-uniform or uniform diameter of gelation ability that constrains the utilization of this technique. A
the island component. For segmented-pie fibers, two polymer con- comprehensive strategy for poly(L-lactic) acid (PLLA) nanofiber man-
stituents are organized alternately along the fiber cross-section peri- ufacturing has been stated by Ma et al. [32] in four major stages as
meter, whereas hollow segmented-pie fibers additionally have a hollow mentioned earlier. The nanofibers prepared utilizing this strategy have
framework together with the segmented-pie fiber features. Segmented- a diameter of 50 nm to 500 nm, and has a porous framework with a
pie framework forms nanofibers and microfibers (diameter from system of endless filaments. Polymer type, solvent type, gelation
500 nm–2 mm) having non-circular cross-section. The bicomponent fi- duration, thermal treatment, and gelation temperature influence the
bers are manufactured by co-extrusion of two polymers melts by means morphology of the nanofibers. The phase separation method is in-
of a spinneret with a required cross-sectional configuration [52]. Sub- expensive, simple, and commonly utilized for the manufacture of na-
sequent to the production of bicomponent fibers, breaking up the nofibers. This technique prepares one by one continuous nanofiber and
constituents or separating one constituent is pursued to prepare nano- large scale manufacturing is conceivable with the phase separation
fibers. Nakata et al. [53] manufactured continuous polyethylene ter- method. On the other hand, it endures some significant drawbacks, for
ephthalate (PET) nanofibers with a 39 nm diameter with additional example, it is time-consuming procedure, absence of structural stabi-
drawing and removal of the sea component. This island-in-the-sea lity, not appropriate for all polymers, and hard to retain porosity [61].
technique for the generation of nanofiber is however a strategy which
could be scaled towards industrial manufacturing.
7
2.6. Drawing movable platen, an acrylic vacuum compartment with SeeZn windows,
an orifice of 0.5 mm diameter for the fiber injection, a vacuum pump
Drawing method is same as the dry spinning method in fiber- and a high-speed camera with a long-range zoom lens. From this study,
forming industry that has the ability to generate extended single na- it was noted that the diameter of fiber relied upon the drawing condi-
nofibers. The drawing process is represented as the dry spinning tech- tions utilized, for example, chamber pressure, fiber supply speed, laser
nique at a molecular level. The aforestated strategy could only be ap- power, and laser irradiation point. A nanofiber produced at a chamber
plied to viscoelastic materials which can undergo an enhanced degree pressure of 20 kPa and a laser power of almost 20 W had a draw ratio of
of deformations, however remaining adequately strong to hold up the 291,664 and an average diameter of about 0.337 μm; and a drawing
stress developed in the course of pulling. This innovation is schemati- speed in the CLSD technique was 486 m/s. This study demonstrated
cally represented in Fig. 1.f. A conventional drawing system needs a that utilizing this basic strategy, i.e. CLSD, the generation of polymer
proper, such as silicon dioxide surface; a micropipette along with a nanofibers with enhanced mechanical properties and prolonged chains
micromanipulator for producing nanofibers. Mostly three stages are can be accomplished.
involved in this procedure, stage 1: application of a polymer solution
millimeter drop on the substrate material, stage 2: the micropipette 2.7. Self-assembly
later descends against the drop edge, and stage 3: contact as well as by
back movement of micropipette, the fiber is ripped out of the droplet of At present, nanofibers can also be produced through self-assembly
polymer at a specific rate and lastly, the liquid polymer is produced in in solution. This technique is schematically represented in Fig. 1.h.
the nanofiber. Utilizing this technique, the manufacturing of synthetic or natural na-
In the aforestated nanofiber production technology, speed-ex- nofibers might be accomplished by means of impulsive association of
tracting fibers should be around 10−4 m/s. The diameter of fiber pre- individual macromolecules into stable and ordered nano-sized supra-
pared using drawing technique is from 2 nm to 100 nm up to a few molecular patterns or structures. For instance, chitin nanofibers self-
micrometers; length will be from 10 mm to a few centimeters from this assembled for generating networks on drying a chitin-squid pen solu-
system. The nature of nanofiber is mostly contingent upon drawing tion in a chitin nanofiber ink [21]. Relative to the nanofibers prepared
velocity, composition of material, and quick solvent evaporation. using the ES technique, the nanofibers manufactured using self-as-
Different polymers, for example, polycaprolactone (PCL), poly(vinyl sembly method have considerably lesser diameter. On the other hand,
alcohol), polymethylmethacrylate (PMMA), polyvinyl butyral (PVB), this method is complicated with low productivity which needs a so-
and polyethylene oxide (PEO) are effectively utilized for the manu- phisticated set-up.
facturing of nanofiber by this method. The drawing technique has Thus, in Section 2, different conventional nanofiber fabrication
several benefits such as the process simplicity, accessibility, adjust- techniques like electrospinning, melt blowing, fibrillated bicomponent
ability, and no requirement for a proficient person to handle the system. fiber extrusion, template synthesis, self-assembly, phase separation, and
On the other hand, this technique has several drawbacks, for example, drawing have been examined. Some of the fabrication methods like MB
the process is very slow, gets exceptionally long single fiber having poor and bicomponent spinning are limited to few polymers. Controlling the
shape, and not suitable for entire polymers. Xing et al. [62] produced fiber diameter is very difficult in methods like self-assembly, phase-
elastic and flexible poly(trimethyleneterephthalate) nanofibers from separation, and drawing. Regulating the physico-chemical properties of
molten state by single step drawing procedure. The obtained results nanofibers and ultimately scaling up to commercial fabrication is the
recommended that the poly(trimethyleneterephthalate) nanophotonic greatest challenges related to its manufacturing. Due to the fact that the
fibers are promising candidates for preparing ultra-compact photonic- ES is still the most commonly employed technique for the nanofiber
integrated circuits and miniaturized photonic devices [62]. fabrication, their parameters influencing the fiber properties is ex-
CO2 laser supersonic drawing (CLSD) is a procedure to effortlessly tensively reviewed in Section 4. An ideal range of entire parameters is
manufacture nanofibers. The CLSD technique utilizes just CO2 laser essential to develop the nanofibers with specified characteristics.
irradiation and have no requirement of any extra procedures or sol-
vents. CLSD restricts the nanofiber scattering in the air due to the fact 3. Emerging strategies for nanofiber fabrication
that the process is carried out under vacuum. Also, this closed frame-
work strategy contributes better ecological safety, relative to MB and Despite the fact that majority of the nanofibers are prepared uti-
ES, that is performed in open frameworks. The nanofibers prepared by lizing the ES technique, this method has got a few disadvantages, for
CLSD technique can be manufactured considerably long, since the fiber example, dependency on electrical properties of polymer solutions,
is provided at a consistent speed and is continually irradiated using a electrical shock risks and low productivity per nozzle. The nanofiber
laser beam. Utilizing a CO2 laser, the original fibers having diameters contribution in different fields will rely upon the advancement of new
range 100 to 200 μm are undergone melting and afterward passed over and cheap innovations, only those which can satisfy the demand of
a supersonic airflow to accomplish the supersonic drawing of nanofi- various sectors. Therefore, ongoing years have witnessed the enhancing
bers dependent on the air force. The CLSD technique has just been development of unique methods for preparing the nanofibers on a
employed for the manufacture of polyethylene terephthalate (PET) larger scale and greater degree of efficiency, as outlined here. We dis-
[63], poly(L-lactic acid) (PLLA) [64], isotactic polypropylene (iPP) cuss here some of the emerging strategies of nanofiber fabrications such
[65], poly(ethylene-2, 6-naphthalate) [66], poly(tetrafluoroethylene- as centrifugal spinning (CS), plasma-induced synthesis, and solution
co-perfluoropropyl vinyl ether) [67], poly(glycolic acid) [68], and blow spinning (SBS) techniques. The aforestated next-generation na-
ethylene tetrafluoroethylene [69] nanofibers, and the aforestated nanofiber production techniques will be focused towards processing se-
nofibers were prepared without separating the second component or curity and increased yields, as the market of nanofiber is expanding.
without utilizing any solvent. Also, this technique can improve the
thermal resistance of nanofibers by just physical treatment with no 3.1. Centrifugal spinning
modification of the molecular framework [70]. Also, a recent research
has newly illustrated the preparation of nylon-66 nanofibers having ES is certainly the most widely utilized method for the production of
superior melting point close to the equilibrium melting point utilizing nanofibers; however, it has a few disadvantages, for example, de-
the technique CLSD [71]. Fig. 1.g demonstrates the apparatus utilized pendency on electrical properties of solutions, high electric field re-
for CLSD in the study performed by Suzuki et al. [70]. It comprises of a quirements, low production rate, and numerous other safety issues
spool for supplying the fiber, a constant wave CO2 laser having about [60,79]. Centrifugal spinning (CS) is a nanofiber preparation strategy
10.6 lm output wavelength and a higher power of almost 40 W, a and it has received broad interest primarily because of its excellent rate
8
of production, that is almost 50 times higher than conventional ES polymer nanofibers, and so forth. The previously mentioned benefits of
technique [80]. Instead of utilizing the electrostatic power, the CS CS method make it a potential candidate for manufacturing nanofibers
process uses the centrifugal force to realize the excellent production in an inexpensive, commercial-scale model. In the case of large scale
rate of nanofibers [81]. CS process can be utilized to manufacture na- manufacturing of nanofibers by CS technique, an enhancement in the
nofibers by employing polymer melts or polymer solutions, without the rate of production can be accomplished by just rising the number of
dielectric constant limitations and the association of extreme voltage spinning heads along with the number of nozzles present on every
electric field. In addition, metal, ceramic and carbon fibers can likewise spinning head. The next point is that, relative to the ES strategy, the CS
be manufactured by CS technique [82,83]. The schematic representa- technique generally utilizes polymer solutions with elevated con-
tion of the experimental set-up of centrifugal spinning method is shown centrations, resulting in marginally thicker fibers. The aforestated could
in Fig. 2.a [74]. It is important to note that the CS procedure was at first be solved by utilizing motors having more advanced rotational speed.
developed by Hooper in the year 1924 to prepare artificial silk fiber The third point is that, the fiber mats assembled in a laboratory-scale CS
from viscose by the application of centrifugal forces to a viscous ma- equipment are packed loosely, and relative to the densely packed fiber
terial [84]. The CS process of nanofibers has attracted immense con- mats manufactured by ES technique, the aforestated loosely-packed
sideration in academia in recent years. The fiber formation procedure in fiber mats probably will not be advantageous in certain utilization. The
CS process depends upon the competition between viscous forces and aforementioned problem could be solved by post-treatments, like hot
surface tension of the polymer jet and applied centrifugal forces. During pressing as well as calendaring, subsequent to the collection of fiber.
the CS, the nanofiber manufacturing procedure can be classified into 3 The fourth point is that, the majority of the presently reported nano-
different phases: Phase 1: jet-initiation for forcing the solution stream of fibers by CS method depend on a simple strong structure. On the other
polymer via the orifice, Phase 2: jet-extension to improve surface area hand, it is conceivable to develop core-shell nanofibers by CS of two
of the forced stream of polymer, and Phase 3: evaporation of solvent to solutions coaxially with a cautiously structured spinning head.
solidify as well as shrink the polymer jet. So as to completely com- Because of its numerous benefits, it can be anticipated that nano-
prehend the nanofiber manufacturing process in CS, the researchers fibers prepared from CS technique are good candidates for utilization in
have carried out simulation along with modeling work and delivered different applications, such as filtration, aerospace, composites, energy
significant knowledge. For instance, Mellado et al. [85] stated a scaling storage, and semiconductors. Also, it can be noted that most of the
structure supplemented by a semi-analytic as well as numerical tech- current investigations on CS are concentrated on generating different
nique for characterizing the regimes of nanofiber manufacturing and materials as well as their utilization; however, more thorough work, for
suggested a hypothetical model for radius of fiber, based on process example, computational modeling on different forces associated with
parameters inclusive of angular speed, viscosity, orifice radius, and the CS process and their effect on the fiber mechanical characteristics,
distance to the collector, which is considered to be significant for reg- and researches on the impact of various temperatures on structure of
ulating the morphological nature of nanofibers prepared by CS process. fiber should be possible to understand completely the procedure as well
Compared to the other traditional nanofiber production techniques, as the structure-property-processing-performance relationships. In the
the CS method has several significant benefits: the method has a simple case that the set-up of device and collection issues could be addressed
set up with low cost, it does not depend on higher electric fields, it has and the procedure could be properly comprehended, CS technique will
great rate of production and it is able to work with viscous polymer become soon the best option for inexpensive, fast nanofiber manu-
melts or concentrated solutions of polymer. Therefore, the CS technique facturing. The aforestated can initiate possibilities for the innovative
can be utilized to generate ceramic nanofibers, carbon nanofibers, work in an industry in addition to academia.
Fig. 2. a): Diagrammatic representation of the experi-

mental setup of centrifugal spinning method. Adapted
from reference [74]; b): Diagrammatic portrayal of the
experimental setup of plasma-induced synthesis tech-
nique. Adapted from reference [75];] c) Schematic re-
presentation of an SBS device displaying concentric
nozzles. Adapted from reference [76].
9
Centrifugal jet spinning (CJS) is a flexible technique and has been with diameters from 15 to 25 nm have been prepared in water.
developed for the generation of nanofibers or microfibers in an in-
expensive, very productive, and high-efficiency mode [80,86,87]. The 3.3. Solution blow spinning
CJS technique has been demonstrated to be very effective on account of
its ability to certainly manufacture high amounts of nanofibers within a Solution blow spinning (SBS) is another scalable strategy for the
shorter duration at less power consumption as well as reduced cost and fabrication of nanofibers where compressed air is utilized for the fiber
for its capability to be scaled-up for an increasing rate of production formation. SBS method has been developed for overcoming the dif-
[88,89]. CJS technique uses a great centrifugal force developed by a ferent limits of traditional ES procedure, for example, the complication
rotating reservoir for extruding the nanofibers. Also, it can be noted in the in situ preparation of nanofibers and the necessities for high
that only few researches exist which have examined the factors asso- electrical potential [20]. The SBS procedure is beneficial for preparing a
ciated with the CJS manufacturing process experimentally [86,88], series of nanofibers and microfibers from polymer solutions. This
with certain studies concentrated on computational modeling [90,91]. system was developed utilizing the components of both melt blowing
In general, the attenuation of polymer jet into nanofibers employing and electrospinning techniques, as an alternative technology for gen-
CJS technique is accomplished by means of the controlled handling of erating nonwoven webs of nanofibers and microfibers having diameters
viscoelasticity, centrifugal force, and mass transfer features of the practically identical with those produced by the ES procedure with the
spinning solutions. Consequently, the evaporation rate as well as the benefit of possessing a rate of fiber production (estimated by the rate of
elasticity of solvent and spinning solution, respectively, will vigorously polymer injection) a few times greater. The diameters of fibers prepared
impact the consequent diameter of the nanofiber prepared [86]. As a using SBS technique varied from 40 nm for poly(lactic acid) (PLA) to a
matter of fact, various solvent-polymer mixes, for example, water- few micrometers for PMMA. The requirements for the SBS system in-
polyvinylpyrrolidone, dichloromethane-polyvinylpyrrolidone, ethanol- clude a concentrated solution of polymer, a coaxial nozzle, along with a
polyvinylpyrrolidone, and dichloromethane-poly(L-lactic acid), were compressed gas source, and hence, the procedure might be possibly
utilized as spinning solutions for the production of nanofibers using the used for in situ deposition of nanofiber mats as well as scaffolds for
technique CJS [86]. Kilic et al. [92] produced silica nanofibers via appropriate coverage of targets that are non-conductive. The coaxial
centrifugal spinning (C-spin) and followed by calcination. Nanofibrous nozzle is the critical element, through which the solution of polymer is
ceramic mats were investigated for their filtration performance. The pumped via the inner nozzle whereas a steady, high-speed gas flow is
reduction in average nanofiber diameter was found to be advantageous maintained via the outer nozzle. Fig. 2.c is the schematic representation
for particle capture performance of the mats. of an SBS device displaying concentric nozzles.
One of the greatest difficulties in any nanofiber manufacturing With respect to the electrospinning procedure, the SBS process can
procedure is understanding the function of the different production be carried out at significantly greater injection rates. Besides, the SBS
parameters which decide the overall chemical and physical properties procedure does not have the requirement of high voltage apparatus or
of the nanofibers prepared. The technique CJS needs a certain funda- an electrically conductive collector, however, it could be utilized for
mental knowledge of fluid mechanics, processing, and polymer chem- coating any sort of material having a more extensive array of solutions
istry [85,93]. The most outstanding benefit of CJS method lies in its of a polymer. Also, this technique is not restricted to electrical prop-
remarkable productivity. In particular, its productivity is considered to erties of solvents and polymers. The SBS technique utilizes processes
be around 500 times greater relative to traditional ES technique. This which are same as those utilized in industrial techniques for the pro-
was demonstrated in a recent report stating the utilization of CJS duction of fiber, that empower its future appropriateness in a com-
technique for the fast generation of adaptable multilevel structured mercial-scale generation. The unique features of SBS contribute a way
silica nanofibers and microfibers, in accordance with the phase se- to investigate the application of nonwoven fiber materials in advanced
paration effect of silica sol-gel prompted by non-solvent vaporization in areas like filtration. The SBS procedure might be exceedingly instru-
the spinning solution [80]. In the aforestated study [80], the CJS set-up mental in endeavors to additionally extend commercial manufacturing
consisted of a hollow spinning chamber, a DC motor, and a few fiber- of nonwoven polymer webs.
collecting posts. Barium titanate nanofibers (approximately 50 nm) In the SBS procedure, the polymer solution concentration, the sol-
were prepared by means of the CJS synthesis technique [94]. vent, and the polymer type utilized are determinants for attaining na-
nofibers and microfibers [95,78,96]. Dias et al. [97] prepared poly-
3.2. Plasma-induced synthesis vinylidene fluoride nanofiber mats using the SBS method utilizing a
commercial airbrush as well as compressor set. Examination of the
Utilizing a pulse direct current, plasma is commonly created from specimen morphology demonstrated smooth nanofibers possessing al-
the discharge between a couple of metal electrodes in solution. In this most 138.4 nm mean diameter. The preliminary test results confirmed
plasma-induced method, nanofibers are produced with the assistance of that there are no configurational or conformational variations in the
plasma generation between the electrodes. The development of plasma material. Hence, it can be confirmed that this advanced procedure is
takes place under water without employing any inert gas or any che- promising for the generation fibers at the nanoscale and microscale.
micals. By using the plasma-induced preparation method, the manu- Other significant points to feature are the affordability, high efficiency,
facturing of nanofiber occurs by the quick bombardment of exceedingly and simplicity of utilizing this method for the generation of film.
energetic radicals on the exterior of electrodes. With the aforestated Thus, in Section 3, various emerging strategies for nanofiber fabri-
action, the vapor of atoms as well as the cloud of atoms is developed in cation like centrifugal spinning, plasma-induced synthesis, and solution
the plasma region. Subsequent to that, the produced cloud of atoms blow spinning have been discussed. The contribution of nanofiber in
condensed with the plasma expansion because of a significant shift in various fields will rely upon the development of new technologies, and
temperature and pressure within the water. Lastly, metallic atoms un- hence developments of several new methods for efficient nanofiber
dergo reaction with oxygen (in-situ reaction) existing in water and preparation is seen in the recent years. The abovementioned recently
generation of nanofibers occurs. A diagrammatic portrayal of the ex- developed strategies like SBS for nanofiber fabrication might overcome
perimental setup of a plasma-induced preparation method is presented certain restrictions like the utilization of higher voltage, and solvent
in Fig. 2.b. The plasma-induced synthesis technique can be performed recovery problems of the ES processes. Also, the CS technique offers
at atmospheric pressure in an open network and will have promising excellent rate of production, which is almost 50 times higher than
utilization in the synthesis of nanomaterials. Recently, a study was conventional ES technique The flexibility and simplicity of these tech-
performed by Hu et al. [75], on the nanofiber preparation using the niques make it practical methods for the fabrication of nanofiber per-
plasma-induced synthesis technique. Here, the copper oxide nanofibers mitting the advancement of new classes of nanofibers which are not
10
H. Saleem, et al.
Table 2
Summary of recently published papers on electrospun membranes for pressure-driven as well as osmotic membrane procedures for filtration applications.
Sl. No. Polymer system Electrospinning experimental set up Characterization Target separation Performance Ref.
1 Polyacrylonitrile (PAN) High voltage applied is 18 kV, Qd: 0.5 mL/h and needle ID: Scanning electron microscope Suspended particle The membrane removed entire 0.1 μm particles present in [130]
0.4 mm, membrane uniform thickness: ~60 μm (SEM), Porosity microfiltration (MF) water and no reduction in the permeate flux
2 Polyurethane (PU)/ Applied voltage - 120 kV, Relative humidity - 50%, Chamber SEM, Capillary flow porometry Stbl4 bacteria and Removal of Stbl4 bacteria (∼98–99%) and micro-particles [131]
Polyethylene terephthalate temperature - 24 °C, Distance between the electrodes-20 cm microparticle - (∼96–99%). High permeation rate – 46,500 L/m2hbar
(PET) Microfiltration
3 Cellulose acetate (CA) and Voltage applied is 17 and 25 kV, TCD of about 10 cm and SEM Ultrafiltration of PEG and 90% enhancement in fouling resistance relative to control [132]
Polysulfone (PSf) needle: 18 and 22 gauges; Relative humidity: 55% and 23% BSA mixtures membranes
4 Polyetherimide Voltage applied is 30 kV, Qd is 15 μL/min, Needle ID is Porosity, FESEM, atomic force Forward osmosis (FO) Superior water flux of 42 L/m2 h, which is 133% rise [133]
0.75 mm, TCD is 12 cm. Humidity of about 50% at microscopy (AFM) relative to control membrane.
23 ± 2 °C
5 Polysulfone/polyacrylonitrile Solvent - DMF/NMP, Drum rotating speed-150 rpm, SEM, Contact angle goniometer, Forward osmosis (FO) Salt rejection - 97.12 ± 0.92, Good permselectivity, Higher [134]
Working distance-16 cm, Applied voltage-20 kV, Flow rate- Gravimetric analysis water flux, Reduction in ICP
11
1 mL/h,
6 Polyethersulfone(PES) Qd of 0.1, 0.4, 0.7, 1.0 and 1.3 mL/h; rotational speed: Tensile test, contact angle Filtration of fungus and Vapor treated membrane prepared in feeding rate of 0.7 and [135]
300 rpm, spinning distance: 22 cm, applied voltage: 17 kV analysis, bubble point, SEM bacteria culture media collecting time of 100 min was suitable for isolation of
and temperature 28 ± 2 °C bacteria
7 CA Needle based ES technique. Turbidimeter analysis River water filtration Final turbidity of about 0.135 NTU for a filtered sample of [136]
Applied electrostatic field:92 kV/m, flow rate: 1.8 mL/h river water
8 Poly(m-phenylene Solution feed rate was about 10 μL/min; distance from the FESEM, capillary flow porometer Water filtration m-aramid nanofiber membranes exhibited increased [137]
isophthalamide substrate to the needle tip was 15 cm at voltages in the range rejection of particle and superior pure water flux
12 kV to 15 kV. 30-gauge needles (inner diameter -
0.159 mm) were employed. Relative humidity (RH)
analyzed at 25 ± 2% and the temperature was 23 ± 1 °C
at the time of ES process
9 PES and PSf High voltage field of about 27.5 kV, Temperature: 25 °C, ATR-FTIR FIB, Surface contact FO Osmotic water fluxed about 2–5 times greater than [138]
TCD: 16 cm, RH: 10% Injection flowrate about 0.6, 0.9 and angle, SEM commercial type
1.2 mL/h
10 PAN Voltage applied is 28.5 kV and flowrate of about 1.0 mL/h. Brunauer-Emmett-Teller (BET) RO, Pressure retarded Membranes exhibited a significant increase of 3.5-fold [139]
Here, the TCD is 16 cm, RH: 50% Ambient temperature FESEM, TEM, Energy-dispersive X- osmosis, FO (water/sodium chloride selectivity) and 7-fold (osmotic
ray (EDX) water permeability), relative to standard commercial FO
membranes
feasible by ES process. well as morphology of the subsequent fiber. Besides the relative hu-
midity, the surrounding temperature additionally affects the solvent
4. Membrane fabrication using nanofibers evaporation rate along with the polymer solution viscosity. The post-
preparing methodologies inclusive of drying conditions, heat treatment
Electrospun nanofiber membranes are innovative membrane tech- as well as hot pressing strategies also significantly influence the sub-
nology which contributes significant flux and higher rejection rates can sequent nanofibers. Material parameters influencing the ES process are
be achievable relative to conventional membranes. Presently, nanofiber polymer concentration, molecular weight, polymer type, surface ten-
membranes prepared using ES technique are an interesting and con- sion, solution conductivity, solution viscosity, and effect of additives.
ceivable solution in the filtration field of technology because of their The polymer solution concentration is a significant factor affecting the
exceptional properties, inclusive of their superior porosity, high per- electrospinnability of the solution. In the case of solution blends, the
meability, adjustable pore size distribution, and completely inter- concentration shifts from a lower value of 1 wt% to a higher value of 40
connected pore framework, as compared to the other conventional to 50 wt% relying upon the type of polymer utilized. The polymer
membrane manufacturing techniques [79,98,99,100]. Thus, electro- molecular weight (MW), is a significant factor that influences the
spun nanofibers and microfibers are broadly achieving consideration electrical (dielectric properties, conductivity) and rheological (surface
for the utilization in separation processes where the aforestated prop- tension, viscosity) properties of the solution. Also, viscosity is a critical
erties are acceptable. As stated before, nanofiber membranes, manu- factor in the electrospinnability, resultant size as well as morphology of
factured using ES technique, have been utilized in numerous separa- the fibers. The surface tension of solution is normally a function of the
tion/purification purposes, inclusive of pressure-driven membranes, inclusion of surfactants into the solution or the solvents utilized. The
pretreatment of feed before NF or RO processes and the MD process. solution surface tension has to be diminished in the course of ES process
Currently, thin-film composite membranes (TFCMs) for RO and NF so as to accomplish a defect-free, smooth nanofiber. All the aforestated
desalination are additionally being manufactured using the ES tech- parameters should be adequately considered so as to obtain the opti-
nique. mized conditions for NFM synthesis.
For extra utilization of electrospun membranes, for example, direct
filtration media, the electrospun polymeric webs could be utilized as 4.2. Various criteria of ideal membranes for pressure-driven, osmotic-
the support layer for the state-of-the-art TFCMs [9]. The TFCMs, in- driven, and thermal-driven processes
clusive of FO, RO, NF and UF membranes, comprises of three major
layers, inclusive of the lower nonwoven fabric layer, central porous Table 2 is the summary of recently published papers on electrospun
support layer, and top ultrathin selective layer. The electrospun nano- membranes for pressure-driven as well as osmotic membrane proce-
fiber membranes are appropriate for pressure-driven membrane pro- dures for filtration applications.
cedures in which the permeated phase is the target item, for example,
most water treatments and wastewater treatments. Because of the 3-D 4.2.1. Pressure driven membrane process
interconnected pore framework of electrospun nanofiber membranes The major function of a filtration membrane is the separation of two
and their superior porosity relative to typical polymeric membranes different phases, preferably regulating one phase by means of a mem-
with the 2-D framework, the separation mechanism is triplicate. Such a brane and simultaneously functioning as a barrier to the second phase.
multi-target separation mechanism is beneficial when the objective is In pressure-driven membrane procedures inclusive of microfiltration,
the removal of impurity from the feed stream. The advanced electro- ultrafiltration, nanofiltration and reverse osmosis, a pressure enforced
spun nanofiber membranes have excellent porosity, over 80%, whereas on the membrane feed side functions as a motivating force to separate
conventional membranes have a porosity of 5–35%. water into two streams: retentate and permeate [102]. Generally, the
retentate is a concentrated solution which needs to be disposed or un-
4.1. Factors influencing the electrospinning process for the fabrication of dergone treatment prior to discharge, and permeate is the purified
membrane water. The specific permeability as well as the selectivity of membranes
control their roles in filtration procedures from microfiltration to re-
In spite of the modesty of the ES process set-up, the manufacturing verse osmosis. Based on the type of technique used, the bacteria, oil
of fibers is complex due to the fact that we need to take into con- emulsions, suspended particles, viruses, colloidal haze, cells, proteins,
sideration a few parameters in favor of enhancement. Nanofiber macromolecules, monovalent ions, divalent ions and sub-molecular
membranes prepared using ES method can be designed in accordance organic groups can be retained from the crude water.
with the desired structure, morphology, and functionalities by con- Even though the present membrane technology is starting to meet
trolling a few operational, environmental, material, and post-handling the aforestated requirements, less throughputs of these membrane
parameters. based separations have prompted the requirement for advanced mem-
Operational parameters such as solution or melt feed rate, set-up brane solution, inclusive of nano-engineered membranes. The primary
configuration, applied voltage, collector design, spinneret or tip size as benefits of ENFMs are the presence of the extremely porous, inter-
well as design, TCD, and speed of drum type influence the ES process connected, three-dimensional fibrous system, that contributes a higher
for the membrane fabrication. The voltage applied in the course of ES internal surface area and henceforth high separation ability in com-
process is usually in the range of 5 kV to 40 kV. A minimal feed rate is parison with standard membranes with a two-dimensional structure. It
required for the steady jet generation and increasingly uniform fiber can also be noted that the ENFMs are appropriate for the pressure-
diameters as well as morphology. The aforestated guarantees a fine driven membrane procedures where the target product is the permeate
balance between the quantity of jet solution leaving with the one phase, for example, water/wastewater treatments. The use of nanofiber
substituting it [101]. The morphology, size as well as the structure of mats or webs in microfiltration, ultrafiltration, and nanofiltration is
the nanofibers which constitute the non-woven membrane are influ- discussed in detail in the Sections 5.1–5.3, respectively.
enced by the tip to collector distance (TCD). The TCD influences the
electric field strength in the framework, with short TCD creating an 4.2.2. Osmotically driven membrane process
elevated electric field. The shape and design of the collector can like- Osmotically driven membrane processes, (also termed as engineered
wise influence the resultant NFMs. osmosis: EO) includes forward osmosis and pressure-retarded osmosis,
Environmental parameters include the ambient surrounding condi- which takes advantage of the natural osmosis phenomenon as the major
tions, for example, chamber temperature and humidity. Surrounding driving force for the membrane based processes [103]. Generally, os-
relative humidity in the course of ES process influences the structure as mosis is the net water movement across a selectively permeable
12
membrane, that permits the flow of water and deny the solute ions or fabrication because of its simplicity. Here, only one nozzle/spinneret is
molecules, driven by a distinction in osmotic pressure across the utilized, for that reason, in majority cases, just a single solution pushed
membrane. The aforementioned procedures can be utilized for extrac- by one syringe pump is needed. The aforestated system is particularly
tion of water and recovery of water, and furthermore, empower the suitable for the lab-scale investigation due to the fact that the small to
harvesting of salinity gradients for the generation of electricity [104]. sufficiently-sized nanofiber membrane specimens are simple to gen-
The forward osmosis process utilizes the osmotic pressure difference erate.
(p) as the driving force for the water transport across the membrane. So
as to improve the performance of membrane in engineered osmosis 4.3.2. Multi-spinneret ES
utilization, it is important to develop membranes with a specifically The process is not only appropriate for single-spinneret structure
designed support possessing low tortuosity and high porosity, which generating single or mixed constituents NFM, but also the generation of
has the capability of mitigating the serious internal concentration po- hybrid NFM consisting of distinctive constituent polymers is con-
larization (ICP) issue. In the recent past, nanofiber membranes layers ceivable. This could be achieved utilizing a double or multi-spinneret
with increased porosity have gained considerable interest as a potential ES framework in which at least two solutions are electrospun at the
scaffold-like porous support to manufacture engineered osmosis mem- same time onto a sole collector surface [110]. Additionally, multi-jet ES
branes. The use of nanofiber membranes in forward osmosis is dis- permits the quicker manufacture of huge-area nanofibers relative to just
cussed in detail in the Section 5.4. single-jet ES.
4.2.3. Thermal-driven membrane process 4.3.3. Coaxial ES

Thermally-driven membrane processes include the evaporative de- This is a variation of single jet ES system in which instead of uti-
salination strategies where energy is utilized to heat water, which later lizing one spinneret single-solution structure, a core-sheath or con-
evaporates and undergoes condensation to obtain clean and pure water. centric tube spinneret is employed permitting the development of two
Due to the fact that this is a pretty energy-consuming process, it is more unique solutions being undergone ES process simultaneously [111].
feasible in power plants or refineries where the waste heat is employed Coaxial ES is a fine technique to utilize for those polymers which are
as the source of heat. Membrane distillation is a thermally-driven se- difficult to dissolve or solutions which are difficult to electrospin. Either
paration process where pure water is separated from a contaminated the sheath or core layer can perform as carrier for the aforestated
water source like saline water (e.g. seawater, brackish water or was- polymers. This type of ES is likewise employed to prepare hollow fiber
tewater sample consisting of non-volatile impurities) [105]. MD func- membranes.
tions at a lesser temperature relative to a conventional thermal desa-
lination process, and at a reduced hydrostatic pressure compared to RO. 4.3.4. Melt ES
MD is a non-isothermal thermally-driven procedure which utilizes a Majority of the studies on ES process utilized solvent-based solu-
hydrophobic microporous membrane as a barrier (for water as the li- tions. However, it is difficult to manufacture membranes from those
quid phase), and just permits the water-vapor phase to flow through. difficult to dissolve, such as polyethylene (PE), polypropylene (PP), and
While lesser surface roughness and increased hydrophilicity of polytetrafluoroethylene (PTFE) [112]. On the other side, some of the
ENFMs are beneficial for the pressure-driven membrane processes; solvents/chemicals employed may be harmful to both environment as
contrarily, super-hydrophobicity, or hydrophobicity, is an important well as health, and will likewise leave a few residuals whenever applied
feature when such membranes are utilized for the MD process. The in industry. Thus, in quest for cleaner manufacturing, the melt ES
membrane distillation process has four main configurations; none- process has been taken into consideration. In melt ES process, molten
theless, in recent times advanced configurations are presented and polymers are utilized and because of the greater viscosity, larger fibers
which could all be effectively utilized for desalination as well as was- are generally prepared that make it not an interesting method as more
tewater/water treatment purposes [106]. Taking into account the conventional spinning procedures are accessible for micron-sized fiber
worldwide scientific research and development endeavors in the manufacture [113]. The benefits of melt ES include the absence of the
membrane distillation procedure, particularly for wastewater/water utilization of solvent, thus no exhaust or ventilation is needed and no
treatment and desalination purposes [107], this technique has not yet issue on residual solvents, and progressively uniform fiber generation.
been scaled to commercial levels. One of the most important obstacles In any case, as the polymer should be melted, heat is generally needed
for this is the absence of explicit and unique membranes for the that increases the expense, and on the procedure, heat is additionally
membrane distillation procedure. The practical membranes in the produced that should be cooled.
membrane distillation procedure must confirm a few specifications
before these membranes could be utilized, for example increased me- 4.3.5. Nanonets formation
chanical/chemical/thermal stability, enhanced liquid entry pressure In ES process, the material as well as process parameters can be
(LEP), superior porosity, and must be hydrophobic [108]. Despite that, designed for enabling the generation of very finer fibers (under 100 nm
the majority of the applied membranes for membrane distillation are diameter) named as nanonets, that are generated commonly because of
those industrially fabricated for microfiltration purposes and prepared the phase separation-induced disintegration in the course of ES process
from hydrophobic polymers. In such manner, ENFMs have demon- of a small charged drop under elevated electric field [114]. The pre-
strated potential features to be utilized in the membrane distillation sence of nanonets gives increased porosity, diminished pore sizes, and
procedure [109]. The utilization of ENFMs in membrane distillation extra surface area for the NFMs. The nanonets are portrayed either as
process is discussed in detail in the Section 5.5. soap bubble, fish netlike or spider weblike form having interlinked one
dimensional (1-D) nanofiber framework, in which the primary elec-
4.3. Set-up strategies for ES membrane fabrication trospun nanofibers function as the support material.
The different ES strategies for membrane fabrication include single- 4.3.6. Three dimensional (3-D) nanofiber membranes
spinneret ES, multi-spinneret ES, coaxial ES, melt ES, nanonets forma- The adaptability of ES process makes it possible to prepare 3-D fiber
tion, three dimensional (3-D) nanofiber membranes, ceramic nanofiber nanostructures or microstructures by means of different ES techniques
membranes and nanocomposite membranes. [115]. One feasible technique for generating 3-D membrane is by
consecutive ES in which layers of fibers are framed over one another
4.3.1. Single-spinneret ES consecutively, may they be similar kinds of polymers or diverse poly-
This system is the most regularly utilized for the membrane meric solutions relying upon the desirable framework.
13
4.3.7. Ceramic nanofiber membranes nanofibers.

The ceramic nanofibers could be in the form of porous nanofibers,
side-by-side, hollow, segmented, and hierarchical structure simply like
those with polymer based nanofibers [116]. The manufacturing of these 4.4.3. Solution blending approach
nanofibers is more complex relative to the preparation of polymeric The solution blending approach is one of the most frequently uti-
nanofibers. Beyond hundred materials have been utilized to generate lized techniques for contributing an alternate function or property to
ceramic nanofibers for several utilizations. the parent material. The aforestated strategy includes blending 2 parts
in a solution succeeded by the ES process. In numerous examinations,
4.3.8. Nanocomposite membranes the blending procedure is utilized where the desired material cannot
A nanocomposite is considered as a multiphase strong material in develop nanofibers and, consequently, an associate electrospinnable
which one of the phases has minimum one dimension of under hundred polymer is employed. Primarily, colloids, where the non-soluble part,
nanometers, or structures with nano-scale repeat intervals between the for example, hydroxyapatite, silica particles, and carbon nanotubes, are
various phases which make up the material. Nanostructure due to its suspended in the solution and undergone electrospinning to develop the
size effects and consequently exceptional chemical/physical properties nanofibers [119]. The other, more frequently included materials are
have been generally utilized in most of the industries. On the other polymers as well as soluble inorganic salts. There are three blending
hand, barely can an individual constituent be multi-purpose; occa- techniques commonly used: the first technique utilizes materials which
sionally specific properties might even be unwanted in explicit de- are dissolvable in a common solvent, the second technique employs
mands. Therefore, the nanocomposite that can either consolidate/en- various solvents for the two materials, and the third technique utilizes
hance the benefits of various nanomaterials or neutralize/control the insoluble materials. Given the possibility of this solution blending
downsides of individual segments has turned into a tendency to the technique, consolidation of the three techniques could be utilized in
utilization of nanostructured materials. Remarkable features of elec- nanofiber ES process.
trospun nanofibers, inclusive of flexibility, porosity, excellent surface
area and adjustable surface properties, prepare them an advanced
4.4.4. Wet chemical treatment
procedure to manufacture nanocomposites [117]. By adding the na-
In this wet chemical treatment method, the moderately inert
noparticles into the pristine polymer to manufacture nanocomposites,
polymer nanofiber is undergone treatment with a chemical so as to
the electrical, thermal, and mechanical properties, morphology, struc-
provide reactive functional groups, for example, hydroxyl (-OH), amine
ture as well as surface wettability of the membrane would all be in-
(-RNH2), or carboxylic (-OH) groups, contingent upon whether the sites
fluenced. The nanoparticles like graphene, nanocrystalline cellulose
on the polymer molecule are susceptible to nucleophilic or electrophilic
(NCC), modified silica, clay, and carbon nanotube could enhance the
attack. The nanofiber material is soaked in an alkaline medium to de-
surface contact angle and increase the performance of membrane.
velop a hydroxyl or carboxylic group on the surface of nanofiber.
4.4. Modification of electrospun nanofibrous membranes
4.4.5. Heat press/hot press treatment
The electrospun membranes might be modified by various surface
This is a basic yet efficient strategy to upgrade the properties of the
treatment techniques and or by including chemical groups. In the fol-
membranes, prepared using ES technique, to diminish pore size and to
lowing section, various types of modification methods will be discussed
enhance the physical integrity of the electrospun nanofiber membrane
which might help future research in desalination and water treatment
[120], thereby increasing its possibilities for the treatment of water by
technologies.
MD, FO, NF, UF and MF [121,122]. In a research study by Yao et al.
[123], the group performed a thorough examination on the impacts of
4.4.1. Layer-by-layer (LbL) technique
pressure, temperature, and time span in heat press treatment process on
The LbL procedure is based on the binding of positively and nega-
polyvinylidene fluoride membranes for membrane distillation utiliza-
tively charged macromolecules on the desired material surface. The
tion. Improved Young's modulus and liquid entry pressure were ac-
benefit of this technique is that the functional groups of the layers can
complished with optimal heat press conditions whereas the porosity
be selected in such a way that either a solitary property can be up-
and contact angle were diminished by 5.0% and 2.1%, respectively,
graded or several properties can be introduced. The higher surface area
relative to the un-pressed condition.
of ENFMs has prompted the researchers to investigate the probability of
fabricating extremely effective membranes for desalination and water
treatment technologies. In spite of the fact that LbL coating is mostly 4.4.6. Chemical depositions
performed by the utilization of alternately charged organic molecules, Here the chemical reaction takes place on the exterior of an ap-
inorganic nanoparticles with positively charge may also be coated on propriate substrate, and therefore the product self-assembles as well as
negatively charged organic molecules. Because of its negatively charged deposits, to form thin-film over the substrate. Generally, semi-crystal-
surface, the cellulose acetate (CA) is considered to be one of the effi- line polymers and crystalline inorganic materials (for example ZnS) are
cient materials for the LbL strategy [118]. Despite that, in order to used in the self-assembled film. In a study performed by Guo et al.
begin the procedure, the material surface should be activated by che- [124], a hydrophilic ENFM was contributed the hydrophobic nature by
mical incorporation. Consequent introduction of alternately charged employing the initiated chemical-vapor-deposition(CVD), and the li-
molecules is utilized to form the layers. quid entry pressure (LEP) improved to 373 kPa from 15 kPa sig-
nificantly, prompting the improvement of MD efficiency.
4.4.2. Functionalization of electrospun membrane
Functionalization contributes extra characteristics to nanofiber from
a single material. A material possessing prevalent chemical stability or 4.4.7. Coating
mechanical strength might be consolidated with other advantageous By the immersion of the membranes into a coating solution, the
properties, for example, chemical sensing, biocompatibility, anti- coating could be accomplished. Recently, dopamine is becoming well-
bacterial effects, and catalytic sensing. Providing extra functional known as an interface because of its easiness as well as effectiveness for
properties to the nanofiber upgrades its efficiency and adaptability adhesion [125]. Also, we noted that in the work by Liao et al. [126],
which could be tailored to explicit utilization. The different methods of they enhanced the contact angle of the MD membranes to 158° from
functionalization might be utilized together to develop multifunctional 138° by applying dopamine as an interface in the coating method.
14
4.5. Difference in nanofiber membrane morphology/structure in various processes like LbL technique, solution blending, heat-press treatment,
technologies chemical depositions, and coating are considered to be beneficial for
upgrading the properties of ENFMs.
The water permeability of nanofibrous membranes are of great
importance to reduce energy expenses and long-term stability of sys- 5. Application of nanofiber membranes in desalination and water
tems. Liao et al. [127] proposed modification of nanofibers surfaces treatment
using silica nanoparticles. The resultant surface provided more effective
liquid areas for the evaporation of water and enhancement in the per- The exceedingly porous and long nanofibers function as a potential
meation. Another important advantage is the high vapor and air en- candidate for various developing environmental utilization, specifically
trapment that reduces the effective thermal conductivity of the mem- in particulate separation and liquid filtration for environmental re-
branes. That results in lower conductive heat losses and more force for mediation and treatment of water, respectively. Both pure and cata-
evaporative transfer. In theory, a perfect support layer for a forward lysts- or adsorbents-functionalized nanofiber materials are effectively
osmosis membrane must possess less tortuosity, be extremely porous, developed for separating or removing contaminants and pollutants of
and should have a very thin structure. On the other hand, in reality sub-micrometer size from gas as well as liquid environments, dependent
present forward osmosis membranes prepared by phase inversion on different chemical and physical strategies, prominently ultrafiltra-
technique have a tortuous sponge-like pore structure in the support tion [22] and adsorption [140]. Usage of nanofiber frameworks as fil-
layers, which is the main obstacle to enhancing water flux. Nanofibrous tration materials has remarkably improved the separation effectiveness.
mats provide an excellent media for FO membranes since they have low The aforestated implies better separation flux and reduced operational
tortuosity, high porosity and availability to be produced in thin thick- energy. Because of higher specific surface area, superior surface-to-
ness. Sponge like morphology of conventional inversion membranes volume ratio, and persistent matrix structure comprising of minor pores
exhibits lower water flux, while nanofibrous mats provide excellent of nanofiber structures, these materials facilitate profoundly effective
supports. Using that strategy Song et al. [128] was able to increase separation process. Nanofiber membranes present an uprising in sea-
water permeability up to 300% because of the lower tortuosity. Because water desalination, water as well as wastewater purification by pro-
of the high-pressure drop and feed velocity, the pore wetting is an viding an economical, and energy-saving process as compared to con-
important issue in air gap membrane distillation and vacuum mem- ventional membranes. In view of this, the nanofiber membranes are
brane distillation. The high porosity and mostly hydrophobic surface of developing as a flexible method with several potential features for the
nanofibrous mats present an important advantage to be used in MD treatment of water. The various membrane-based desalination and
systems. However, the high liquid entry pressure of water reduces pore water purification procedures, for example, RO, MF, NF and UF and in
wetting over time. For that reason, triple layer NF based membranes recent times, developing technologies, for example, FO, MD, capacitive
were fabricated, which is composed of a hydrophobic NF, a wet casted deionization (CDI) and pressure retarded osmosis (PRO) have attained
mid layer and a hydrophilic NF layer [129]. Highly hydrophilic bottom exponential interest. The membranes utilized in the aforestated proce-
layer will facilitate absorption of condensed water molecule from the dures vary predominantly on their material properties and pore sizes.
mid-layer and reduces the resistance to pore wetting. Fig. 3 presents the Henceforth, a few investigations have been done for the utilization of
differences in membrane morphology/structure where the nanofibers nanofibers as support layers and pre-filter for desalination and various
are used for various technologies. water treatment processes.
Consequently, in Section 4, various factors influencing the ES pro- The RO procedure needs superior quality feed water for efficient
cess for membrane fabrication have been discussed. It was found that separation, and henceforth feed water pretreatment procedure is ne-
the nanofiber membranes manufactured using ES method can be de- cessary for improving the water quality to the level that would result in
signed in accordance with the desired structure, morphology, and the stable activity of the RO membranes. UF and MF are hypothetically
functionalities by controlling a few operational, material, environ- the most excellent pre-treatment for RO, separating from the feed water
mental and post-handling parameters. The various criteria of ideal majority of the potential components responsible for membrane
membranes for pressure-driven, osmotic-driven, and thermal-driven fouling, for example, bacteria, turbidity, particles, and enormous mo-
processes have been analyzed and the ENFMs proved to be a suitable lecular weight organic matters. The nanofiber membranes can be pro-
candidate for the aforestated processes. Also, the different modification ductively used for the UF and MF processes. Through the appropriate
Fig. 3. (a) As produced nanofibrous membranes (b) Hot pressed nanofiber membranes (c) Surface treatment on nanofibrous membranes (d) Nanofiber membranes
with modified surface for MD processes (e) Composite nanofiber membranes with thin PA layers - FO (f) Composite nanofiber membranes for MD applications.
15
modification of nanofiber membrane, the water-treatment utilization of high impact strength, high thermal stability, better chemical stability,
these membranes can be additionally extended to the separation of and good hydrophilicity. It is important to take note of that ENFMs do
increasingly complex colloidal solutions, for example, oil/water sus- not possess straight-through pores, in the event that they are properly
pensions, that involves the separation of an organic solute. Further, the manufactured. Rather, particles can pervade through the membrane by
addition of nanoparticles into nanofiber membrane help to upgrade the means of convoluted pathways; subsequently, such membranes exhibit
membrane efficiency (both salt rejection and flux); accordingly, the apparent/equivalent pore sizes normally in the range 0.1–10 μm, that is
utilization of nanotechnology in current desalination technologies can desirable for microfiltration. Also, the ENFMs comprise of randomly
result in the superior membrane performance. For all membrane pro- overlaid nanofibers; relative to ordinary microfiltration media, and
cedures, selectivity and flux are the two most significant factors to be these membranes regularly display remarkably superior flux values and
considered in addition to the fouling issue. In the next sections, we considerably reduced degrees of fouling with no reduction in the re-
demonstrate the utilization of nanofiber membrane in microfiltration, jection fraction of particle [143,144]. Generally, the waterborne mi-
ultrafiltration, nanofiltration, forward osmosis, and membrane dis- croorganisms are bigger than 0.2 μm [145]; subsequently, it is essen-
tillation. We can categorize them on the basis of different polymers and tial/significant for the filtration membrane to accomplish increased
nanoparticle used, and the various techniques utilized in each process. rejection fractions of 0.2 μm particles in water. Furthermore, the ENFMs
are undergone modification by post spinning treatments to diminish the
5.1. Microfiltration apparent/equivalent pore sizes subsequently to acquire 0.2 μm particle
rejection fractions [144]; despite that, these treatments/modifications
The standard pore sizes of non-woven NFM from several hundred would extensively enhance the expense of the resultant membranes. As
nanometers to a few microns range make it perfect for the utilization in an illustration, poly(vinyl alcohol) based ENFMs with approximately
microfiltration (MF). Out of the various membrane separation pro- 100 nm fiber diameters could remove/reject over 90% of 0.2 μm par-
cesses, MF (that is, removal/rejection of contaminants with particle ticles [144]; while the poly(vinyl alcohol) membranes should undergo
sizes 0.1–10 μm range) is a significant procedure which has been chemical stabilization for restricting the nanofibers from dissolving in
broadly adopted in the purification of water (for example, cleaning of water, and the membranes must be substrate supported (for example,
the surface and groundwater). MF is a basic procedure to separate PET) to obtain the mechanical properties required.
undesirable contaminants or for separating components particularly as Vast majority of the materials being used in ES process are solution-
a pre-filter, and separation of microorganisms, for example, bacteria based polymers, for example, polyvinylidene fluoride, polyacrylonitrile
which have sizes > 0.3 μm [141]. Numerous commercially used mem- (PAN), and polyether sulfone (PES), however, one significant difficulty
branes are presently accessible with 0.2 μm nominal pore sizes for the in the manufacture of these polymers is that the organic solvents uti-
application as microfilters. The benefit of NFMs relative to commer- lized regularly need solvents recycled from the diluted air steam,
cially used membranes includes its controllable size of the pore, high making this procedure expensive, or the solvent employed must be
porosity, and simplicity of manufacture. On the other hand, the nano- burned off. Hence, water-soluble polymers turn into a progressively
fiber membrane has insufficient mechanical strength, and consequently acceptable candidate for the ES process so as to accomplish an eco-
the majority of MF researches need typical support layer to provide friendlier and economical production process. In the research per-
mechanical strength, however, some researches have notified in- formed by Liu et al. [146], ES process was utilized to manufacture
dependent nanofiber membranes with better performance. When a nanofiber membranes for MF utilization and the group had chosen
membrane is prepared, two major factors determine its practicality: flux polyvinylalcohol as the ES material, which is moderately cheap, ther-
as well as selectivity. The selectivity is regulated by the membrane mally and chemically stable, and non-degradable under majority phy-
surface properties which distinguishes the class of species which can go siological conditions [147]. Despite that, the poly(vinyl alcohol) na-
through while flux depicts the transportation rate of species through the nofiber membranes, manufactured from ES process, must be treated
membrane. The aforestated two factors are influenced by the morpho- with cross-linking agents for preparing a 3-D waterproof system
logical as well as structural properties of the membrane, for example, [15,30], before being utilized as water filters. The impact of two pro-
wettability, thickness, pore size and distribution, transmembrane cessing factors, inclusive of solution concentration and applied voltage,
pressure and porosity. The data assembled on the flux and selectivity is were properly examined by the group. The test results confirmed that at
basic in deciding the use of the membrane in separation processes and an elevated voltage of 32 kV, the poly(vinyl alcohol) solution con-
in particular its performance. The three sequential steps involved in the centration of 10 wt% and 10 cm spinneret-to-collector distance, the
current pre-treatment of water are coagulation, flocculation and ulti- development of uniform nanofibers without any beads could be ac-
mately sedimentation. By the proper designing of the module, electro- complished. It has been demonstrated that the mean pore size dimin-
spun nanofiber membranes can be utilized instead of the aforestated ished with the thickness of the membrane under 30 mm and could be
three-stage pretreatment process. There is an additional possibility of kept practically steady when the thickness achieved 40 mm and above.
applying these membranes as pre-filters preceding nanofiltration or Because of the superior porosity, the electrospun poly(vinyl alcohol)
ultrafiltration to limit the chances of fouling as well as contamination nanofiber membranes, dependent on various thicknesses, indicated
from microparticles or microorganisms and furthermore to isolate cells three to seven times increased pure water flux, as compared to the
[142]. Here, we can categorize on the basis of polymers and techniques commercially used Millipore GSWP membrane with 0.22 mm nominal
employed during the microfiltration. For the utilization in microfiltra- pore size. Additionally, it was illustrated that with a 40 mm thickness or
tion application, the categorization can be done based on the basis of greater thickness, the pure water flux of the electrospun poly(vinyl al-
the polymers, such as (1) polyvinyl alcohol (2) polyethersulfone (3) cohol) nanofiber membrane continued approximately the same despite
polyacrylonitrile (4) polyvinylidene fluoride (5) polysulfone and (6) the fact that the membrane has become thicker. From the rejection test,
polyurethane, for improving the membrane efficiency. Further, dif- it was found that the membranes with a thickness of 20 mm or greater
ferent treatments such as chemical treatment, hot-pressing method, are able to remove over 98% of the polycarboxylate 0.2 mm micro-
heat post-treatment etc. in the nanofiber membrane for upgrading the sphere particles, that was greater than the rejection ratio of the com-
membrane performance has been illustrated. mercially used Millipore GSWP membrane with 0.22 mm nominal pore
size. In spite of the “cake layer” development at the time of the rejection
5.1.1. Polyvinyl alcohol nanofibers for MF membranes test, electrospun nanofiber membranes could be retained at 1.5 to 6
Different polymer materials are utilized for the fabrication of the times increased permeate flux, as compared to the commercial Milli-
ENFMs; and out of them, polyvinyl alcohol has been given increased pore GSWP membrane. Taking into account the superior filtration rate
attention because to its unique properties like better tensile strength, as well as rejection efficiency, the ENFM with a thickness of > 20 mm
16
ought to be a decent candidate for the application in water purification. biocompatible polymer utilized in commercial membrane manufacture,
The electrospun poly(vinyl alcohol) nanofiber membrane can con- and this polymer has superior thermal, mechanical and chemical re-
ceivably be an incredible candidate to efficiently separate micro- sistance. The aforestated features make this polymer a potential can-
organisms, bacteria or microparticles from wastewater at a moderately didate in the separation industry [148]. In the investigation carried out
lower expense. by Khezli et al. [149], PES nanofiber composite membranes were
ENFMs (with distinct fiber diameters as well as various membrane manufactured by ES process and the impact of concentration of the
thicknesses and porosities) have been investigated by Wang Z et al. polymer, temperature and solvent type on PES ES procedure was ana-
[130] as advanced microfiltration media for the very proficient and lyzed. For obtaining bead free nanofibers, the ES process parameters
economical separation of contaminations with particle sizes of 0.2 μm have been optimized. For manufacturing the PES nanofibrous compo-
from water. In this research study, the porosity of electrospun polyvinyl site membranes with changing properties, five diverse flow rates of
alcohol nanofiber membrane has been reasonably controlled/adjusted polymer solutions (1.3, 1.0, 0.7, 0.4 and 0.1 mL/h) were employed.
by a simple hot-pressing strategy; and the relationships between mi- Solvent dimethyl sulfoxide (DMSO), temperature of 28 ± 2 °C and
crofiltration performances and membrane properties were methodically concentration of 20% were chosen as the ideal conditions for the
examined. Upon optimizations/variations of the diameter of fiber, manufacture of bead free PES electrospun nanofibers. Solvent vapor
porosity, and thickness of the membrane, the ENFMs could be openly treatment has been performed to enhance the mechanical character-
used as superior microfiltration media to economically and effectively istics of the nanocomposite membranes by enhancing the adhesion of
expel 0.2 μm particles from water. Also, the aforestated research work fiber. The membrane morphology has been examined using SEM, and
has confirmed that the thickness of the membrane does not influence mechanical characteristics were assessed by tensile test. Utilizing the
the apparent/equivalent pore size, excluding the situation where the bubble point technique, the membrane pore size was evaluated. A re-
membrane is slender enough to possess defects/pinholes. Furthermore, tention test was carried out employing nanoparticle suspensions con-
the simple hot-pressing strategy was demonstrated to be very efficient sisting of identically sized particles and the water flux was estimated by
to enhance the rejection fraction and diminish the porosity of poly way of dead-end filtration system. Results demonstrated that the
(vinyl alcohol) based ENFMs. Relative to typical spinning strategies membrane thickness, fiber adhesion, and fiber diameter have a re-
which can just manufacture fibers with diameters in the range from a markable influence on water flux, potential membrane retention, and
few to tens of microns, the ES system could manufacture fibers with bacterial separation. The water flux in porous membranes is ex-
diameters in sub-microns and even in nanometers. The microfiltration ceptionally dependent on permeability and porosity [150]. Thin fibers
performances of the manufactured ENFMs have been tested in dead-end contribute increased porosity and with the increment in the porosity,
filtration mode at 10 psi applied pressure. It is to be noted that an the enhancement in water flux occurred, as represented in Fig. 4. Re-
elevated rejection fraction is constantly accompanied by a lesser lative to the treated PES membranes, the increased porosity of effec-
permeate flux for any kind of filtration media/membranes. The results tively movable fibers in untreated membranes brought about elevated
proved that porosity along with apparent/equivalent pore size are the pure water flux. Ultimately, the manufactured membranes have been
deciding factors for rejection fraction. Moreover, with lesser rejection utilized for filtering out fungus as well as bacteria from culture media.
fractions, the increment in thickness of membrane did not extensively The bacterial separation test demonstrated that the vapor treated
enhance the rejection fractions, whereas the values of flux were no- membrane prepared in collecting time: 100 min (MT8) feeding rate: 0.7
ticeably diminished. The aforestated results evidently demonstrated has been an ideal membrane for the isolation of bacteria.
that if particles have been caught on the exterior of the membrane,
enhancing the thickness might not be a proficient method to increase
the rejection fraction. Accordingly, the electrospun poly(vinyl alcohol) 5.1.3. Polyacrylonitrile nanofibers for MF membranes
nanofiber membranes had remarkably diminished apparent/equivalent Nanofibrous polyacrylonitrile-polyvinylaclohol composite mem-
pore size, making these membranes promising candidate as advanced branes were manufactured by Liu, X. et al. [151], using the two-nozzle
microfiltration media with superior performance like excellent rejec- ES method, for removing the heavy metal ions with opposite charges:
tion fraction, high flux value, reduced degree of fouling, and lesser Cd (II) as Cd2+ and Cr (VI) as CrO42− from polluted water, subsequent
operating pressure. to surface modifications. Both cadmium (II) and chromium (VI) ions
display carcinogenicity as well as higher toxicity, and might lead to
severe problem to the human health which should be addressed in top
5.1.2. Polyethersulfone nanofibers for MF membranes priority [152]. From several previous studies, it was found that the
Polyethersulfone (PES) is a very common, economical as well as functional additives along with nanofibers, can contribute significantly
Fig. 4. Diagrammatic portrayal of filter efficiency progress with a decrease in fiber diameter.
Adapted from reference [149].
17
increased adsorption of heavy metal ion to MF membranes variations in properties of membrane, for example, the nanofiber dia-
[153,154,155,156]. In the study by Liu X et al. [151], two diverse meter, Young's modulus and morphology. The structural properties of
modification procedures, hydrolysis and surface grafting, were per- the membranes should also be additionally explored to guarantee long-
formed to issue functionality specifically to one of the nanofiber com- term integrity under the trans-membrane pressure with no utilization of
ponents (polyacrylonitrile). These composite membranes with in- an extra non-woven substrate for structural assistance. Also, it is sig-
tegrated nanofiber network frameworks showed magnificent nificant to observe that the piezo-electric initiation needs an energy
mechanical properties, confirmed by cross-sectional as well as surface input which has not yet been optimized. Application of lower voltages
morphologies of the membranes. It could also be noted that the com- and intermittent initiation are promising methods which can decrease
posite membrane mechanical properties, subsequent to surface cross- the consumption of energy at the time of fouling mitigation. Further, it
linking as well as grafting, were similar to that of certain polyethylene is critical that the piezo-electric initiation has just been shown at the
terephthalate nonwoven mats. The utilization of the polyacrylonitrile bench scale and effectiveness are probably going to be observed at the
modified composite membranes in MF processes with both metal ion full scale operation. In the event that piezo-electric nanofiber mem-
adsorption ability and filtration ability was illustrated. Rejection ratios branes can lessen or delay the biofouling with less energy input, then
of the composite membranes were noted to be > 99.3% against 0.5- these advanced membranes can easily compete against the commer-
micrometer-particles and the better selectivity against 0.3-micrometer cially used membranes utilizing the standard fouling control techni-
and 0.5-micrometer microspheres was seen from hydrolyzed poly- ques.
acrylonitrile-polyvinylaclohol membrane. Additionally, the adsorption
capability of amino-groups modified polyacrylonitrile-polyvinylaclohol 5.1.5. Polysulfone nanofibers for MF membranes
nanofiber composite membrane was 66.50 mg/(g membrane) against There are numerous investigations utilizing nanofiber scaffolds or
the Cr (VI) ions, that was noted to be three times greater than that of electrospun nanofiber membranes as pre-filters for the removal of
single polyacrylonitrile nanofiber membrane with a polyethylene ter- particulate through MF application. The most referenced disadvantages
ephthalate substrate. In addition, the negatively charged hydrolyzed of ENFMs are their lower mechanical strength and the trouble in
polyacrylonitrile-polyvinylaclohol membrane displayed the adsorption handling them subsequent to ES process. A few techniques were pro-
capability of 33.60 mg/(g membrane) against the Cd (II) ions, that posed to overcome these issues before their utilization in filtration
additionally showed great adsorption proficiency. The modified poly- process: addition of nanoparticle, heat treatment, hot-pressing, solvent
acrylonitrile-polyvinylaclohol composite membranes can be recycled as induced inter-nanofiber bonding, polymer blending, plasticization, and
well as reused for several times, as confirmed by the regeneration utilization of crosslinking agents [102]. One of the best methodologies
proficiency of over 90% subsequent to 3 recycle operations. is to upgrade the bonding at junction points in the nanofiber mat by
welding the nanofibers each other, such as by the application of heat
5.1.4. Polyvinylidene fluoride nanofibers for MF membranes post-treatment (HPT).
ENFMs are a potential technology for addressing the essential bar- In the research work performed by Arribas, P et al. [160], the fil-
riers related to membrane filtration: low flux and high capital cost. tration properties of polysulfone ENFMs were upgraded by the utiliza-
Accordingly, electrospun MF membrane manufacture is a promising tion of HPT. The morphology and structure of self-sustained ENFMs are
field of research [157]. Despite that, irreversible and serious fouling, a the important determining factors of membrane performance for fil-
typical problem of numerous commercially used membranes, remains tration utilization. In the aforestated study [160], HPT strategy was
the primary disadvantage of ENFMs. The ENFM manufactured with employed to adjust the morphological and structural properties of
piezoelectric polymer is an alternate method to deal with fouling con- polysulfone based ENFMs, to upgrade their filtration efficiency and to
trol which might result in low energy utilization, increasingly sustain- develop membranes appropriate for the treatment of wastewater. MF
able operation, and remarkable cost savings. The piezo-electrically ac- tests were carried out utilizing humic acid (HA) model solutions having
tivated membranes can regulate fouling in-situ, inhibiting first 15 mg/L concentration at a pH value of 11. Enhancing the heat post-
deposition of foulants on the exterior of membrane by means of active treatment time or temperature, prompted an increment in the mean
deformation of the surface of the membrane [158]. The polymers, for nanofiber diameter and a lessening of the mean size of the inter-fiber
example, polyvinylidene fluoride, a regularly utilized polymer in spacing, the void volume fraction, and the water contact angle of the
commercially used membranes, could crystallize in a piezo-electric membranes.
phase if an electrical field is available in the course of crystallization. The ENFMs treated with a longer time and greater heat post-treat-
Poly(vinylidene fluoride) has 3 principle crystalline phases, namely α, ment temperature showed increased nanofibers inter-connectivity and a
β, as well as γ-phases, of which the γ and β-stages are regarded as piezo- compact framework with a small size of interfiber spacing. Under a
electrically dynamic. The polymer electrical charging, through either similar microfiltration operation conditions, a commercially used PES
ES or electrical poling, could be utilized to induce the crystallization of based microfiltration membrane (HPWP, Millipore) exhibited low fil-
poly(vinylidene fluoride) in its β-phase. tration performance (for example, low performance index, PI value of
The piezo-electrically activated membranes [159], accomplished about 82.0 kg/m2 h) relative to the heat post-treated treated optimized
stable flux with less trans-membrane pressure at the time of continued polysulfone. The test results obtained confirmed the better efficiency of
filtration of a synthetic biofouling solution. ES process was illustrated as the fabricated polysulfone ENFMs for microfiltration utilization. The
an appealing manufacturing strategy for membranes with adjustable remarkably higher pure water permeability of polysulfone ENFMs re-
parameters for optimizing the piezo-electric properties of fabricated lative to the commercially used flat sheet filtration membranes permits
membranes. Dimethylformamide demonstrated to be the most ap- the utilization of lesser pressures and in this way diminishes energy
pealing solvent for the fabrication of nanofiber membrane as well as utilization in the course of filtration. Along with their shorter fabrica-
filtration performance. Despite that, the results recommended that ad- tion time, this property makes polysulfone ENFMs manufactured with
ditional optimization of dimethyl sulfoxide ES (for example, by in- the optimized heat post-treatment conditions very potential candidates
crementing the acetone ratio) might upgrade performance, assuring to lessen the overall expenses and energy utilization of microfiltration
further examination given the lower contamination risk of dimethyl utilization.
sulfoxide compared to dimethylformamide and N-methylpyrrolidone.
Future research is additionally required to explain the mechanism of 5.1.6. Polyurethane nanofibers for MF membranes
fouling prevention of piezo-electric initiation to give in-depth knowl- The polyurethane nanofiber has been receiving considerable atten-
edge for enhanced fouling mitigation. The aforestated will need a de- tion in several research zones, because of its unique properties, for
liberate examination of the dynamic deformation that justifies the example, excellent nanofiber morphology, and flexible mechanical
18
properties for a wide range of utilization [161]. furthermore it can accomplish the ideal elimination of bacteria.
The needle ES arrangement suffers from a few disadvantages, for
example, needle clogging, industrial utilization restriction, low spin- 5.2. Ultrafiltration
ning rate, and it is a non-continuous system. Hence, for overcoming the
aforementioned limitations, different needle-less ES techniques were Ultrafiltration (UF) is a pressure driven procedure utilized in nu-
established. In the work by Moslehi M et al. [131], wiry needle-less ES merous industrial processes in which immense separation performance
procedure was utilized to fabricate ENFMs with increased rate in a is needed, inclusive of purification of water and biological filtration.
continuous system. In the aforestated study [131], an advanced process Most preferably, the structure of a UF membrane ought to have a su-
for the fabrication of MF membrane based on a two-layered poly- perior porosity, a thin skin layer, and a limited pore distribution [162].
urethane/poly(ethylene terephthalate) nanofiber mat modified by In addition to this, hydrophilicity contributes a UF membrane with
multi-step IP process was presented. The impact of the process para- superior wettability, that enhances permeation of water and hinders the
meters like concentration of monomer, reaction time, and the number fouling development. For improving the performance of the membrane,
of reaction cycles, on the amount of PA development (that is, yield), several past researches have explored the feasibility of two significant
were explored. The pore sizes of the modified polyurethane/poly- modification techniques. In particular, researchers have integrated
ethylene terephthalate ENFMs, ranged in 0.25 μm and 0.46 μm, can be molecules into the membrane body or they have modified the mem-
regulated by the aforementioned reaction parameters. These type of brane surface. The effectiveness of UF process basically rely upon the
membranes have the ability to separate micro-particle as well as bac- structure of the pore and pressure utilized in the course of separation
teria contamination at the same time. Specifically, the fabricated [163], which are controlled by operating parameters, for example, salt
membranes were able to totally separate micro particles (approximately concentration, pH, system hydrodynamics, and permeate flux. The en-
96–99%) and Stbl4 bacteria (approximately 98–99%) by means of size gineering plastics commonly utilized as UF membranes are poly
expulsion and retaining a superior permeation rate (about 23,200 (L/ (ethersulfone) [164,165], polyacrylonitrile [166,167], polysulfone
m2hbar) and almost 46,500 (L/m2hbar) for 0.25 μm and 0.46 μm, re- [163], and poly(vinylidene fluoride) [168,169] because of their ex-
spectively). Efficiency of these nanofiber membranes was compared to ceptional mechanical properties, and chemical stability. Despite that,
the commercially used membranes. Test results demonstrated that the the hydrophobic nature of these materials regularly results in sig-
modified ENFMs showed excellent filtration performance when com- nificant membrane fouling in the process of separation because of
pared to the commercially used types of comparable mean pore size. membrane–solute hydrophobic interactions. The hydrophilic mod-
The concentration of bacteria suspension in permeate and feed solu- ifications, for example, grafting, plasma treatment, and composite
tions was estimated by means of a photometer and the results demon- synthesis have been endorsed to diminish the fouling as well as enhance
strated that the two types of membranes exhibited superior perfor- the flux. For ultrafiltration application, the classification can be done on
mance and subsequent to the filtration, no turbidity or contamination the basis of the polymer nanofibers employed, such as (1) cellulose (2)
was seen as presented in Fig. 5. The bacteria rejection of PU/PA polysulfone (3) polyacrylonitrile (4) polyaniline polyethersulfone and
(0.46 μm) [PU/PA is the PU/PET nanofiber membrane modified with IP (5) polyvinylalcohol, used individually or as blend, for improving the
process, PA], PU/PA (0.25 μm), commercial microfiltration membrane membrane efficiency. Further, the application of multiwalled carbon
(0.45 μm) and commercial microfiltration membrane (0.22 μm) MF nanotubes (MWCNTs), single-walled carbon nanotube (SWCNT), and
were almost 98.80%, almost 99.90%, almost 98.90%, and almost hydrous manganese dioxide (HMO) nanoparticles in the nanofiber
99.90%, respectively. The results confirmed that controlled pore size membrane for improving membrane performance has been illustrated.
ENFMs showed superior efficiency in flux, when compared to Minisart®
Syringe Filter membranes of comparable mean flow pore size and re- 5.2.1. Cellulose and polysulfone nanofibers for UF membranes
tained a higher rejection level in the micro-particle retention test and In the membrane industry, cellulose as well as polysulfone are
Fig. 5. The bacteria removal of PU/PA [polyurethane/poly(ethylene terephthalate) nanofiber membranes modified with IP process, PA] and commercial MF
membranes.
Adapted from [131].
19
considered to be two commonly utilized polymers. Polysulfone (PSf) is arsenate micelles from the polluted water. The authors also suggested
a hydrophobic polymer possessing superior mechanical and chemical that the performance of TFCM can be upgraded by diminishing the
robustness. Further, cellulose is considered to be the most plentiful thickness of the topmost layer or modifying its composition.
natural polymer; and this polymer is hydrophilic in nature and can
smoothly experience additional chemical modifications. 5.2.3. Polyaniline nanofibers for UF membranes
The membrane efficiency can be improved by the insertion of na- Polyaniline is a conjugated polymer which has been utilized to
nofibers into the bodies of membranes [132]. Dobosz et al. [132] en- manufacture membranes for gas separation and pervaporation because
hanced the performance of UF membrane using electrospun nanofibers. of its easy acid/base doping/dedoping chemistry, ecological stability,
The nanofiber layer with immense porosity contributes an adjustable facile synthesis and exceptional electronic properties. In recent times,
platform which has no impact on the structure of base membrane. For electrified commercialized Polyvinylidene Fluoride ETNA10PP UF
decoupling the effects that nanofiber morphology as well as chemistry membranes known as electro-UF membranes have been considered
have on the performance of the membrane, two polymers regularly with the desire of more efficiently diminishing the fouling and up-
utilized in the membrane industry, polysulfone (PSf) and cellulose, grading the selectivity [171]. With this sort of membrane, the rejection
have been electrospun into a layer which has 50 μm thickness and and flux, that principally rely upon concentration polarization and pore
comprised of arbitrarily accumulated fibers of 1 μm-diameter. By the size distribution, could be improved by the usage of an electrical field in
incorporation of either PSf or cellulose nanofibers to a UF membrane, the filtration module. Increased control of fouling in electro-UF has
the selectivity continued as before; on the other hand, the compaction been credited to the improved electroosmotic and electrophoretic
time varied at low transmembrane pressures. The composite membrane phenomena along with electrochemical reactions taking place at the
flux performance deviated with an increment in the applied pressure. electrodes [172]. Several researchers have stated critical improvements
Also, it was noted that at less transmembrane pressure values, the flux for the separation of organic acids, arsenic, cryptosporidium, biopoly-
of the nanofiber enhanced membranes was equivalent to the control mers, and humic acid with electro-nanofiltration or electro-UF
membranes and are not dependent on nanofiber chemistry. At trans- [173,174,175]. Hence, the advancement of functionalized UF mem-
membrane pressure values > 3.5 bar, just the PSf NFM exhibited a branes with electrochemically switchable separation properties and
linear permeance relationship that might be credited to the distinct enhanced hydrophilicity can be of extraordinary interest. In recent
elongation properties of PSf nanofibers, relative to cellulose nanofibers. years, polyaniline (PANi) nanofiber films have exhibited super-
PSf NFM had an increase of 35% in pure water flux and 47% increment hydrophilicity due to their porous nanostructures and high surface
in permeance, relative to control UF membranes, at 3.5 bar trans- energy [176]. Liao Y et al. [22] developed electrically conducting ul-
membrane pressure. Also, it was found that the PSf NFM and cellulose trafiltration membranes by combining polyaniline/SWCNT nanofibers
nanofiber membrane showed a 90% increase in fouling resistance than into a PSf matrix. By choosing the extent of nanofibers and utilizing a
the control membrane, probably due to the fact that the existence of the flash welding procedure, the bovine serum albumin (BSA) rejection,
nanofibers diminished the contact time between the membranes and porosity, chemical structure, conductivity, permeability, thermal sta-
protein by 50%. Dobosz et al. [132] demonstrated for the first time that bility, and hydrophilicity of these composite ultrafiltration membranes
the addition of a nanofiber layer to a UF membrane contributes a right can be regulated. The incorporation of the PANi/SWCNT nanofibers
method to functionalize a membrane without unfavorably affecting the developed critical enhancements in the permeability of the membrane,
properties of the base membrane. We propose that such type of com- converting into 2.5–7.3 times original permeability of water and re-
posite membranes contribute an advanced model for further surface taining significant rejection of BSA from 39.8 to 73.7%, relative to
modifications. pristine PSf membrane. By controlling the flash welding intensity, the
BSA rejection, permeability, and conductivity could be upgraded by
5.2.2. Polyacrylonitrile nanofibers for UF membranes approximately 1.5, 2, and 600 times, respectively. The aforestated
Arsenic (As) is an exceptionally toxic element, and its drinking thermally stable and robust PANi/SWCNT composite membranes hold
water contamination is a worldwide issue, commonly reported in the guarantee for the advancement of electro-UF modules for treatment of
literature. For overcoming this issue of As drinking water contamina- water because of their hydrophilicity, adjustable conductivity, solute
tion, different procedures have been reported so far. Among the re- rejection, and permeability.
ported procedures, the membrane based separation process is con-
sidered to be an ecologically safe and cost effective method. Out of the 5.2.4. Polyethersulfone nanofibers for UF membranes
different membrane based processes, UF membranes have noted to have Polyethersulfone (PES) has been generally utilized as an ultra-
numerous utilization in water as well as wastewater treatment. filtration membrane material in numerous industrial areas because of
Bahmani, P et al. [170] developed an advanced TFCM using a poly- its superior performances. Despite that, the hydrophobicity of poly-
acrylonitrile coating layer, an electrospun nanofiber polyacrylonitrile ethersulfone membrane makes this polymer problematic to separate
middle layer, and a nonwoven polyethyleneterephthalate substrate and water from water/oil mixtures and sensitive to fouling. This causes a
observed to be efficient in the removal of As. reduction in water flux permeability in long run and abbreviates life
A cetylpyridinium chloride (CPC) surfactant was included in the span of membrane. The properties of membrane, for example, pores
aforestated study as a pretreatment to develop the cationic surfactant structure, hydrophilicity, and surface roughness are essentially re-
micelles, that bind with the As ions. The TFCM perfromance was as- sponsible for the performance of membrane. Various approaches to
sessed utilizing 3 different parameters namely rejection efficiency of upgrade the hydrophilicity as well as antifouling ability of polymer
cetylpyridinium chloride from aqueous solutions, rejection efficiency of membranes include surface modification, chemical grafting, and phy-
arsenate, and flux rate. The comparison of UF membrane and TFCM sical mixing with hydrophilic components. A basic and generally uti-
demonstrated the predominance of TFCM with a noteworthy increase in lized method is to simply blend the pre-developed nanoparticles with
pure water flux, arsenate rejection efficiency and aqueous solution flux. the polymers in solution.
Furthermore, a descending trend in the rejection was illustrated. To Al-Husaini et al. [177] fabricated an advanced type of UF ENFM
assess the fouling issue, variations in contaminant rejection and flux containing the nanoparticle hydrous manganese dioxide (HMO) with
were assessed with alterations in the filtration time. Fouling in TFCM the aim of enhancing the PES-based membrane properties for the ap-
was delayed given the three-dimensional porosity of nanofibers in thin- plication in the treatment of synthetic oily solution. In comparison with
film composite membranes. In brief, the thin-film composite mem- the commercially used nanomaterials, the nanoparticle HMO is ob-
brane, with a superior flux, comparatively better rate of rejection, and served to be progressively hydrophilic in nature. This can be ascribed to
moderately less cost, is a magnificent candidate for separating the the superhydrophilic nature of HMO due to the enormous amount of
20
-OH functional groups. Two types of treatments were performed in the 5.3. Nanofiltration
investigation by Al-Husaini, I. S. et al. [177] for improving the hydro-
philicity and mechanical property of the polyethersulfone-based Nanofiltration (NF) is a membrane-based procedure placed between
membrane without reducing its water permeance and porosity. Also, UF and RO processes and is utilized for softening of water, separation of
heat treatment was utilized as an efficient way to reinforce and avoid bacteria, viruses, other micropollutants and suspended solids from
delamination of the nanofiber mat in the course of the ultrafiltration water [180]. NF has been developed for desalting low sodium chloride
process. The HMO-added ENFMs showed a great oil rejection (94.04% content water, for example, brackish water. The NF membranes have
and 97.98%) and a water flux recovery (71.10% and 89.29%) when the salt rejection ability of 20–80% with increased rejection ability
utilized to treat a synthetic oily solution consisting of 10,000 or towards the multivalent ions like SO42−, Mg2+, and Ca2+. Presently,
5000 ppm oil, respectively. The optimum favorable HMO added ENFM NF process is rising as a reasonable alternate to typical water treatment
showed significantly higher magnitude of water productivity processes, since it can function at lesser pressures, contribute superior
(> 7000 LMH) with no reduction in oil removal rate. In particular, this flux and more energy-saving relative to reverse osmosis process. It has
nanoparticle included membrane demonstrated remarkably lower level been demonstrated that the permeate flow can be doubled with nano-
of flux decrease because of enhanced surface resistance against oil filtration, relative to reverse osmosis and by replacing reverse osmosis
fouling and is promising for longer term operation with increased with nanofiltration membranes almost 20% of electric power can be
lifespan. Superior antifouling and mechanical properties of the ENFMs spared [181]. One of the major benefits of NF over RO is that the NF
is conceivably applicable in the effective treatment of industrial oily operation can be carried out at remarkably lesser pressure and hence
effluents when challenged with oil-in-water emulsions. the expense of operation can be diminished considerably. Here, we can
categorize on the basis of polymers and nanoparticles using in ES
process.
5.2.5. Polyvinylalcohol nanofibers for UF membranes In recent times, nanofibrous membranes were used for ultrafiltra-
The extremely liquid-permeable electrospun nanofiber membranes tion (UF) and MF applications due to their propensity to diminish the
were noted to be outstanding candidates as the porous supporting layer water flow resistance (that is, superior water flux) [182]. When elec-
below the topmost barrier layer for contributing superior flux TFCMs trospun nanofiber membranes were modified using a thin barrier film,
because of their interconnected pores with both surface porosity as well they displayed better NF performance with lesser fouling. At the point
as bulk porosity of 80% range [178]. On the basis of the aforemen- when the treatment of water requires significantly reduced pore sizes as
tioned benefit, the thin-film nanofiber composite membranes should compared to microfiltration membrane, for example, in the case of NF
demonstrate remarkable flux rate for filtration of water, relative to as well as UF, precisely utilizing the nanofiber membrane is not prac-
typical thin-film composite. You et al. [179] developed an advanced ticable because of their huge sizes of the pore. Henceforth for NF and
class of superior efficiency thin-film nanocomposite UF membrane UF operations, the NFMs are generally utilized as a supporting layer to
based on a polyacrylonitrile nanofiber substrate combined with a hy- the dynamic thin-film layer prepared by different strategies. In majority
drophilic thin nanocomposite barrier layer manufactured by ES strategy cases, TFCMs are utilized for RO, NF, and UF applications to isolate
coupled with solution treatment technique, and has been utilized as a extremely smaller constituents from feed water. Ordinary TFCM has a
UF media to isolate an oil/water emulsion. Hydrophilic nanocomposite center layer generally prepared by phase inversion (PI) technique and
barrier was made out of crosslinked polyvinylalcohol thin layer in- works either as a support layer or as a filtration layer apart from the
tegrating surface oxidized MWCNTs, and was manufactured by the dynamic barrier layer. Despite the fact that these TFCMs have attained
immersion of electrospun polyvinylalcohol-MWCNT/polyacrylonitrile appropriate efficiency, there is a chance to furthermore upgrade the
nanofiber double-layer mats into optimized solution of acetone/water membrane design by using a nanofiber layer as a center layer to en-
and afterward chemically crosslinked by glutaraldehyde in acetone/ hance the porosity and eventually the permeation of the entire mem-
water solution. The electrospun polyvinylalcohol-MWCNT nanofiber brane. The electrospun nanofiber membranes as a support for thin-film
topmost layer was swollen to combine gradually into an integrated composite (TFC) NF film manufacture have several extraordinary
barrier film on the supporting layer of polyacrylonitrile. Results ob- characteristics than the UF membranes inclusive of superior porosity,
tained from the positron annihilation lifetime spectroscopy (PALS) ex- interconnected voids as well as nanocomposite structure of barrier
amination demonstrated that the polyvinylalcohol-MWCNT/poly-
acrylonitrile thin-film nanocomposite membrane free volume enhanced
especially with the increment in the concentration of MWCNTs in the
layer of polyvinylalcohol, and also the filtration assessment proved that
the addition of MWCNTs into barrier layer of polyvinylalcohol can
enhance the water flux remarkably, which confirmed that greater effi-
cient water channels have been developed in the nanocomposite barrier
layer with the addition of MWCNTs into the barrier layer of poly-
vinylalcohol. In order to economize the consumption of energy, the
water efficiency of nanocomposite membranes was explored at ex-
tremely lower feeding pressure of 0.1 MPa. Fig. 6 demonstrated the
filtration efficiency of the resultant polyvinylalcohol-MWCNT/poly-
acrylonitrile thin-film nanocomposite membranes with 0, 5.0, 10.0, and
15.0 wt% of MWCNTs at low feeding pressure (0.1 MPa). The stable flux
has been seen during the experimental time limit without noticeable
fouling. The polyvinylalcohol-MWCNT/polyacrylonitrile thin-film na-
nocomposite membrane (10 wt% MWCNT) had superior water flux
(270.1 LMH) with 99.5% rejection rate at lesser feeding pressure. The
results confirmed that the polyvinylalcohol-MWCNT/polyacrylonitrile
thin-film nanocomposite membrane had remarkable anti-fouling prop- Fig. 6. Filtration efficiency of the poly(vinyl alcohol)-MWCNT/PAN thin-film
erties and a superior flux at less feeding pressure. Besides, the poly- nanocomposite membranes with 0, 5.0, 10.0, and 15.0 wt% of MWCNTs at low
vinylalcohol-MWCNT/polyacrylonitrile composite membranes dis- feeding pressure.
played excellent overall mechanical properties. Adapted from reference: [179].
21
layer. The aforestated benefits of thin-film nanofiber composite NF a charged NF membrane has been manufactured by mixing sulfonated
membrane contribute excellent flux and comparative rejection rates, polyether ketone (SPEEK) with PES in casting solutions. The in-
relative to the traditional nanofiltration membranes [21,22]. In the case corporation of sulfonated polyether ketone will be able to concurrently
of nanofiltration application, the categorization can be done on the enhance the salt rejections and water flux of the membranes. Fig. 7
basis of the polymer supports employed, such as (1) polyethylene ter- demonstrates the water flux and the salt rejections of the membranes
ephthalate (2) polyacrylonitrile and (3) kevlar for improving the with various sulfonated polyether ketone contents in the casting solu-
membrane efficiency. Also, we illustrate here the usage of nanoparticles tions. By the addition of 2–3 wt% (optimized addition content of
like graphene oxide (GO) in the separation process. SPEEK), the membranes displayed 80% salt rejection and approxi-
mately 75 LMH flux. Under the testing condition with identical feed
5.3.1. Polyethylene terephthalate (PET) nanofibers for NF membranes solutions, the manufactured electrospun nanofiber membrane sup-
Polyethylene terephthalate (PET) is a notable commercialized ported NF membrane showed an equivalent rejection of 60 to 80% than
polymer utilized as nanofiber support because of its suitable specialties, some typical phase inversion membrane [193,194], however, displayed
for example, recycle capability, superior electrospinning ability, low a considerably higher flux. Additionally, different types of materials as
cost, melt-electrospinning capability, great nanofiber morphology, as well as modification technologies for the outermost layer could be
well as mechanical properties [183,184]. utilized in these membranes, showing that the aforestated advanced
In a research performed by Mahdavi et al. [185], thin-film nanofiber membranes have incredible potential in novel NFs.
composite membranes based on self-supported nanofiber mats were
prepared. PET nanofiber supports were developed by the ES method
5.3.2. Polyacylonitrile (PAN) nanofibers for NF membranes
and then heat treatment was done to improve the mechanical stability
Currently, numerous research studies have been concentrated on
of the nanofiber mats. Later, the IP process was performed for preparing
graphene along with graphene oxide (GO) sheets to prepare nanofil-
thin-film nanofiber composite NF membranes. For the sake of com-
tration media. The GO sheets along with the subsequent membranes
parison, the TFC NF membrane was manufactured by similar conditions
have captivated considerable interest as potential materials for pur-
based on polyethersulfone (PES) UF membrane developed using the PI
ification of water (especially nanofiltration) because of the ultra-fine
technique. So as to avoid nanofiber layer deformation, the bond be-
two dimensional (2-D) framework and most importantly, the small in-
tween the nanofibers has been reinforced by choosing the correct pro-
tersheet nanochannels in the stacked lamellar membrane [195]. GO
portion of mixed solvents (Trifluoroacetic acid/dichloromethane), ES
sheet layer could be easily prepared by filtration of a diluted suspension
process and heat treatment. The filtration efficiency was explored by
over the support membrane [196]. However, it is fairly hard to man-
the water contact angle, rejection, water flux, and molecular weight
ufacture a uniform GO or reduced-graphene oxide (r-GO) sheet layer on
cut-off (MWCO) analyses. It was demonstrated that NF efficiency of the
as-ENFM because of the elevated surface roughness. A very thin layer of
thin-film nanofiber composite membrane is superior to TFCM; the flux
GO on as-electrospun nanofiber membrane will create numerous cracks
of thin-film nanofiber composite membrane was four times greater re-
in the course of drying, probably because of uneven membrane surface
lative to TFCMs and the rejection of thin-film nanofiber composite
topology. This issue could be significantly reduced by just hot pressing
membrane has also been noted to be higher. The enhanced flux in thin-
as-ENFMs, that remarkably enhances the nature of the filtered graphene
film nanofiber composite membranes is probably because of the en-
oxide sheet layers. The aforestated simple and efficient processing
ormous open-pore framework, the lesser hydraulic resistance of the
method is anticipated to enable extensively spread utilization of elec-
nanofiber support and nanocomposite arrangement of fine layer up-
trospun nanofiber membrane for the manufacturing of 2-D materials
grading the water transport capacity. Then again, the efficiency of the
based separation media/membranes. In an examination by Wang Z
PET thin-film nanofiber composite NF membrane was compared with
et al. [197], the group easily overlaid GO sheets over the hot-pressed
other thin-film nanofiber composite NF membranes and it was seen that
PAN based ENFM to develop a crack-free and continuous layer by
the aforestated membrane had a suitable NF efficiency.
simple filtration. The GO layer thickness was adjusted by fixing the
The incorporation of electrospun nanofiber membranes into the
amount of aqueous suspension of GO. The resultant bilayer membranes
phase inversion induced nanofiltration membranes is a practicable
have been independent and delamination-free even after the GO sheet
technique to improve their water flux and reduce the operating pres-
thermal reduction into r-GO sheets. The even surface of hot-pressed
sures at the same time retaining the benefits. The most important factor
PAN nanofiber membrane has been the authorizing factor for the
in manufacturing such membranes is regulating the separating layer
aforementioned type of suitable manufacture. The rejection fractions of
thickness with nanofiber mats below [186]. However, one point that
should be focused on is the casting solution penetration into the elec-
trospun nanofiber membrane pores because of the enormous pores
[187]. Accordingly, modifications are generally employed prior to the
utilization of the electrospun nanofiber membranes. LbL assembly,
which has been developed by Decher [188], is being extensively uti-
lized as a technique for the modification of the filtration membranes
[189], inclusive of electrospun nanofiber membranes [190,191]. High
flux NF membranes were manufactured by Xu et al. [192] by con-
solidating the techniques of electrospinning (ES), LBL assembly as well
as phase inversion. The membranes showed a three-dual structure
consisting of nonwoven supports, layer-by-layer assembly modified
electrospun PET nanofiber mats and PES coating layer. This advanced
kind of electrospun nanofiber membranes supported NF membranes
with surface separation layer of approximately 10 μm was manu-
factured by PI on the layer-by-layer assembly modified PET electrospun
nanofiber membranes. Further, it was proved that the modification by
LBL assembly was essential for effective membrane manufacturing.
With the optimized technical conditions, the membrane displayed ex- Fig. 7. Water flux and the salt rejections of the membranes with various sul-
cellent separation efficiency with 50–60% salt rejection and 50–60 L/ fonated polyether ketone (SPEEK) contents in the casting solutions.
m2/h (LMH) flux. So as to additionally enhance the rejection property, Adapted from Reference [192].
22
GO-based PAN membranes for NaCl and MgSO4 have been 40% or greener and non-corrosive solvent, which might open up new possibi-
lesser because of the moderately extensive nanochannels (approxi- lities and techniques for developing Kevlar into NF membranes appli-
mately 0.79 nm) present in the GO layers. Following the thermal re- cations.
duction for 12 h at 150 °C, around 90% MgSO4 was separated essen- Piperazine (PIP)-based nanofiltration membrane synthesized from
tially because of size exclusion of the resultant r-GO layer. Also, the the IP process between the trimesoyl chloride (TMC) in the organic
water flux values of the PAN-r-GO and PAN-GO membranes have been phase and piperazine in aqueous solution are standard nanofiltration
extensively greater as compared to the values of other NF media/ membranes [205,206,207]. The piperazine-based nanofiltration mem-
membranes detailed in the literature, and this was to some extent as- brane generally have a better flux and an excellent multivalent rejection
cribed to the superior porosity of hot-pressed PAN electrospun nano- (> 95%), while the rejection of monovalent ion ranges from 0 to 60%
fiber membrane. Hence, the hot-pressed electrospun polymeric nano- [208,209,210,211,212,213,214]. A unique m-phenylenediamine-based
fiber membranes stated in the work could be a common platform to thin-film composite nanofiltration membrane was effectively fabricated
assist different 2-D sheets for exceedingly effective and affordable se- by Li Y. Wong et al. [215] through IP process on a nanofiber hydrogel
paration of (hydrated) ions and dissolved components (for example, substrate succeeded by solvent treatment. Dimethylformamide solvent
organic molecules) and from water. treatment adjusted the surface morphology of the membrane by the
removal of the top “leaf-like” polyamide layers and diminished the
5.3.3. Kevlar nanofiber for NF membranes membrane surface roughness. Also, the surface hydrophilicity of the
Kevlar possesses a superior chemical resistance in harsh conditions membrane improved remarkably and the surface zeta potential di-
and has an extraordinary resistance to the most generally utilized sol- minished when exposed to dimethylformamide. The desalination effi-
vents due to the higher amount of intermolecular hydrogen bondings, ciency of the aramid nanofiber TFCM moved from reverse osmosis into
and could only be dissolved in conc. sulphuric acid, that makes it an nanofiltration. Nanofiltration tests illustrated that the aramid nanofiber
ideal polymer for the manufacturing of solvent resistant membranes. TFCM had superior rejections of divalent ions and a higher rejection
However, the utilization of aggressive conc. sulphuric acid as solvent rates of monovalent ions. When compared to the commercially used
for preparing dope solutions significantly restricts the use of Kevlar in membranes (NF90, NF270), the fabricated membrane demonstrated a
the membrane technology area. The utilization of firmly corrosive competitive separation efficiency in molecular separation as well as in
sulphuric acid as solvent in the preparation of membrane not just makes water desalination. The aramid nanofiber TFCM likewise out-performed
the membrane manufacturing process not “green”, however it also in- the recently reported superior piperazine-based nanofiltration mem-
volves significant danger. Hence, the fabrication of solvent resistant branes with respect to salt rejection. The recently designed aramid
Kevlar membrane by utilizing a noncorrosive as well as greener solvent nanofiber thin-film composite NF membrane has incredible potential in
would be a significant improvement in the advancement of Kevlar into scaling-up for industrial utilization because of the simple synthesis
membrane application. process and the reproducible as well as great desalination performance.
Membrane science, particularly organic solvent nanofiltration
(OSN), is a green procedure with respect to its operational stability, 5.4. Forward osmosis
lower energy utilization, and superior efficiency, and in this manner
performs a significant role in the reuse and purification of solvents Forward osmosis (FO) is considered to be a naturally happening
[198,199]. In general, the organic solvent nanofiltration membranes physical phenomenon and is the water transportation over a selectively
are utilized to isolate solutes from solvents having a molecular weight permeable membrane forced by the osmotic pressure variation over a
cut-off extending from 200 Da to 1000 Da, and pore size ranging from membrane [216]. The FO membrane perfectly permits just the water
0.5 nm–2.0 nm [200,201]. The OSN membranes are developing as an molecule passage across it whereas dismissing the movement of solute
effective separation technology in chemical procedures, for example, molecules or ions. The difference in concentration of solute present in
organics extraction, solvent recycling, and catalyst recovery [202,203]. the solutions isolated by the membrane can cause a distinction in os-
Polymer OSN membranes have received immense attention in the motic pressure, that forces the natural motion of water from the solu-
field of OSN because of their relatively lower expense and simplicity of tion consisting of low solute concentration (feed solution) against the
scaling up. On the other hand, the manufacturing process are still solution with high solute concentration (draw solution). FO became
complicated, and utilize a huge amount of vigorous solvents and in well known back in the 1800s and it has got extensive applications.
some cases pose a safety risk in synthesis, bringing about a negative Besides the fact that it was utilized for water treatment and desalination
ecological impact. In the investigation performed by Yuan S et al. of seawater, this process is also being utilized in food preservation, food
[204], thin Kevlar nanofiber organic solvent NF membranes were processing, and anti-microbial applications [216,217], however, it is
manufactured by means of a simple as well as green thermal treatment considerably less examined and developed relative to other desalination
by utilizing greener solvent. Rather than conc. sulphuric acid, a greener and water treatment processes, in particular, RO. One of the reasons
solvent, that is, a Dimethyl sulfoxide- Potassium hydroxide/water behind this constraint in the research and advancement of forward
mixture was utilized for developing a dope solution consisting of the osmosis is the absence of membranes that are specifically designed for
Kevlar nanofibers. Subsequently, preparation of hydrogel UF mem- forward osmosis [218,219]. Currently, TFCMs are the most manu-
branes was done and a thermal treatment was applied to change the factured and utilized membranes for the osmotic procedure. Primarily
hydrogel UF membrane into a solvent safe NF membrane with no intended for pressure-driven procedures, for example, RO [220], the
consumption of extra solvents as well as crosslinking agents by the TFCMs are commonly made out of a very thin PA selective layer over
hydrogen bond regeneration. The obtained nanofibrous membrane porous membrane support. The active PA layer is produced by means of
possessed a Rose Bengal (water soluble dye) rejection of about 95.4% IP process of two monomer solutions, organic multifunctional aromatic
surpassing most of the other polymer based pristine organic solvent acid halide and aqueous aromatic amine [221]. Nanofiber-supported
nanofiltration membranes generated by PI method. The aforestated TFCMs utilized for water-based separation procedures have become the
contributes the Kevlar membrane a superior baseline for additional topic of different examinations during the past [128,138,222,223,224].
modification so as to enhance the efficiency. Further, the Kevlar NF The electrospinning technique for nanofiber membrane is a useful and
membranes retain a comparatively constant rejection of dye in the non-expensive strategy, however, this technique is still constrained by
course of filtration of a dye solution for 6 h and maintain a rejec- the optimization of electrospinning condition, choice of explicit mate-
tion > 94% after being treated by various solvents for seven days, re- rials appropriate for specific applications, post-treatment of nanofiber
presenting an increased solvent resistance. Moreover, this study enables [225], swelling of membrane [226], strength and stability of nanofiber
the fabrication as well as utilization of Kevlar fibers in membranes by a [227], and weak bonding of the selective PA layer with the nanofiber
23
membrane support [138]. The aforestated drawbacks have been fo- nature first experienced heat-press treatment before poly(vinyl alcohol)
cused on in different researches, yet cost, practicability, and stability of dip coating and the crosslinking process so as to lessen the swelling of
the technique still could not seem to be completely optimized. The the membrane in water and further to improve the mechanical prop-
TFCMs for FO process have demonstrated in the past to have the ability erties of the membrane. The mechanical properties of polyvinylidene
to accomplish remarkably increased water flux and rejection of salt, fluoride heat-treated support, polyvinylidene fluoride non-heat treated
relative to the first generation of commercially-used CA membrane support and polyvinylidene fluoride-poly(vinyl alcohol) support at wet
[228]. A perfect FO membrane ought to have superior water flux, as well as dry conditions are presented in Fig. 8. The variations in the
minimal concentration polarization (ICP), and less salt reverse, mechanical properties among wet and dry specimens for the three
[229,230]. The addition of bulky polymers [231], nanomaterials [232], membranes were actually under 10%, which did not appear to be very
and surfactants [233], or a molecular LBL IP technique [234], might be important. The aforementioned demonstrated the remarkable benefit of
carried out to upgrade the selectivity of the PA selective layer. Despite utilizing hydrophobic electrospun polyvinylidene fluoride nanofiber
that, an increase in water permeability usually improves salt perme- mat having hydrophilic poly(vinyl alcohol) dip coating in place of a
ability too; subsequently, a balance between the two parameters of the completely hydrophilic electrospun support mat which swells as well as
membrane should be accomplished. The electrospun nanofiber mem- loses its mechanical properties on water wetting due to the fact that the
branes display excellent porosity by means of its interconnected pore hydrophobic characteristics of electrospun polyvinylidene fluoride re-
framework [218] and this characteristic enables it an appropriate strict the swelling of membrane [218]. The poly(vinyl alcohol) nano-
candidate for the membrane substrate for FO utilization. Different types fiber dip coating remarkably upgraded the hydrophilicity of membrane
of polymers such as polysulfone (PSf) [138], polyacrylonitrile (PAN) without reducing the porosity of membrane support. This, therefore,
[235], polyvinyl alcohol [222], polyethersulfone (PES) [128], and brought about a remarkable decrease in the ICP effects and subse-
polyvinylidene fluoride [218] could be utilized for the ES process. The quently enhancements in the efficiency of FO with respect to water flux
polymeric membranes for FO procedures could be manufactured by as well as the ratio of solute fluxes to water fluxes. The most reduced
means of different methods such as electrospinning, phase inversion structural parameter value of 154 μm was accomplished for the thin-
and hollow fiber spinning [236,237]. In general, superior osmotic flux film composite-FO membrane coated with poly(vinyl alcohol) and its
and less structural parameter values have been accomplished for performances were practically identical with other superior perfor-
ENFMs, permitting it an appropriate strategy for the manufacture of mance forward osmosis membranes stated in the same literature [225].
forward osmosis membranes. For the FO utilization, the categorization Therefore, this investigation demonstrated that poly(vinyl alcohol) dip
can be done based on the polymer supports utilized, such as (1) poly- coating of the nanofiber membrane support is a beneficial technique for
vinylidene fluoride (2) polyacrylonitrile (3) polyimide and (4) poly- enhancing the membrane support layer hydrophilic property and it very
sulfone, used either individually or as blend for improving the mem- well may be a practical choice in the manufacturing of superior per-
brane efficiency. formance thin-film composite-FO membranes. Despite the fact that
numerous positive as well as promising results are stated on the na-
nofiber utilization as the center layer for forward osmosis process,
5.4.1. Polyvinylidine fluoride nanofibers for FO membranes formation of a uniform, robust, dynamic layer over a rough surface of
A quicker way towards generating commercially used superior- nanofiber is as yet a challenge.
performance forward osmosis membranes is to adopt practical methods In the specific examination carried out by Gonzales R et al. [239], a
during the manufacturing of membrane. PVDF is an established mem- realistic consolidation of molecular LbL method, electrospinning, and IP
brane material which is characterized by its better chemical and me- was done for improving the selectivity and hydrophilicity of the
chanical stabilities. On the other hand, the PVDF hydrophobicity might membranes, along with the proper bonding of the selective PA layer on
not be appropriate for forward osmosis membrane due to the fact that the nanofiber membrane support. Here, a superior performance elec-
the existence of the hydrophobic support layer of the forward osmosis trospun polyvinylidene fluoride nanofiber-supported TFCM was effec-
membrane induced the membrane wettability as well as the solvent tively manufactured subsequent to molecular LbL polyelectrolyte de-
transport [238]. Further, the membrane dehydration effectively hap- position. The negatively charged electrospun polyacrylic acid (PAA)
pens particularly when extreme salinity water is utilized as the draw nanofibers have been deposited on electrospun polyvinylidene fluoride
solution (DS), which lessens the effective area of diffusion thereby en- nanofibers for generating a support layer comprising of PAA and
hancing internal concentration polarization (ICP) and diminishing for- polyvinylidene fluoride nanofibers. This developed an extra hydrophilic
ward osmosis flux. support relative to the original polyvinylidene fluoride nanofiber
Hydrophobic electrospun polyvinylidene fluoride NFM support was membrane support. The PAA-polyvinylidene fluoride support later ex-
effectively modified by Park et al. [225] through poly(vinyl alcohol) dip perienced an LbL deposition of PAA and polyethylenimine for gen-
coating along with acid-catalyzed crosslinking utilizing glutaraldehyde erating a polyelectrolyte layer on the surface of nanofiber preceding IP
(GA) to manufacture a superior performance thin-film composite-FO process, that generates TFCM film composite membrane displayed
membrane. The polyvinylidene fluoride nanofiber with hydrophobic
Fig. 8. Mechanical properties of polyvinylidene fluoride (PVDF) heat-treated support, PVDF non-heat treated support and PVDF-poly(vinyl alcohol)(PVA) support at
wet as well as dry conditions.
After courtesy of [225].
24
Fig. 9. Comparison of the efficiency of the polyvinylidene fluoride (PVDF)-LbL TFCM and PVDF TFCM in the course of FO process at FO mode and pressure retarded
osmosis (PRO) mode, and then compared with the effectiveness of the commercially used CTA membrane having DI water and 0.5 M NaCl as the feed and draw
solutions, respectively.
improved porosity and hydrophilicity, without compromising the me- 5.4.2. Polyacrylonitrile nanofibers for FO membranes
chanical strength. The Fig. 9 demonstrates the efficiency of the poly- Developing pollutants, inclusive of pharmaceuticals, disinfection
vinylidene fluoride LbL TFCM and polyvinylidene fluoride TFCM in the byproducts, and personal care products, are of enhancing concern, that
course of forward osmosis process at forward osmosis mode and pres- could damage the ecological security and human health. In an in-
sure retarded osmosis (PRO) mode, and then compared with the ef- vestigation performed by Pan S. F et al. [240], self-sustained electro-
fectiveness of the commercially used CTA membrane having deionized spun PAN nanofiber supported PA based TFCM (PA/PAN-eTFCM) was
water (DI water) and 0.5 M NaCl as the feed and draw solutions, re- fabricated, and examined for the treatment of simulated tetracycline
spectively. Out of the 3 membranes tested, the membrane poly- (TC) wastewater. The fabrication of nanofiber supported TFCM was
vinylidene fluoride-LbL showed the greatest water flux values of 28.3 diagrammatically represented in Fig. 10, which was categorized into
and 24.1 LMH for PRO and FO mode, respectively, succeeded by the two separate stages: (1) manufacturing of nanofiber support and (2)
polyvinylidene fluoride-based TFCM with values about 10.4 LMH (for interfacial polymerization (IP) of PA layer. Particularly, a poly-
pressure retarded osmosis mode) and 8.0 LMH (for forward osmosis acrylonitrile nanofiber support was manufactured by electrospinning
mode). In the case of commercially used CTA membrane, the water with no backing layer. The polyacrylonitrile nanofiber support was
fluxes of PRO mode and FO mode was 6.7 LMH and 5.4 LMH, respec- subsequently laminated using a paper laminator. This laminated na-
tively, and this membrane was the least efficient one, relative to the nofiber support showed great hydrophilicity as well as mechanical
other two membranes. Furthermore, the commercially used CTA properties with strain, stress, and water contact angle of 68 ± 0.28%,
membrane demonstrated the most reduced water flux values, it ad- 13 ± 0.77 Mpa, and 32.3 ± 1.3°, respectively. The PA composited
ditionally displayed increased specific reverse salt flux, relative to the membrane developed consequently exhibited an increased permselec-
TFCMs. It can be clearly noted that all the three membranes showed tivity (A = 1.47 LMH bar−1 and B = 0.278 LMH), low structural para-
decreased reverse salt flux as well as water flux under the forward os- meter (S = 168 μm), and accomplished > 57 LMH water flux utilizing
mosis mode, relative to the pressure retarded osmosis mode, and this 2 M salt as the draw solution. The PA/PAN-eTFCM was effectively
was due to the dilutive internal concentration polarization (ICP) inside utilized in a membrane distillation−forward osmosis (MD–FO) hybrid
the membrane support layer, that remarkably decreased the osmotic process for simulated TC wastewater treatment and production of water
pressure difference in the course of FO mode [225]. Also, the poly- for the first time. The rejection of TC was > 99.9%, and a water re-
vinylidene fluoride-LbL TFCM demonstrated low structural parameter covery of about 15–22% was attained after 7 h running in the MD–FO
value and increased pristine water permeability of 221 μm and hybrid operation. At the same time, the PA/PAN-eTFCM displayed a
4.12 Lm−2h−1bar−1, respectively, considerably better relative to moderately longer stable performance in the hybrid framework. The
commercially used FO membrane. Thus, the authors concluded that the aforestated results demonstrate the utilization of PA/PAN-eTFCM as a
LbL deposition of polyelectrolyte is hence a practical and useful mod- potential FO membrane for wastewater treatment.
ification technique for manufacturing superior performance nanofiber There still exist a few issues for nanofiber-based FO membrane, for
supported TFCM. example, poor interfacial strength between support layer and active
Fig. 10. Diagrammatic representation of fabrication of electrospun nanofiber supported TFC membrane.
25
layer, easy deformation, and low separation. In a study by Shi Jie et al. chloride (TMC), aqueous phase monomer m-phenylenediamine (MPD),
[241], the polyacrylonitrile nanofiber was undergone surface mod- and aqueous phase co-solvent ethanol, the thin-film composite FO
ification using the hydrolysis technique to develop a hydrophilic na- membrane was prepared by two interfacial polymerization procedures,
nofiber surface, in order to enhance the permeability and diminish the as presented in Fig. 11. The initial interfacial polymerization procedure
internal concentration polarization (ICP) effect in forward osmosis with the unusual order (i.e., the membrane was first immersed in the
process. Subsequently, the hydrolyzed nanofiber-based forward osmosis trimesoyl chloride organic phase, subsequently in the co-solvent
membranes were fabricated as well as tailored by including a chitosan ethanol-water m-phenylenediamine aqueous phase) was utilized to re-
(CS) sub-layer to bind as well as bridge active layer and nanofiber mat. duce the pore size of polyimide microporous nanofiber membrane
The physical property and structure of polyacrylonitrile/chitosan support for the preparation of the PA layer. The second interfacial
composite support layers were optimized by modifying the concentra- polymerization procedure was utilized to develop the moderately dense
tion of CS. The results demonstrated that increment in the concentra- PA layer with the conventional order (i.e., the membrane was first
tion of CS caused a continual decrease in the water flux of composite immersed in the co-solvent ethanol-water m-phenylenediamine aqu-
forward osmosis membranes and the salt flux diminished first and later eous phase, and then in the trimesoyl chloride organic phase). The test
increased. The salt rejection attained 97% and the reverse salt flux was results demonstrated that greater ethanol concentration resulted in
just 0.93 g/m2·h in forward osmosis mode when the CS casting solution relatively increased pure water permeability in reverse osmosis process
concentration was 3.5% (CS-3.5), that displayed the least value among and osmotic water flux in forward osmosis process, whereas the salt
the nanofiber-based forward osmosis membranes mentioned in litera- rejection in reverse osmosis process diminished and the reverse salt flux
tures. The extensive performances of CS-3.5 accomplished an ideal enhanced. The obtained results could be credited to the impact of the
level, possessing both better filtration performances and appropriate addition of ethanol into aqueous phase on the surface morphology,
mechanical strength. Also, the aforestated study illustrated that the hydrophilicity and PA layer structure.
manufactured composite forward osmosis membranes with poly-
acrylonitrile/chitosan composite support layers accomplished 90 Mpa 5.4.4. Polysulfone/Polyacrylonitrile blend nanofibers for FO membranes
Youngs modulus and 30 Mpa tensile strength, which was similar to A perfect membrane for the forward osmosis process must have the
most of the published nanofiber-based and phase inversion substrates. below mentioned features: higher rejection of solute, better water
The subsequent water flux of the optimum composite forward osmosis permeability, adequate mechanical strength, and lower ICP. ICP is
membrane was 55.05 LMH in FO mode. The structural parameter of considered as an inevitable phenomenon in osmotic pressure-based
Chitosan-3.5 was about 203 μm. The inclusion of chitosan sub-layer membrane process which happens inside the membrane support layer.
contributes a miraculous effect on the mechanical and filtration per- For diminishing the ICP, different methods to upgrade the hydro-
formance of forward osmosis membrane, which is significant to break philicity of the FO membrane support could be utilized. The polymer
the obstructions in forward osmosis process. blending is one of the efficient strategies to accomplish advanced
properties of the polymer solution with less intricacy. The blending of
5.4.3. Polyimide nanofibers for FO membranes the polymers not just upgrades the properties of single polymer fabri-
Polyimide (PI) material is known for its exceptional chemical re- cated membrane but also upgrades the membrane water flux by the
sistance, thermal stability, and mechanical property. Relative to the decreasing ICP flux of the membrane. In fact, the membranes demon-
commonly utilized substrates, the average pore size of the PI nanofiber strate higher permeability relative to membrane developed from single
substrate is comparatively bigger, which is designed for minimizing the polymer.
permeability resistance. Polysulfone (PSf) is regarded as a perfect polymer in the membrane
In the case of hydrophobic substrates, the modification is used to industries due to its superior properties, for example, thermal, che-
deal with the decrease in the mechanical properties of the fibers in the mical, and mechanical resistance, along with its low cost. However, PSf
course of forward osmosis process. Because of hydrophilicity mod- is a hydrophobic polymer, that must be undergone modification using
ification, the aforestated substrates show better wettability for inter- suitable techniques. The mixing of polysulfone along with a polymer
facial polymerization (IP) with no swelling. Mainly, there are two pri- possessing increased spinnability and hydrophilicity (for example
mary methods for hydrophilicity modification. First one is the surface polyacrylonitrile, PAN) could be utilized to diminish the ICP. The work
modification, and the other one is the blending modification of different by Shokrollahzadeh S. et al. [134] examined the impact of an advanced
hydrophilicity additives. A unique IP process on PI microporous na- polymer blend of polyacrylonitrile/polysulfone (PAN/PSf) nanofibers
nofiber membrane support with 1.27 μm mean pore size was reported fabricated by means of electrospinning procedure as substrate to de-
by Chi, X. Y et al. [242]. Utilizing organic phase monomer trimesoyl velop thin-film composite FO membrane. In the electrospinning
Fig. 11. Schematic portrayal of the manufacturing of TFC forward osmosis PI based nanofiber membranes.
26
process, the solvents were optimized. A thin-layer of PA was effectively low maintenance and operating costs, great control of membrane
manufactured on the electrospun nanofibrous substrate by means of IP fouling, excellent control of concentration polarization, and further-
process. The efficiency of the nanofiber-based TFCM was compared more economical production [252]. Out of the different techniques to
with the in-house-made (PAN/PSf) TFCM, where its substrate was generate MD membranes, electrospinning is considered to be a viable
manufactured by PI process. The nanofiber-based TFCM showed re- and straightforward approach to manufacture persistently polymeric
markable enhancement in water permeability as well as hydrophilicity, nanofiber membranes with nanoscale and microscale fibers. These
and the reverse salt flux was decreased. Further, the structural para- membranes, prepared from the electrospinning process, possess great
meter (S) value of the manufactured nanofiber-based TFCM diminished surface-to-volume ratio and superior porosity, which facilitate the ap-
significantly, which indicated the decrease in the ICP during the for- plication in filtration operations [142]. At the same time, the uniform
ward osmosis process. The aforestated results were because of the nanofiber structures prepared by plain polymer dopes with no hydro-
structural characteristics of the nanofiber, for example, interconnected phobic additives are normally not considered to be superhydrophobic
open pore structure and better porosity. The impacts of various salts as [253]. In general, the LbL assembly is introduced into the electrospun
draw solutions (MgSO4, MgCl2, KCl, NaCl) on the osmotic performance fibers for generating a surface with superhydrophobicity [254]. Taking
of the TFCMs and nanofiber-based TFCMs were assessed. The water flux into account the properties of effective membranes, nanofibers appear
of the fabricated forward osmosis membranes as a function of various to be a decent candidate for the process MD. For majority cases, the
draw solutions are presented in Fig. 12. Out of the various salts tested polymer polyvinylidene fluoride is favored because of its spinnability as
under the equivalent osmotic pressure, the greatest water flux was at- well as its solubility [8,255].
tained utilizing the KCl draw solution, whereas the MgSO4 draw solu- At present, the electrospun nanofiber membranes (ENFMs) has re-
tion showed the worst performance in both the TFCMs and nanofiber- ceived considerable attention in membrane distillation because of its
based TFCMs. The nanofiber-based TFCMs displayed greater water flux benefits such as increased porosity, interconnected pore structure, and
compared to that of the TFCM for KCl draw solution. controllable pore size, that are noted to be the fundamental factors
which affect the permeability. On the other hand, the longer term
5.5. Membrane distillation durability in the course of membrane distillation process should be
additionally considered because of the lack of the surface hydro-
Membrane distillation (MD) is one of the developing desalination phobicity. Consequently, more consideration has been focused on the
technologies for the generation of clean water. This is a thermally- study of the explicitly designed superhydrophobic membranes due to
driven water separation procedure, wherein just vapor molecules can the lifting-up effect for membrane distillation flux and the improved
pass through a permeable hydrophobic membrane. Relative to other wetting resistance, which made these membranes potential candidates
alternative systems, MD possess numerous benefits, for example, for membrane distillation process with improved salt rejection, per-
greater rejection of salt, lesser energy utilization and lesser functioning meability along with fouling resistance. Also, it can be noted that the
temperature than typical distillation processes. Also, the hydrostatic superhydrophobic surface possessing the self-cleaning nature will be
weight pressure encountered in this process is lesser than that utilized much advantageous to cause the feed liquid sliding over the surface of
in pressure-driven membrane operations such as RO. In this manner, membrane like the lotus effect instead of adhering and subsequently
MD is anticipated to be an economic process, that requires lower de- penetrating into the interfiber spacing simply like the petal effect [256].
manding of membrane features as well. In this respect, more affordable By the introduction of readily roughened nanomaterials or/and
material can be associated with it, for example, plastic, thus reducing hydrophobic agent, substantial efforts have been devoted to develop
corrosion issues. As indicated by the standard of vapor–liquid equili- superhydrophobic surfaces dependent on nanofibers for membrane
brium, the membrane distillation procedure has an elevated rejection distillation, inclusive of surface modified electrospun nanofiber mem-
factor. In actuality, entire separation happens. Also, the pore size of the branes [257,258], composite electrospun nanofiber membranes
membrane needed for MD is moderately bigger relative to those for [259,260,261,262], and mixed matrix electrospun nanofiber mem-
alternate membrane separation procedures, for instance, RO. In this branes [263]. For instance, the manufacture of self-roughened super-
manner, the MD procedure experiences reduced fouling. Also, the hydrophobic ENFMs was reported by the modification of PVDF nano-
membrane distillation structure has the possibility to be joined with fiber surface with fluorododecyltrichlorosilane (FTCS) utilizing the
other separation procedures to make an integrated separation frame- solution immersion strategy, demonstrating an increased water contact
work, for example, with an RO unit [243] or with UF unit [244]. The
process MD is competitive for desalination of seawater as well as
brackish water [245]. Besides, MD can use alternate energy sources, for
example, solar energy [246]. Also, MD has been utilized for the
radioactive waste treatment, where the safe discharge of the product to
the environment could be achieved [247]. Additionally, MD is a com-
petent procedure for separating organic along with heavy metals from
wastewater [248], and from aqueous solution [249]. At the same time,
the MD process has some drawbacks, for example, lower permeate flux,
great susceptibility permeate flux to the temperature and concentration
of the feed conditions because of the temperature and concentration
polarization phenomenon.
Various kinds of membranes, as well as filtration systems, are uti-
lized in water treatment procedures dependent on their particle filtra-
tion and pore sizes. For the process MD, the polymer membranes ought
to exhibit superior permeability in addition to hydrophobicity with
absence of wetting, good chemical stability, thermal stability over a
wide scope of temperatures, narrow pores, and have superior me-
chanical strength [250,251]. Membranes must be arranged as mem-
brane modules which could be a plate, spiral wound, and hollow fiber Fig. 12. Water flux of fabricated thin-film composite and nano-fiber based thin
type for practical utilization. For a proficient membrane module, the film composite membrane.
principal factors are a membrane possessing superior packing density, After courtesy of [134].
27
angle (WCA) of about 160.2° [264]. As regards the mixed matrix surface along with superior hydrophobicity. In addition, the heat-
electrospun nanofiber membranes, the nanomaterials or their pre- press post-treatment is regarded as an essential procedure for
cursors have been straightly blended with polymer solutions for improving fresh NFM integrity, to increase the permeation flux of
creating extra roughness in the course of electrospinning process, at the water and assist to preclude membrane pores from wetting during the
same time, the hydrophobic agents were generally used to bring down DCMD process. The polyvinylidene fluoride post-treated NFMs had the
the surface free energy. Particularly for composite ENFMs, the multi- option to contribute a consistent water permeation flux of around
layer framework comprised of an overlayer deposited onto a porous 21 kg m−2 h−1 across the whole trial of 15 h, that was noted to be 100%
nanofiber scaffold, that have different utilizations in the domain of higher relative to the untreated original membrane. The benefits of the
water treatment because of their benefit of increased rejection as well post-treated membranes relative to original membranes include the
as great permeability [265]. During the MD process, the polymeric enhancement in permeation flux and extraordinary reduction in
coating only or consolidated with nanomaterials were developed onto membrane pore wetting. Clearly, even the heat-press treatment
the nanofiber support, where the porous scaffold-like nanofibrous diminished the electrospun membrane porosity, the advantages
substrate demonstrated lower resistance for vapor transport and great acquired from adaptive heat-press treatment are above the negative
mechanical support and the thin top barrier layer contributed the se- effects of membrane distillation utilization. The obtained conclusions
lectivity role. Despite that, the utilization of nanomaterials as well as were superior to those of commercially used polyvinylidene fluoride
hydrophobic agent may cause security issue along with environmental membranes and the nanofiber polyvinylidene fluoride-clay membrane
contamination, and the complicated modification procedure and lower stated in the same article, recommending the proficiency of
usage of functional additives embedded in polymer matrix likewise polyvinylidene fluoride ENFMs for DCMD utilization.
enhanced the cost of membrane cost [263,266]. There are a few research studies reported so far on unsupported
Typically, there are four distinctive membrane distillation config- dual-layered hydrophilic/hydrophobic ENFMs for desalination by air
urations inclusive of air gap membrane distillation (AGMD), vacuum gap membrane distillation and DCMD [269]. Khayet M. et al. [270]
membrane distillation (VMD), direct contact membrane distillation showed that double layered ENFMs comprising of two polymers of
(DCMD), and sweeping gas membrane distillation, where the heat and distinct hydrophobicities exhibit better direct contact membrane dis-
mass transfer happen simultaneously [267]. In the following section, tillation desalination performance relative to single layer ENFMs fab-
we can categorize the application of nanofiber membranes on the basis ricated under similar electrospinning time. The membrane was fabri-
of different membrane distillation configurations. It has to be noted that cated using the hydrophilic polymer polysulfone (PSF) and the
ENFM utilization in membrane distillation are mainly concentrated on hydrophobic polymer PVDF. The manufactured double-layered ENFMs
the DCMD, even though both AGMD and VMD have insufficiently re- showed a table and cohesive fiber structure with an irregular fiber
ported, these techniques also have been considered in this paper. distribution and more open polysulfone layer web framework relative
However, there is not much information available on the utilization of to the poly(vinylidene fluoride) layer. The direct contact membrane
nanofiber membranes for the sweeping gas membrane distillation distillation permeate flux of the double layered ENFMs was observed to
configuration. be greater relative to the single-layered poly(vinylidene fluoride) ENFM
and it enhanced with increment in the thickness of the polysulfone
5.5.1. Direct contact membrane distillation (DCMD) layer. The direct contact membrane distillation permeate flux of the
Relative to other three procedures, DCMD is considered to be the double layered ENFMs attained values of 53.6, 49.9 and 47.7 LMH and
simplest and well-known function mode, confirmed by the reality that salt rejection factor of 99.99% for the dual layered membrane with
over 60% of researches based on MD are about DCMD [268]. In general, 80 °C feed temperature, 20 °C permeate temperature and a salt con-
the hydrophobic nanofiber membranes have superior hydrophobicity, centration of 0, 12 and 30 g/L, respectively. Despite that, under iden-
adjustable pore sizes, great surface porosity, flexible membrane thick- tical conditions, the direct contact membrane distillation permeate flux
ness, that enable them an interesting candidate as a membrane for the of the electrospun single layer poly(vinylidene fluoride) ENFM was
MD process. One of the benefits of ENFMs is the diversity of the poly- noted to be lesser (that is, 36.1, 34.0 and 32.9 LMH) with additionally
mers in manufacturing the membrane distillation membranes. Instead higher salt rejection factors.
of the limited option of the polymers for commercially utilized MD The antiwetting ability of ENFMs can be lowered by diminishing the
membranes manufacture, different kinds of polymers could be em- pore size or enhancing the surface hydrophobicity. The accessibility of
ployed to manufacture the ENFMs. For the DCMD utilization, the uniquely designed membrane distillation membranes, that can satisfy
classification can be done on the basis of the polymers used, such as (1) the necessities for membrane distillation procedure, for example, su-
polyvinylidene fluoride and (2) fluoropolymers for improving the effi- perior hydrophobicity for avoiding wetting of membrane and great
ciency of membrane. porosity to improve permeation of vapor, is one of the problems to be
handled for membrane distillation industry utilization. Basically, the
5.5.1.1. Polyvinylidine fluoride nanofibers for DCMD utilization. In a techniques used to accomplish superhydrophobic surfaces are to en-
research carried out by Liao Y et al. [255], the team explored the hance roughness of the surface and later surface modification with
achievability and optimization of electrospun polyvinylidene fluoride energy-efficient as well as non-polar molecules. It can also be noted that
nanofiber membranes utilized for DCMD procedure to generate surface roughness is generally more significant than the less surface
drinking water. For enhancing and stabilizing the performance of the energy, due to the fact that both exceptionally hydrophobic and mod-
nanofiber membrane in the DCMD procedure, the properties and erately hydrophobic materials can have comparable superhydrophobic
structures of resultant membranes were optimized by regulating a characteristics whenever it is roughened. In the research carried out by
range of factors inclusive of spinning parameters and polymer dope Yuan Liao et al. [126], a simple technique for the generation of nano-
compositions. From the experimental results, it was noted that fiber membranes with superhydrophobicity by surface modification
electrospinning process parameters and polymer dope solution was investigated. Two types of polyvinylidene fluoride nanofiber
properties are principal factors for determining the structure of the membranes with superhydrophobicity, i.e., surface-modified and in-
membrane. By controlling the concentration of polymer and including tegrally-modified polyvinylidene fluoride membranes, were effectively
appropriate additives in the polymer dope solution, the nanofibers manufactured by ES technique succeeded by modification of surface,
having a short diameter can be manufactured and membranes that involves dopamine surface activation, deposition of silver (Ag) as
developed by the nanofibers have limited pore sizes. From the surface well as hydrophobic treatment. The aforestated modification is ad-
contact angle analysis, it was noted that the entire electrospun vantageous on account of wide applicability and mild reactions. These
polyvinylidene fluoride nanofiber membranes showed a rougher unique composite nanofiber membranes were characterized by several
28
measures and tested against commercially used polyvinylidene fluoride and 50 °C, respectively). The longer stability of F-TR-ENFM is also
flat sheet membrane for membrane distillation utilization. From the found to be > 250 h of operating time.
different characterizations, it was recognized that the modifications
have changed the topology as well as the morphology of the membrane 5.5.1.3. Polysulfone nanofibers for DCMD utilization. Polysulfone is an
surface and contributed superhydrophobic property to the membrane interesting membrane material utilized in various filtration processes
because of their hierarchical structures. Relative to the unmodified because of its good mechanical properties, remarkable thermal
membrane, the integrally-modified membrane (I-PVDF) accomplished a stability, and superior chemical resistance. Despite that, because to its
stable and high water flux of 31.6 LMH utilizing a 3.5 wt% concentra- greater tendency to biofouling, different surface modification
tion of NaCl as the feed solution, when the permeate and feed tem- techniques have been established for improving its hydrophilicity
peratures have been fixed at 293 K and 333 K, respectively. As indicated [273].
by Yuan Liao et al. [126], the results attained were better than all other In the research work by Li, X et al. [256], unique self-cleaning
polyvinylidene fluoride flat-sheet membranes tested under the com- polysulfone-polydimethylsiloxane-x-y ENFMs with modest direct con-
parative conditions, that was presumed to be ascribed to the slight tact membrane distillation performance have been fabricated by ES
thickness and open-surface pore framework of the polyvinylidene process of polysulfone nanofibers with subsequent poly-
fluoride NFM with the assistance of ES. The superhydrophobic char- dimethylsiloxane modification along with cold-press post-treatment.
acteristic of the surface of the membrane caused by the integral mod- Because of its simplicity, this ENFM fabrication technique could be
ification on entire nanofibers provides the membrane superior anti- effectively scaled up. The results demonstrated that poly-
wetting characteristics although maintaining great water flux. dimethylsiloxane adhesion or/and accumulation was developed on the
It is a major challenge to develop a perfect as well as super- surface of ENFM with the increment in the concentration of poly-
hydrophobic skin layer by polymer on an exceptionally porous nano- dimethylsiloxane, initiating the super hydrophobicity and self-cleaning
fiber support layer with no cooperation of some effectively intercepted property because of the surface hierarchical roughness and low surface
nanomaterials due to the simple penetration of the coating solution energy of polydimethylsiloxane. The cold-press pre-treatment pressure
[260]. In the work by Deng Li. et al. [271], an exceptional double layer showed a significant influence on the membrane surface morphology as
composite membrane comprising of a superhydrophobic selective skin well as structural features. With the enhancement in the cold-press post-
from amorphous polypropylene (aPP) and an electrospun PVDF nano- treatment pressure, the liquid entry pressure of water of the poly-
fiber support was fabricated by means of a facile vacuum filtration sulfone-polydimethylsiloxane-x-y ENFMs was upgraded remarkably,
technique. Benefiting from the superior tackiness as well as less surface whereas the void volume fraction as well as the size of the inter-fiber
free energy of amorphous polypropylene, the robust double layer spacing were diminished, however, at the same time larger than those
amorphous polypropylene/PVDF membranes not only can show ex- of the polysulfone-y ENFMs because of the physical flexibility of the
ceptional improvement in hydrophobicity together with liquid entry polydimethylsiloxane under pressure. During the direct contact mem-
pressure of water (LEPw), however, it can also tune the pore size with brane distillation tests, the polysulfone-y ENFMs experienced wetting
no serious compromise in the porosity. The superhydrophobic amor- because of its inadequate hydrophobicity and lower values of liquid
phous polypropylene porous skin functioned as extra hindrance to entry pressure of water. It was noted that the cold-press post-treatment
surface wetting and combined the interconnected nanofiber support to for polysulfone-polydimethylsiloxane ENFMs is a vital procedure to
contribute direct pathways to vapor transportation, prompting superior fabricate good as well as high performance membranes layers. The
DCMD performance. Substantially, the ideal superhydrophobic amor- polysulfone-polydimethylsiloxane-x-y ENFMs with y ≥ 4 and x ≥ 1
phous polypropylene/PVDF membrane displayed an ultrahigh were observed to be promising in membrane distillation application
permeate vapor flux of about 53.1 LMH and a stable permeate con- due to their steady direct contact membrane distillation performance
ductivity for 40 °C transmembrane temperature (salt feed 3.5 wt% (that is, extremely low electrical conductivity of the permeation in the
NaCl) > 50 h operation. It was found that the aforestated direct contact course of 12 h DCMD process). This study exhibited the practicality of
membrane distillation performance was greater than twice that of designing and fabricating self-cleaning polysulfone-poly-
conventional commercially used poly(vinylidene fluoride) membrane dimethylsiloxane ENFMs for membrane distillation applications. In
and much better than those of modified ENFMs reported up until now, order to further upgrade the liquid entry pressure of water of the
demonstrating extraordinary applicability for MD desalination. polysulfone-polydimethylsiloxane-x-y ENFMs, in future research work
we suggest the utilization of various solvents to improve the compact-
5.5.1.2. Fluoropolymer nanofibers for DCMD utilization. In the past few ness of polysulfone ENFMs and include inorganic hydrophobic nano-
years, researchers have recommended different types of electrospun particles into the polydimethylsiloxane layer to enhance the surface
membranes utilizing hydrocarbon polymers as well as fluoropolymers. roughness as well as hydrophobicity, and lessen the inter-fiber spacing
The fluoropolymer is a potential candidate for membrane distillation of these ENFMs.
utilization because of its intrinsic hydrophobicity. In spite of the fact Very limited research studies have been performed on the in-situ
that PTFE demonstrated better hydrophobicity out of different surface modification of electrospun nanofibers. In the research work
fluoropolymers, studies on polytetrafluoroethylene ENFMs have not carried out by Khayet, M. et al. [274], bead-free and superhydrophobic
been performed due to its complicated process ability. The fluorine electrospun nanofibers were effectively fabricated utilizing a blend of
atoms are non-polar in nature and possess a lower interaction energy polysulfone, a host hydrophilic polymer, and a limited quantity of an
with molecules of water and a lower packing density. Park, S. H et al. oligomeric fluorinated polyurethane additive (FPUA), for example, at
[272] fabricated fluorine-containing thermally-rearranged ENFMs (F- least 3 wt% FPUA in the polysulfone blend. We have also noted that
TR-ENFMs) for membrane distillation utilization for the first time. only limited researches have been concentrated on the utilization of
These F-TR-ENFMs demonstrated upgraded hydrophobic properties, for lower amounts of fluorinated active additives in the dope solution (that
example, high water contact angle (143°), increased effective is, under 10 wt%) for the fabrication of electrospun superhydrophobic
evaporation area (EEA), and high LEP with water (LEPw) (1.3 bar) and electrospun nanofibers [275]. In the process of ES, an impulsive
because of the inclusion of fluorine atoms thermally rearranged FPUA segregation to the surface of nanofiber was identified through X-
membrane backbone. The fabricated F-TR-ENFMs displayed ray photoelectron spectroscopy (XPS) at various take-off angles. The
extraordinary membrane distillation performance (water flux increment in the FPUA amount the polysulfone blend generated nano-
−114.8 kg m−2 h−1, and salt rejection > 99.99% at permeate and fibers with greater diameters and more wide diameter distributions
feed temperatures of 20 °C and 80 °C, respectively) and superior because of the remarkable improvement in the viscosity of the ES dope,
energy efficiency (52.1% at permeate and feed temperatures of 20 °C despite the fact that its electrical conductivity was enhanced and the
29
surface tension was diminished. The FPUA blended polysulfone ENFMs thermal radiation energy of antimony-doped tin oxide increased the
fabricated with FPUA amounts up till 4.5 wt% (PSf-4.5, PSf-3 and PSf- temperature of hybrid membrane by almost 13 °C, that diminished the
1.5) demonstrated to be satisfactory for desalination by DCMD tech- effect of temperature polarization clearly. It was found that the infrared
nique with stable as well as competitive permeate fluxes. For instance, radiation advanced the permeate flux of the entire poly(vinylidene
by the ENFM fabricated with 4.5 wt% FPUA in the polysulfone blend fluoride)/antimony-doped tin oxide membranes.
(PSf-4.5), at a permeate temperature of 20 °C and a feed temperature of CNTs are found to be the perfect hydrophobic material and these
80 °C a permeate flux of almost 53.8 kg/m2 h was accomplished, when nanoparticles are generally utilized to manufacture membranes. For
30 g/L NaCl feed aqueous solution was treated by DCMD. The electrical example, the immobilization of the nanoparticle carbon nanotubes in
conductivities of the permeate were less (< 5.1 μS/cm) with re- polymer membrane matrices could enhance the wetting resistance of
markably higher rejection factors (> 99.99%). In the course of direct MD [277]. The ENFMs mixed with carbon nanotubes demonstrated
contact membrane distillation desalination for these ENFMs, no inter- increased water contact angle relative to commercially used PVDF
fiber space wetting was identified. membrane [278]. On the other hand, during the fabrication process of
CNT-nanocomposite ENFMs, there exist a problem of agglomeration of
5.5.2. Vacuum membrane distillation (VMD) the nanoparticles, due to the fact that the carbon nanotubes were very
In the subsequent part, some discussions on the utilization of na- difficult to totally distribute in an aqueous environment, or reaggregate
nofiber membranes on vacuum membrane distillation system have been in electrospun polymer solution because of comparatively longer
provided. The application of polymers such as PVDF, PTFE and nano- manufacturing time. In an investigation carried out by Yan, K. K et al.
particles like CNTs has been analyzed. [279], the group introduced a simple surface coating method for the
manufacture of superhydrophobic ENFMs by means of a spraying
5.5.2.1. Polyvinylidine fluoride nanofibers for VMD utilization. The technique. In this strategy, the lesser content of carbon nanotubes dis-
polymer PVDF is noted to have good chemical resistance, persion with an appropriate solvent performs a significant job to restrict
hydrophobicity and thermal stability. The functional inorganic the CNT agglomeration. Since PVDF based ENFMs can be totally wetted
nanoparticles possessing infrared (IR) effect (i.e., SiO2, AZO, ATO, by ethanol, isolate drop cannot develop on the surface of the mem-
TiO2, Al2O3, etc.) have been generally utilized in heat insulating glass. brane, in this way the CNT agglomeration was restrained during the
The most commonly utilized aforestated type of inorganic nanoparticle entire ethanol quickly evaporated procedure. The network of CNTs
is antimony-doped tin oxide (ATO), which is the blend of Sb2O3 and remarkably upgraded the liquid entry pressure and hydrophobicity of
SnO2 with a specific mass ratio. Presently, there are numerous reports membranes. The VMD results showed that the membranes coated with
on the temperature polarization phenomenon in the membrane CNTs showed best performance both in water flux as well as anti-wet-
distillation process, however there are not many researches done on ting in the desalination process. The CNTs coated membranes' proper-
the best way to tackle it. Huang, Q. et al. [276] proposed a unique ties showed no significant variation subsequent to vacuum membrane
technique for upgrading the membrane distillation performance by the distillation tests. The aforestated method to manufacture super-
temperature polarization suppression. In this research work, the team hydrophobic membranes has the great potential in several industrial
manufactured poly(vinylidene fluoride)/antimony-doped tin oxide utilizations. We found that the vacuum membrane distillation perfor-
hybrid nanofiber membranes which had better infrared-stimulated mance of this CNT coated ENFMs were significantly better than several
thermal effects. It was shown that photothermal heating produced by other nanofiber membranes in other different studies [278,280,281].
poly(vinylidene fluoride)/antimony-doped tin oxide hybrid nanofiber
membranes significantly increased the surface temperature of the 5.5.2.2. Polytetrafluoroethylene nanofibers for VMD utilization. PTFE
membrane. In comparison with the poly(vinylidene fluoride) nanofiber membranes utilized for VMD was prepared by Zhou T.
nanofiber membrane without antimony-doped tin oxide loading, the et al. [282] by sintering polytetrafluoroethylene/polyvinyl alcohol
Fig. 13. NaCl rejection of 10 h continuous vacuum membrane distillation application.

30
H. Saleem, et al.
Table 3
Summary of recently published papers on the membrane and separation properties of nanofiber membranes for MF, UF, NF FO and MD in desalination and water treatment applications.
Sl. no. Membrane Method Membrane properties Separating property Process Ref.
Pore size (μm) Porosity (%) Flux (kg/m2 h) Solute rejection (percent) Stable time
(hours)
1 CNTs coated superhydrophobic ENFMs/Spraying Electrospinning/CNT spraying 0.19 70.2 28.4 Salt - > 99.9 26 Vacuum membrane [279]
method distillation
2 Heat pressed dual-layer nanofiber nonwoven Electrospinning/heat press post 0.18 85.3 15.5 Salt - > 99% – Air gap membrane [269]
membranes treatment distillation
3 Fluorine containing thermally-rearranged ENFMs Electrospinning/thermal rearrangement 0.8 ± 2 81 ± 2 114.8 Salt - > 99.99% 250 Direct Contact Membrane [272]
Distillation
4 Amorphous polypropylene/PVDF composite Electrospinning/hot press heat treatment 0.46 79.7 135.3 Salt - > 99.99% 50 Direct Contact Membrane [271]
31
membrane Distillation
5 CF4 treated ominophobic polyvinylidene fluoride Electrospinning/CF4 plasma treatment 0.80 ± 0.02 86.4 ± 1.3 15.2 Salt -~100% Air gap membrane [258]
ENFMs (15 min treatment) distillation
6 Hydrolyzed PAN supported nanofiber-based FO Electrospinning/interfacial – 79.8 55.05 Salt-97% Forward Osmosis [241]
membranes Polymerization
7 Polyimide supported microporous nanofiber Electrospinning/interfacial 1.27 - 11.6 ± 2 Salt −49.8 ± 2% Forward Osmosis [242]
membrane polymerization
8 TFC FO membrane having electrospun polysulfone/ Electrospinning/phase inversion – 84.3 ± 3.6 3.68 ± 0.23 Salt −97.12 ± 0.92% Forward Osmosis [134]
PAN blend nanofibers as porous substrate method/interfacial polymerization
9 TFC NF membrane based on Polyethylene Electrospinning/reverse interfacial 0.0018 85 34 ± 2.3 Salt-78 ± 2% Nanofiltration [185]
terephthalate nanofiber support and PA topmost layer polymerization
10 Three-dual structure high flux NF membranes prepared Electrospinning/LbL assembly/phase – – 75 Salt-80% Nanofiltration [192]
with various SPEEK conc. inversion
11 Polysulfone ENFM Electrospinning/heat post-treatment 3.06 – 232 Humic acid-63.9 Microfiltration [160]
12 Polyvinylalcohol-MWCNT/Polyacrylonitrile Electrospinning/solution treatment – – 270.1 Salt-99.5 Ultrafiltration [179]
electrospun nanofiber membranes. Subsequent to the sintering process properties translate to superior salt rejection (~100%) and flux
at temperature 380 °C for almost 30 min, exclusive moniliform fiber (15.2 LMH) performances of P/CF-15 (15 min treatment time) even
network with a porosity of almost 80%, water contact angle > 150°, with the inclusion of up till 0.7 mM sodium dodecyl sulfate in the actual
and applicable strength was developed. In addition to this, by reverse osmosis brine feed in the course of air gap membrane
enhancing the thickness of membrane, high LEP value membranes distillation process. The results imply the great capability of the
presented in vacuum membrane distillation configuration was attained. tetrafluoromethane plasma modified nanofiber membrane in the
A membrane possessing a thickness of 156 μm and a LEP value of about treatment of challenging feed solutions which might consist of
165 kPa was utilized in vacuum membrane distillation process. Salt organic contaminants, for example, wastewater from coal seam gas
rejection and pure water permeability were examined. The pure water (CSG) exploration.
flux attained a high value of about 15.8 kg/m2 h when feed temperature
is 80 °C and the trans-membrane pressure is 30 kPa, and the membrane 5.5.3.2. Poly(vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP)
demonstrated a steady rejection of salt > 98.5% for 10 h operation nanofibers for AGMD utilization. In the recent past, the ES process has
when the feed salt concentration is almost 3.5%. The results in Fig. 13 been advanced to manufacture polyvinylidenefluoride-co-
illustrated the long-standing stability of the polytetrafluoroethylene hexafluoropropylene nanofibers and fiber films for utilization in air
ENFMs in vacuum membrane distillation utilization, which also shows gap membrane distillation. It must be noted that the morphology as
its possibility as well as prospect in commercial application of this well as measure of ENFMs are very much controllable relative to the
membrane. phase-inversion hollow fiber membranes, which is obtained by
changing the solution properties, for example, conductivity, surface
5.5.3. Air gap membrane distillation (AGMD) tension, concentration and processing conditions like tip-to-collector
AGMD has been reported to possess significant potential for com- distance, flow rate, and voltage. In the work by Hemmat A et al. [283],
mercial sustainability since it possesses the greatest thermal efficiency. the impacts of three salt additives inclusive of calcium chloride (CaCl2),
The existence of an air gap gives contributes better heat transfer re- lithium chloride (LiCl) and calcium carbonate (CaCO3), on the
sistance because of lesser thermal conductivity of air relative to the permeation efficiency and morphology of polyvinylidenefluoride-co-
membrane material, that lessens the heat losses, and gives increased hexafluoropropylene membranes were analyzed. It was discovered that
heat energy to be utilized for water evaporation in comparison to direct the incorporation of slight quantity of salt additive shifts the
contact membrane distillation. With regard to temperature polariza- morphology of fibers from beaded fiber to a homogenous fiber
tion, the air gap membrane distillation is superior to DCMD process framework. From the scanning electron microscopy images, it was
because of increased hear transfer resistance, that results in lengthier noted that the contact angle of polyvinylidenefluoride-co-
operation time with stable flux along with salt rejection performances. hexafluoropropylene membrane declined with the incorporation of
Despite that, the flux in air gap membrane distillation is usually less salt and accordingly membrane M1 (20 wt% PVDF with no salt
than those in VMD or DCMD due to the enhanced mass transfer re- additive) has the greatest contact angle, 136.0, relative to other
sistance because of the existence of stagnant air, which is a major issue membranes. Additionally, it was seen that the greatest porosity of
constraining the utilization of air gap membrane distillation. In the about 89% was obtained for the M2 membrane (20 wt% PVDF with
coming section, some discussions on the utilization of nanofiber 0.02 wt% LiCl as the additive). It was confirmed from this study that the
membranes on air gap membrane distillation system have been pro- polyvinylidenefluoride-co-hexafluoropropylene ENFM can be utilized
vided. in air gap membrane distillation process to generate pure water from
3.5 wt% salt feed aqueous solution, where the water flux was noted to
5.5.3.1. Polyvinylidine fluoride nanofibers for AGMD be 13.6 L/m2 h for the M2 membranes with LiCl as the additive salt.
utilization. Providing omniphobicity to the ENFM is an interesting It was noted already that the dual layered ENFMs comprising of two
technique to take advantage of its increasingly porous as well as polymers of diverse hydrophobicities demonstrated superior direct
multi-layered structure with moderately rougher surface. Out of the contact membrane distillation desalination performance relative to the
several surface modification techniques, the plasma treatment is single layer ENFMs manufactured under identical electrospinning time
considered to be an extendable way to provide resistant coatings on [270]. Similarly, for desalination by AGMD, Woo, Y. C. et al. [269]
the surface of the membrane. Specifically, tetrafluoromethane (CF4) prepared dual-layer nanofiber nonwoven membranes by a simple ES
plasma treatment permits etching, replacement or polymer method. Clean single and double layer ENFMs made out of a hydro-
modification of the membrane, improving its anti-wetting properties. phobic polyvinylidenefluoride-co-hexafluoropropylene (PVDF-HFP) top
Shon et al. [258] stated a technique of surface modification by layer with distinct supporting hydrophilic layer composed of either
tetrafluoromethane plasma on ominophobic polyvinylidene fluoride polyacrylonitrile (PAN), nylon-6 (N6), or polyvinyl alcohol (PVA) na-
ENFMs for the utilization in the air gap membrane distillation. In the nofibers were manufactured without and with heat press post-treat-
aforestated work, PVDF membranes were effectively manufactured by ment. The surface characterization demonstrated that the active layer
ES technique and subsequently modified by tetrafluoromethane plasma (i.e., PVDF-HFP) of all ENFMs displayed a rough, hydrophobic and
treatment. The manufactured and modified ENFMs were assessed via profoundly porous surface, whereas the other side was hydrophilic with
AGMD process utilizing the actual RO brine from coal seam gas (CSG) changing porosity. The heat-press post treatment of the membrane
produced water as the feed. The results recommend the effective brought about smaller pore size and thinner thickness. In a co-current
chemical modification of the membrane by tetrafluoromethane flow set-up, the air gap membrane distillation tests were performed
plasma treatment without remarkably modifying the morphology as with consistent inlet temperatures at the permeate and feed streams of
well as its physical properties, thereby contributing enhanced 20 ± 1.5 °C and 60 ± 1.5 °C, respectively. The air gap membrane
fluorination particularly through the development of CF2-CF2 and CF3 distillation module had a membrane area of about 21 cm2 and the
bonds, with the treatment duration. The aforestated prompted the airgap thickness was almost 3 mm. The clean single and double layered
advancement in the wetting properties of the modified membrane, due ENFMs illustrated a water permeate flux of almost 10.9–15.5 LMH
to the fact that the plasma treatment reduced its surface energy and utilizing 3.5 wt% salt solution as feed, which was a lot higher relative to
provided omniphobic property to the membrane. The optimal commercially used PVDF membrane (approximately 5 LMH). The ar-
treatment duration was noted to be 15 min, getting the maximum rangement of a hydrophilic layer at the lower layer improved the air
hydrophobicity as well as superior wetting resistance to low surface gap membrane distillation performance relying upon the wettability as
tension liquids, for example, ethylene glycol, mineral oil, and ethanol, well as the characteristics of the support layer. The PVDF-HFP/N6
and subsequently high LEP of about 187 kPa. The aforestated upgraded double layer ENFM manufactured under the optimum condition
32
H. Saleem, et al.
Table 4
Benefits and challenges of the different nanofiber membranes for various technologies in water treatment and desalination utilization.
Sl. no. Membrane Benefits Challenges Process Ref.
1 Amorphous polypropylene/PVDF composite Membrane fabricated by taking entire benefit of the synergistic effect of the Some susceptible flaws were noticed on the surface of skin layer, that caused DCMD [271]
membrane superhydrophobic amorphous polypropylene skin layer as well as nanofibrous larger maximum pore size and smaller LEP with water. Therefore partial
support layer. This type of 3-D network tuned the size of pore without severe pore wetting will occur when the water meniscus is damaged at the
compromise in the porosity and also improved the hydrophobicity and LEPw, membrane defect openings in the course of long time DCMD process
that efficiently eliminated salt intrusion and allowed vapor permeation with an
ultrahigh flux.
2 CNTs coated superhydrophobic ENFMs/Spraying This method resolves the problems of bead development and embedding of The inclusion of nanoparticles in the membrane matrix generally requires a VMD [279]
method nanoparticles in nanofibers. The increased efficiency in MD performance is due membrane post-treatment that in turn enhances the membrane preparation
to the thin layer of CNTs network on the surface of membrane cost
3 CF4 treated ominophobic polyvinylidene fluoride The test results suggest the increased possibility of this ENFM in the treatment of Optimization of the processing parameters to attain required nanofiber AGMD [258]
ENFMs (15 min treatment) challenging feed solutions which might contain organic contaminants like properties and morphology is hard.
wastewater from CSG exploration.
4 Hydrolyzed PAN supported nanofiber-based FO The test results demonstrated a synergistic impact of multiple elements inclusive Process depends on several variables. FO [241]
membranes of hydrophilicity, crystallinity, internal structure, roughness, and surface
33
morphology on separation as well as permeability performance and ICP
behavior, which was presented by chitosan sub-layer between active layer and
hydrolyzed nanofiber mat.
5 Polyimide supported microporous nanofiber This TFC forward osmosis polyimide membranes can help to reduce ICP and Solvent emission (ethanol) into air and increased expense of solvent FO [242]
membrane avoid the loss of draw solutes. Thus, these membranes display exceptional recycling
performance in forward osmosis process. The attained test results could be
credited to the effect of the inclusion of ethanol into aqueous phase on the
surface morphology, hydrophilicity as well as polyamide layer structure
6 TFC NF membrane based on polyethylene The enhanced flux in this membranes is because of the huge open pore The nanofibrous structures prepared using two-axial technique have limited NF [185]
terephthalate nanofiber support and PA topmost configuration, the lower hydraulic resistance of the nanofibrous support as well assembling configurations as well as functionalities
layer as nanocomposite format of thin layer increasing the water transportation
capability.
7 Three-dual structure high flux NF membranes With less SPEEK content, the impact of increased surface hydrophilicity Fabrication process is cumbersome. Material waste during LbL assembly NF [192]
prepared with various SPEEK conc. overpowers the decreased porosity, resulting in the enhanced water flux process
8 Two-layered PU/PET nanofibrous mat The interconnected pore structure and outstanding porosity of the PU/PA In needle-less ES set-up, fiber morphology as well as quality are not MF [131]
nanofiber membranes lead to two or three times greater flux relative to the accurately controlled, the raw materials which could be used are restricted,
commercially used membranes in desired pressures extent. which in turn limits flexible fiber fabrication and the process parameters as
well as flow rate cannot be controlled.
9 Polyvinylalcohol-MWCNT/Polyacrylonitrile The generated nano-scaled cavities between MWCNTs and polyvinylalcohol Solvent emission (acetone) into air and high cost of solvent recycling. UF [179]
chains acting as the advanced water channels can contribute increased free Process depends on several variables.
volume in the topmost barrier layer, leading to an increase in the water
transportation capability of the barrier layer when oxidized MWCNTs were
included into the cross-linked polyvinylalcohol barrier layer
displayed salt rejection and flux of 99.2% and 15.5 LMH, respectively. consolidated with ES technique. Nanofibers along with their network
From the observation of the results, we can see that these dual layered structures are commonly delivered with superior porosity, which are
ENFMs comprising of two polymers of diverse hydrophobicities can be beneficial for isolating particulates for purification of water. In order to
potentially utilized for desalination by air gap membrane distillation satisfy the ascending needs, there must be a considerable advancement
with stable flux as well as rejection of salt in the feed temperature from in the efficiency of nanofibers as a potential candidate for the treatment
50 to 60 °C. of water as well as ecological remediation. For accomplishing this, the
Table 3 is the summary of recently published papers on the mem- manufacture as well as uses of nanofibers with adjustable physico-
brane and separation properties of nanofiber membranes for MF, UF, chemical characteristics in addition to properties are totally required.
NF FO and MD in desalination and water treatment applications. In Despite that, a few challenges should be considered and overpowered to
addition to this table, we have also included Table 4 to highlight the pass beyond the present state of nanofiber preparation and utilization
benefits and challenges of the different nanofiber membranes for var- towards accomplishment in industrial and commercial settings. The
ious technologies in water treatment and desalination utilization. The aforestated difficulties are insignificant, however, they are not over-
main challenges relating to the fabrication processes are addressed in whelming.
the table such as cost issues, solvent emission and recycling issues, Primarily, it is essential to develop unique nanofiber preparation
limited assembly configurations etc. Also, the benefit of each technique techniques equipped for integrating the superior features of all present
utilized for improving the performance are discussed. The entire re- and developing methods to manufacture excellent quality nanofibers
search papers discussed in this work illustrated that each kind of the with an enormous industrial scale production capability. However, the
nanofiber membrane fabrication technique improve one or more fea- majority of the nanofiber-based composite structures and nanofibers
tures of the membrane and might demonstrate an adverse impact on are manufactured on the basis of the conventional ES strategy. On the
some different features of the membrane or have no impact by any other hand, as stated in this review paper, ES process has a few dis-
means. advantages, for example, high voltage, low throughput, a necessity for
Thus, in Section 5, the potential application of ENFMs in desalina- specific equipment, conducting targets, as well as trouble in accom-
tion and water treatment utilization such as MF, UF, NF, FO and MD plishing in situ nanofiber deposition. Simultaneously, the electrospun
have been discussed. The versatile ES technique could be utilized to nanofiber networks normally have less mechanical strength because of
manufacture high-performance ENFMs with a homogenous pore dis- its reduced crystallinity along with irregular alignment as well as the
tribution, increased pore interconnectivity, a high surface area-to-pore orientation of nanofibers. Therefore, it is important to improve the
volume ratio, and a higher surface area. The consolidation of ES process present ES technique. To enhance the throughput of the nanofiber
and flexible surface treatments (for example, LbL, coating etc.) make it preparation, advanced modifications of the typical ES, for example,
specifically appropriate to manufacture water treatments membranes needleless and multi-needle ES, might be additionally developed. For
for application in MD, FO, UF, NF and MF. It is clear that the choice of presenting the required functionalities as well as complexities into na-
appropriate materials and suitable incorporation routes for introducing nofibers and to improve their physical characteristics for additional
the required functionality, after or during electrospinning, are im- elaborate and explicit applications, choice of appropriate materials
portant to develop the right nanofiber membrane system for meeting combined with novel methodologies in controlling nanofiber structures,
the specific needs. For NF and UF applications, the NFMs are generally inclusive of the smaller dimension of fiber, inter-fiber adherence, and
utilized as a supporting layer to the dynamic thin-film layer prepared by fiber surface functionalization, are important. State-of-the-art nanofiber
different strategies Further, it was also noted that the addition of a configurations like multicomponent, multilayer, and core-shell nanofi-
nanofiber layer to a UF membrane is a right method to functionalize a bers might be manufactured through strategies like co-axial ES process.
membrane without unfavorably influencing the properties of the base Consolidating nanofiber preparation with different methods, for ex-
membrane. Also, dual layered ENFMs comprising of two polymers of ample, plasma treatment, control of fiber arrangement, heat treatment,
diverse hydrophobicities can be potentially utilized for desalination by and chemical grafting is captivating to additionally enhance the phy-
membrane distillation with stable flux as well as rejection of salt. The sicochemical characteristics of nanofibers. Ultimately, integrated na-
ENFMs display excellent porosity by means of its interconnected pore nofiber preparation techniques that can contribute the best properties,
framework and this characteristic enables it an appropriate candidate for example, in situ nanofiber deposition of SBS, excellent throughput
for the membrane substrate for FO utilization. (i.e., as a top layer). Till of CJS, improved nanofiber frameworks of co-axial ES, and so forth., are
now, ENFMs, as top active selective/barrier layers, have only been ef- exceedingly acceptable and ought to be the supreme objective in the
ficiency utilized in ultrafiltration-separation applications, that suggest quest for nanofiber manufacture methods.
future ENFM-growth opportunities in MD operating environments. Regulating the pore size of nanofiber systems is an important pro-
Unfortunately, advancement of the ES strategy to a commercial scale cedure for improving the nanofiber filtration efficiency. Further, com-
still continues to be a challenge. Hence, increased consideration has bination with different nanostructures might be important to contribute
been given to the greater durability as well as stability of the ENFMs to nanofibers with extra functionalities. In general, a reassuring perspec-
eliminate this issue. tive is absolutely awaiting the utilization of nanofibers for the treat-
ment of water as different manufacture procedures are developed fur-
6. Future scope ther to prepare nanofibers and analogous devices with incredible
filtration efficiency.
As the latest generation of filtration media, the electrospun nano- Thus, the future outlook of using ENFMs, specifically with those
fiber membranes show enormously advantageous features that should capable of dealing with desalination and water treatment application, is
prompt the progression of forthcoming commercial filtration systems. tremendously bright. On the other hand, the quality requirement for
Academic investigations, as well as research, on 1-D nanofibers are water treatment membrane is also greater. The aforestated suggests that
advancing at an extraordinarily quick pace. Unique preparation the accurate control of membrane homogeneity, support layer thick-
methods and utilization of nanofibers are being stated in the publica- ness, barrier layer thickness, and pore size distribution should be ac-
tions at an enhancing rate and there is no indication of deceleration. complished by ES in industrial scale. Without question, the ENFMs have
Significant improvement has been illustrated in the usage of nanofibers already become an exceptionally promising platform for several se-
for desalination as well as ecological remediation. paration as well as purification applications.
For improving the topographical and morphological features of
ENFMs, various techniques, inclusive of in-situ polymerization, mole-
cular bonding and the insertion of molecular dopants can be
34
7. Conclusion filtration systems. Conclusively, we trust that the nanofibers are at the
frontline of nanotechnology. It is anticipated that the nanofiber market
The utilization of nanotechnology for seawater desalination and will have exponential growth in the immediate future. Despite that,
water treatment is winning immense momentum throughout the world. there is no denying that there are still difficulties that should be con-
The unique features of nanomaterials, as well as their consolidation sidered to completely understand the maximum capabilities of NFMs,
with current technologies, present a great future towards re- however, the present scientific developments are in the correct path in
volutionizing desalination and water/wastewater treatment. accomplishing this objective.
In this review, the current status as well as the forthcoming ad-
vancement in nanofiber technology are discussed, with special atten- Declaration of competing interest
tion on its synthesis along with its application in seawater desalination
and water treatment. We discussed here the conventional techniques in The authors state that there is no conflict of interest for submitting
the nanofiber synthesis, like electrospinning, melt blowing, fibrillated this manuscript.
bicomponent fiber extrusion, phase separation, drawing, template Thanks.
synthesis, and self-assembly, along with its benefits and limitations.
Also, we presented the developing nanofiber preparation techniques, Acknowledgement
such as centrifugal spinning, plasma-induced synthesis, and solution
blow spinning. The membrane-based techniques utilize membrane sci- The authors would like to acknowledge the support of this research
ence and nanotechnology, and are more appropriate for desalination to Qatar University's IRCC research program through grant number
and water treatment processes. The aforestated membrane-based IRCC-2019-004.
techniques include MD, FO, RO, NF, MF, and UF. Nanofiber membranes
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Recent advances in nanofibrous membranes: Production and applications in T

ARTICLE INFO ABSTRACT

1. Introduction categorized as electrical, chemical, mechanical, and thermal energy

Fig. 2. a): Diagrammatic representation of the experi-

4.2.3. Thermal-driven membrane process 4.3.3. Coaxial ES

4.3.7. Ceramic nanofiber membranes nanofibers.

Fig. 13. NaCl rejection of 10 h continuous vacuum membrane distillation application.

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