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J Mater Sci (2016) 51:41734200

DOI 10.1007/s10853-016-9741-x

REVIEW

Hybrid adsorbent nonwoven structures: a review of current


technologies
Hooman Amid1 Benot Maze1 Michael C. Flickinger2,3 Behnam Pourdeyhimi1,2

Received: 12 October 2015 / Accepted: 11 January 2016 / Published online: 21 January 2016
Springer Science+Business Media New York 2016

Abstract Adsorptive nonwoven substrates are composite


media that contain adsorbent materials within their fibrous
structure; the methods to incorporate adsorbents in nonwoven webs determine their adsorption capacity. The key
objective for hybridization is to immobilize the adsorbent
while controlling the packing density and pressure drop of
the composite media. Loading percentage of adsorbents,
the accessible portion of their surface area, their attachment
and stability within the structure, and time/cost/process to
incorporate them is different for each hybridization technique. The general limitations associated with hybrid
adsorptive nonwovens are summarized as surface area loss,
process control, and production time/cost. The primary
focus of this review is on hybridization techniques that
incorporate activated carbons and/or metal-organic frameworks (MOFs) in nonwoven structures, used in gas

& Hooman Amid


hamid@ncsu.edu
Benot Maze
bmaze@ncsu.edu
Michael C. Flickinger
mcflicki@ncsu.edu
Behnam Pourdeyhimi
bpourdey@ncsu.edu
1

The Nonwovens Institute, College of Textiles, North Carolina


State University, 1000 Main Campus Dr., Raleigh,
NC 27695, USA

Department of Chemical and Biomolecular Engineering,


North Carolina State University, Raleigh, NC, USA

Biomanufacturing Training and Education Center, North


Carolina State University, 850 Oval Dr, Raleigh, NC 27695,
USA

filtration. It was concluded that coating, thermal bonding,


lamination, and coform methods have higher throughputs
compared to electrospinning. In addition, coform method
provides better control over accessible surface area of
adsorbents.

Introduction
The growing environmental awareness about the removal
of pollutant gases from bulk gas streams is accelerating the
investigation of adsorptive nonwoven filters. Adsorbents
are bed(s) or layer(s) of highly porous solid materials or
fine particles [13]. They generally exhibit large specific
surface areas (SSA) that result from high micropore volume [2, 4]. Adsorbents high SSA provides numerous sites
for capture of toxic/unwanted molecules through adsorption process. Adsorption type determines the bonding
energy between the molecules and surface, lower energy
for physical adsorption, and higher energy for chemical
adsorption [57].
The most common types of porous adsorbent materials
are activated carbons (AC), carbon nanotubes, carbon
molecular sieves, activated alumina, pillared clays, silica
gels, synthetic polymers, zeolites, aluminosilicate zeolites,
zirconia, and metalorganic frameworks (MOFs) [1, 2, 4,
814]. Rigidity and anionic nature of aluminosilicate
frameworks, high production costs, absence of homochirality, and functionalization difficulties are some of the
limitations of traditional adsorbents. ACs are the most
common adsorbents because of their reasonable price and
commercial availability. MOFs are interesting to study
because of their extraordinary high SSAs, versatile synthesis approaches, and functional tunability [10, 12, 13,
1520].

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Applications of ACs and MOFs in gas purificationfiltration include odor and irritant/toxic vapor control in
enclosed areas (vehicles, buildings, etc.), control of Volatile Organic Compounds (VOC) emissions in industrial
locations, and personal protective gears (clothing, face
masks, and respirators) [13, 14, 21].
In practice, adsorbents are immobilized or entrapped
within hybrid nonwoven structures [22] in two major
forms: non-flexible packed beds [23], or flexible fibrous/
polymeric substrates [21]. Packed beds offer high loadings
of adsorbents but suffer from high pressure drops and nonflexibility. Fibrous nonwoven substrates, however, are
flexible backbones for supporting or entrapping adsorbent
materials. They offer unique properties such as engineered
porosity and pressure drop, versatility of the chemistry of
base materials and production processes, and engineered
chemical/physical functionalities [2428].
Generally, adsorbents are immobilized within the nonwoven structure in three fashions: (1) there are physical
bonds between adsorbent(s) and fibers, (2) adsorbents are
mechanically entrapped within the structure, or (3) combination of both. The physical bond is achieved using some
binder materials and/or thermal fusion of either of the
components (adsorbents and fibers), causing a loss of SSA.
In the case of mechanical entrapment, porosity of adsorbents remains unmasked; however, they are susceptible to
shed out from the hybrid web [28].
Structures, properties, and applications of composite
nonwovens are discussed in the literature [21, 29]. However, to the best our knowledge, there is no comprehensive
critical review of how to incorporate adsorbents into nonwoven structures and how these methods compare to each
other. Since each of these techniques will result in nonwovens with different properties, in the present review, we
discussed and characterized them separately. The primary
focus of this review is on hybridization techniques that
incorporate ACs and/or MOFs in nonwoven structures,
used in gas filtration.

Hybridization objectives
Generally, using nanomaterials-polymer composite structures is a common practice to fix the nanomaterials and
incorporate their properties into flexible polymeric structures. These properties include mechanical, thermal, optical, catalytic, wastewater filtration, gas transport and
separation, etc. [3045]. Polymer chains are often functionalized to efficiently embrace and immobilize target
nanoparticles.
Because of the way they pack, adsorbents cannot be
used as freestanding media without large pressure drops;
hence, they need a support to contain them [26, 46].

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Nonwoven structures can contain the adsorbents and offer


high filtration efficiencies, and this is especially true of
electrospun, meltblown, and spunbond structures [10, 13,
14, 2527, 4648].
The common aim of hybridization is to create a nonshedding composite medium with minimal covering
(masking) of the adsorbents surface [28, 49]. Properties of
these hybrid structures are application-driven; however,
regardless of the application, three main design objectives
are (1) immobilizing the adsorbents and tailoring the
medium flexibility, (2) controlling the packing density of
the medium, and (3) improving the filtration capacity of the
final composite structure.
Immobilization and flexibility tailoring
Immobilizing the adsorbent within the filter medium is
critical. Many applications, such as water treatment and
air/gas filtration, introduce a hydrodynamic feed stream to
adsorbent materials. Due to the extremely minute size and
low density of adsorbent particles, they can be swept away
by the flow of the bulk stream. This phenomenon is known
as dusting (or shedding). Pollutant particles face and hit the
filter medium with different impact energies depending on
their properties (size and relative density) and stream
velocity [47]. In ultra-fine gas filtration applications, the
nominal velocity within the media is between 0.3 and 3.5
m min-1. Considering the flow rate ranges for specific
applications, 45,000 l min-1 for water filtration and
120 l min-1 for respirators, freestanding adsorbent particles are susceptible to dusting [46].
Beside the actual operational conditions, there are other
reasons to immobilize adsorbents within the filter media.
Filter media undergo some manufacturing and packaging
processes that impose many mechanical and thermal
stresses on the materials. Therefore, manufacturability and
durability of the filter media require sufficient strength,
resistance to corrosion and abrasion, flexibility, chemical
and thermal stability, and elasticity. The latter, along with
fatigue properties, are important in the case of expansion
and swelling during the application. Expansions occur in
pulsed and fluctuating flow rates and swelling happens in
polymeric supports in the presence of moist bulk gas
stream [46, 47]. In addition, handling and reuse (regeneration of adsorbent) of such composite filters are easier
when adsorbents are immobilized in the structure [50].
Media flexibility is another significant design parameter
in filters. Packed-bed adsorptive media (adsorption columns and filter cartridges) contain adsorbents in rigid cages
(or vessels constrained by the walls). These non-flexible
structures cannot be implemented in filtration devices
where flexibility is crucial to operation, such as facemasks
[46]. Nonwoven substrates can provide not only a flexible

J Mater Sci (2016) 51:41734200

mechanical support for the adsorbent component, but also a


fibrous medium with particulate filtration functionalities
[29].
Controlled packing density
Among typical properties of a filter medium, pressure drop,
filtration efficiency, and dust holding capacity are the most
important properties reported in filter specifications. Pressure drop is critically important and is tailored according to
the porosity and size (area and thickness) of the filtration
unit. The proportion of voids to the overall volume of a
material defines its porosity.
Pressure drop in hybrid adsorptive media depends on the
porosities of its components (web and adsorber) and the
distribution/packing of adsorbents within the structure.
Adsorbers porosity is inversely proportional to its hydrodynamic resistance (pressure drop) and mechanical
strength [46]. High adsorption capacities in small filtration
units are achieved by employing adsorbents with higher
microporosities or higher loadings of adsorbents; either of
these options lead to higher pressure drop [13, 46].
Therefore, packing density of adsorbent materials is
designed not only to meet the dimensional requirements of
the unit but more importantly to reach a compromise
between hydrodynamic resistance and filtration efficiency
[46].
Packing density of adsorptive media is designed based
on the requirements of target application. Gas storage
devices ensure maximized storage capacity by adopting
compacted adsorbent media. Filtration devices, however,
require adsorbents to be uniformly dispersed through the
media and to create the lowest pressure drop [4, 13]. In
separation processes, binders are employed to increase the
mechanical strength of medium and reduce pressure drop
[12].
Nonwoven media are characterized by having low
pressure drops (\350 Pa) and highly porous structures
(*90 %) [46]. They can create filtration media with sufficient depths, affording designable dwelling time for
contaminant molecules that adsorb at different rates. The
depth of the filtration media should offer a compromise
between the hydrodynamic flow resistance, adsorption
rates, and desired filtration efficiency [1, 46]. For instance,
spunbond-meltblown-spunbond (SMS) composite nonwovens can provide strong isotropic beds for adsorbent
materials [5155]. They can withstand high working
pressures (*7 bar) and carry heavy loads of contaminant
per unit area (*150 g m-2) [31, 46, 56].
Therefore, nonwovens provide the opportunity to create
adsorptive structures with engineered packing densities and
pressure drops. Tailoring the packing density of the
adsorbents in filter media requires considering a number of

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factors. (1) If water is present in hydrophilic polymeric


housings, there will be a substantial increase in the backpressure resulting from swelling of the fibers [13]. (2)
There is an optimum increase in the thickness above which
the filtration efficiency would not increase [46]. (3) Bulk
density and SSA of adsorbent materials are according to
both volumetric and gravimetric capacities of the adsorber
[57].
Hybridization techniques
Although hybridizing the adsorbent materials with nonwoven beds would create an ideal adsorptive medium, the
technique and mechanism by which the adsorbent is
incorporated and anchored in the structure is a matter of
concern [58]. Based on their foundation, these techniques
are categorized and reviewed critically below.
Conventional finishing/coating/padding methods
Implementation and technology
Most of the techniques that fall in this category require the
use of some kind of binding agent. Classical coating processes such as spray drying, foam coating, dip coating (dip
and squeeze), and padding are useful immobilization
techniques [13, 5967]. Since particular specifications are
meant to be imparted to the substrate, this technology can
be referred to as a finishing process [13, 59, 60]. These
conventional techniques are generally divided into two
main subclasses of wet and dry particle insertion [13, 27,
59, 68].
In practice, wet particle insertion is accomplished in two
manners. The first way is to mix the adsorbent particles
with binder material(s), such as latex, and then fluid-coat
the nonwoven substrate with the binder-adsorbent mixture.
The second approach is to apply the binding agent onto the
substrate and then introduce the adsorbent materials to the
coated substrate. The coating can be applied by knives,
rollers, bars, sprays, foam, or impregnation of the substrate
in the binder bath [13, 21, 59, 6973]. Different knife
coating methods such as knife-over-roll, air knife, or
blanket knife are employed. The coating dough can be a
compound of powdered or granular activated carbon (PAC
or GAC) and the binder polymer, such as polychloroprene.
In this process, the ratio of AC to binder is constant and the
mass of add-on is monitored [27, 74]. Next, the coated or
impregnated substrate will be heated (air or irradiation) and
cured [13, 59, 69].
Dry coating methods can be generally performed via
calendering, melt coating, electrostatic spraying (in
Charged media section), or lamination (in Lamination
section). Calendering is the process where the target

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material(s) are spread on the substrate and the substrate is


then passed through a set of heated calenders to fix the
adsorbent materials onto the nonwoven fabric. Melt coating
is done via inert powder coating (technically similar to
calendaring). In extrusion coating, the target adsorbent
layer is extruded and laid on the top of the substrate [21,
59, 75, 76].
Since some MOFs and ACs are conductive, Wie et al.
proposed a sputter coating method for impregnating these
materials into the nonwoven structures [13]. They sputter
coated a PP spunbond nonwoven fabric with a nanolayer of
copper. After washing and drying the substrate, copper
deposition was accomplished by a Magnetron sputter
coating system. They found that after increasing the coating thickness to 100 nm, nonwoven pore size and pore size
distribution decreased. They hypothesized that it is possible
to produce hybrid adsorptive nonwovens by coating the
substrate with conductive MOF materials, which are
intrinsically porous [77].
Another way to perform dry particle insertion is by
airflow. Figure 1 demonstrates the schematic of this process [13, 78].
The particle insertion/penetration depth is due to the
pressure gradient across the nonwoven substrate. Additionally, particles can be inserted by spraying, where there
is no pressure gradient and particles retain their positions
near the surface [13]. This can be accomplished by fluidized bed spray systems followed by substrate lamination
in order to fix the particles and increase the particle
retention of web (in Lamination section) [78].
Alternatively, to decrease the differential pressure, some
commercial filters are manufactured by coating open-pored
polyurethane with PAC and GAC. This is done by
impregnating polyurethane foam in a slurry of latex binder
and AC [78, 79]. The thickness of the media can be
between 2.0 and 30.0 mm [80].
In another study, electrospun nylon 6,6 was placed
directly on the top of a porous AC-loaded polyurethane
foam. The electrospun coating was supposed to eliminate
the penetration of aerosol particles through the foam layer
by taking advantage of minuscule porous structure of the
Fig. 1 Principle of the airflow
method

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electrospun web [81]. Figure 2 shows the structure of these


two membranes separately.
Characteristics and considerations
In wet coating processes, the nature of the solvent and
transportation media are important. Not only do these media
need to be compatible with both adsorbent materials and
nonwoven bed, but also they need to meet the requirements of
the final product. Some issues in this regard include
biodegradability and non-toxicity of the solvent system, mass
transport properties, chemical effects on the adsorbents,
avoiding particle agglomeration, and ease of reusing and
regeneration of the solvent [13]. The major problem of this
method is the blockage of adsorbent surface and diminished
surface area functionality and adsorption capacity [60, 82,
83]. Using granular adsorbents is advantageous over their
powdered counterparts since the coating process covers a
smaller portion of the adsorbent, and the larger portion of the
surface will remain uncovered and functional [84]. Additionally, the penetration depth and stability of the particles
within the structure are critical, especially in the case of foam
coating [13, 59]. The energy cost of wet particle insertion is
mainly associated with moving the solvent/water around and
curing/drying the coated substrate [13].
In dry particle insertion methods, namely gradientpressure airflow and spray methods, parameters of interest
include (1) particle mechanical stability; (2) physical
properties of particles (e.g., size, shape, hydrophobicity,
hydrophilicity); (3) properties of nonwoven materials (e.g.,
mass, density, water and/or air permeability, pore size); (4)
particle energy during the penetration process; and (5)
particle acceleration before the dissipation of required
kinetic energy [13]. Therefore, the optimal relationship
between particle size, substrate pore size, and particles
kinetic energy are necessary factors to prevent structural
disintegration of the substrate.
Calendering process requires adsorbent materials to
have sufficient mechanical stability to withstand the calenders nip pressure and maintain their structural integrity
[13, 59]. In addition, both calendering and melt coating

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Fig. 2 a Porous polyurethane foam containing AC (scale bar 200 lm); b electrospun nylon 6,6 nanofiber coating sprayed onto surface of the
foam (scale bar 2 lm). Reprinted from [81] with permission from Elsevier

would lead to partial blockage of adsorbents pores and


reduced functionality [13, 83].
Sputter coating methods are more expensive with lower
deposition rates compared to other coating/finishing
methods. Although particles are dispersed more uniformly
in sputter coating [59], stability of nanoparticles in substrate raises a major concern for application of these
structures in filtration [13, 59].
In general, coating methods are inexpensive and commercially developed/available. This is opposite to some
other techniques (Direct growth on the substrate section)
and Electrospinning section) that are not widely examined and still need further study.
Wet coating processes induce partial blockage of pores
and reduced functionality of adsorbent materials, true about
some other hybridization techniques (in Compounding
adsorbent materials with base polymer, Thermal bonding
of adsorbent to substrate, CoForming sections). Compared to other techniques, solvent/water system that is used
for applying adsorbent materials raises some environmental issues (also true about wetlay technique in Incorporation of adsorbent materials in the wetlay process
section) and additional energy/cost issues.
Among the methods in this category, the airflow method
maintains the functionality and structural integrity of
adsorbent materials and can be performed in-line with the
nonwoven production. Nonetheless, there is no physical
bonding between adsorbents and nonwoven media, so the
media are vulnerable to dusting. This is also the case in
wetlay process (in Incorporation of adsorbent materials in
the wetlay process section).
Compounding adsorbent materials with base
polymer
Implementation and technology
Functional nanoparticles of interest, PAC/GAC and/or
MOFs in this case, can be added to the polymeric support

material or resin in the meltspinning/meltblowing process.


The mixed melt is extruded in the form of filaments/nonwovens [8588]. Besides meltspinning, the prepared
adsorbent-containing mixture can pass through a coagulation bath to form filaments from which nonwoven substrates will be produced [44, 60, 89, 90]. Carbon nanotubes
can be compounded with the polymer solution in the
coagulation bath to enhance the mechanical properties
[38]. Such immobilization and hybridization techniques are
common practice for the wastewater treatment (copper
removal) where PAC is mixed with hydrophilic polyurethane liquid prior to the foam formation [50].
Characteristics and considerations
Meltblowing compounded resins and properties of resulting products are influenced by the following factors: particle weight %, particle uniform dispersion, molecular
weight of the molten polymer, particle properties (dimensions, shape, and density), and processing parameters
(screw configuration, number of screws, temperature profile, etc.) [9093].
Polymer-particle melt compound undergoes huge rheological changes. The most significant rheological parameter
is melt viscosity (or melt flow index) that determines the
spinnability of the polymer. Melt viscosity of the compound depends on original polymer properties, polymerparticle interactions, and weight percentage (concentration)
of the added functional particles [9295].
The most important limitation to this technique is the
loading amount of adsorbent materials in molten resin
mixture. This is due to the profound effect of compounding
on shear rate and extensional viscosity of the melt [33, 96
98]. In addition, depending on the production speeds and
shear rates, the compounded melt shows different rheological properties and shear viscosity behaviors [97, 98].
This complex behavior of compounded melt at high particle concentrations is a major impediment for meltblowing, a fast single-step nonwoven web formation process

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[99102]. High concentrations of added material in viscoelastic polymers can have the following negative effects:
(1) low and non-processable melt flow index (high melt
viscosity), (2) reduced melt elasticity and resulting die
swell phenomenon, (3) likelihood of particle agglomeration, (4) diminished moldability, and (5) induced polymer
degradation (based on polymer-particle chemical compatibility and interfacial surface chemistry). There is no
specific range for this concentration since each polymerparticle system would behave differently [9395, 103,
104]. Adding compatible surfactants [9092], using endfunctionalized polymers [105], and using ultrasonic particle dispersion can help reduce the particle agglomeration
[93].
The other limitation/consideration is the dimensions of
target adsorbent particles relative to fiber diameter. This is
important as the functionality of adsorbent (accessible
surface area and pore) depends on how it is attached to the
fiber; i.e., contained in the fiber structure or point-attached
on the fiber surface. It is reported that the radial placement
of particles relative to fiber axis depends on particle size.
Larger particles tend to cluster on fiber surface and smaller
particles agglomerate in the center of fiber [106108].
Since particles are partially bonded to the fibers/web, the
filter media do not suffer from dusting as much as wetlaid
(in Incorporation of adsorbent materials in the wetlay
process section) or coform (in CoForming section)
hybrid structures [60, 91]. For the same reason, the filter
media will have a uniform 3-D distribution of the adsorbent
component. This method is environmentally benign since
no solvent system is involved in the production [51, 92,
109]. However, this hybridization method will potentially
block the adsorbent materials pores and adversely influence the mechanical properties of fibers and nonwoven
fabrics.
Thermal bonding of adsorbent to substrate
Implementation and technology
In general, this method refers to all techniques by which
either the nonwoven substrate or the adsorbent material is
heated to make bonds at points of contact between the two.
The nonwoven fabric is produced by different methods,
such as dry-laying, wet-laying, spunbonding, or meltblowing [110].
Approaches to introduce heated adsorbent component to
nonwoven fabric include (1) spraying an air stream containing the heated solid particles onto the substrate; (2)
dropping or sprinkling the heated solid particles onto the
substrate; (3) passing the substrate through a shaking
reservoir/chamber containing heated particles; (4)
immersing and passing the fibrous sheet through the heated

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particles; and (5) exposing the substrate to a fluidized bed


stream of heated particles [95, 110, 111].
When heating the substrate, adsorbent materials can be
sprinkled over the nonwoven fabric in the first step and
then the coated layer enters a heating zone. In this way,
softening or partial melting of the nonwoven fabric occurs
and particles will bond to the fibrous structure [59, 112].
The fibrous support can be electrostatically charged before
entering the particle-dispensing zone. This will enhance the
deposition ratio by the added contribution of electrostatic
deposition to the normal gravitational deposition [112] (in
Charged media). Figure 3 shows the complete configuration of such a device.
Heating through radiation is advantageous when using
dark adsorbent particles, such as AC. In addition, the
blower fan stabilizes the deposited sunk particles on the
structure [112].
Commercially available particle-coated filters are AC
air filter media from Permatron. Polyester nonwoven
substrates are impregnated with finely ground coatings, and
subsequently heat-set so that the coatings will be retained
in the filter media even when the media are rinsed or
vacuumed. Filter media thickness ranges between 0.47 and
1.27 mm that is mostly composed of GAC [113].
Alternatively, nonwoven substrate is made of bicomponent sheath/core fibers (BiCo) [114, 115] and adsorbent
particles (or ACF [116]) are heat-bonded to the sheath
component [13, 95, 110, 111, 117121]. Bicomponent
nonwoven structures, webs comprised two fiber types, are
also reported to be useful in this regard [122]. The fibrous
structure comprises high-melting-temperature fibers, as the
support, and low-melting-temperature fibers into which
adsorbent component fuses upon heating the substrate
[123]. In this method, adsorbent materials are applied on
the substrate by some means, such as spraying, and the web
is subsequently heat treated. Upon heating the web (or
particles), the sheath component softens and particles
adhere to surface of the fiber [13, 117]. The same concept
occurs for low-melting-temperature fibers in bicomponent
nonwoven structures [59, 124].
Characteristics and considerations
Control parameters for thermally bonded hybrid nonwovens include the temperature, relative density, kinetic
energy, heat capacity, and size of the heated particles.
Melting temperature and weight percentage of sheath and
core polymers, air permeability, and pore size distribution
of the nonwoven fabric are other determining factors of the
process [110, 111, 117].
If the temperature of air stream, containing the heated
particles, is more than 200 C higher than the melting
temperature of nonwoven fabric (or core component of

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Fig. 3 Device for


manufacturing carbonpowdered nonwoven fabrics 1
roller; 2 nonwoven fabric; 3 letoff drive; 4 string electrode 5
container; 6 active carbon; 7
feeder; 8 heating radiator 9
blower fan 10 chute 11 take-up
roll; 12 take-up drive. Reprinted
from [112] with permission
from Fibres & Textiles in
Eastern Europe

sheath/core fibers), there will be an undesirable shrinkage


in the web. In case of single component nonwoven webs
and such high-temperature gradients, there might be broken
threads rather than just shrinkage [95, 110, 111, 117]. In
such high temperatures, the heat stability of the adsorbent
component is also important [60]. The dwell time or travel
rate of substrate is adjusted according to the amount and
type of adsorbent particles, and the nonwoven fabric
properties (material, web thickness, and basic weight)
[112]. Generally, it is preferable to maintain the temperature of particles 80100 C above the melting temperature
of the fibers, and to have the core-component weight percentage of more than 90 % [95, 110, 111, 117].
To avoid dusting, functional particles should have an
average size of equal to or less than 1/3 of the average
diameter of the fiber [95, 110, 111].
Substrates pore size distribution and adsorbents relative size determine uniform distribution of particles in final
structure include [95, 110, 111]. In terms of loading, it is
preferable for the polymeric component to be about
1025 wt% of a particle-loaded web [117].
The main disadvantage of heat-bonding technique is the
partial blockage of adsorbents pores. Many functional
particles would be excessively buried in fibers and less than
50 % of total surface area would be effectively available
[95, 110, 111, 117]. Another drawback of this method is
the high energy required to heat-treat (or subsequently
calendar [111]) the substrate [13]. In addition, these particles are susceptible to abrasive removal if the filter
medium is subject to high processing/operation stresses
[117].
In general, heat bonding of adsorbent materials would
be an effective hybridization technique when production
time and environmental issues are matters of concern.

Incorporation of adsorbent materials in the wetlay


process
Implementation and technology
Activated carbon fibers and particles can be incorporated in
nonwoven beds via wetlay process to produce Chemical
Protective Clothing (CMC) and filtration media [26, 121,
125128]. Nonwoven substrate is the supporting bed for
the AC constituent that serves to adsorb dangerous chemicals and toxic vapors.
The AC constituent is mixed with the wetlay fiber slurry
to yield a single-layer hybrid wetlay structure [26, 125,
127, 128]. Generally, there are three steps to produce such
media; (a) a suspension of staple fibers (usually cellulosic
fibers such as pulp) and adsorbent component is prepared;
(b) the aqueous suspension is deposited onto a papermaking-forming perforated surface; and finally (c) water is
removed via vacuuming to yield the hybrid fibrous medium
[83, 129131].
Industrially, these structures are made for filtration/
prefiltration [128, 132] where three layers of wetlay nonwovens, with the middle one or all containing the carbon
constituent, are laminated into a single pleated filter [133].
FACT filtration media are commercially available from
KX Technologies where adsorbent particles are immobilized by non-cellulosic fibrillated nanofibers [134]. The
adsorbent component is immobilized within wetlay nonwoven structures using fibrillated fibers, such as fibrillated
acrylic fibers [26, 127, 135138]. In general, AC particles
or fibers are suspended in the slurry containing acrylic
fibrillated fibers; subsequently, the suspension is wet-laid
using conventional papermaking process [26, 127, 135
139].

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Fibrillation of fibers is done by high speed shearing of


fibers at temperatures greater than 30 C; enzymes may be
employed to accelerate the fibrillation process [127, 136
138]. Wet-end additives, fluctuating agents, and surfaceactive agents can facilitate the web formation process [127,
135138, 140]. Chemical post-treatments are available to
impart different functionalities and properties such as
abrasion resistance, toughness, or improved adsorption
[129].
Characteristics and considerations
Hybrid wet-laid adsorptive media have medium-to-high
production costs. They are characterized by having
improved sheet flexibility, high sorptive characteristics,
high porosity to fluid flow, processing speeds normally
associated with papermaking processes, and a wide range
of applications from military uniforms to gas separation
media [130, 137].
To modify the mechanical and/or physical properties of
final product (such as higher mechanical strength or operational temperature), short glass fibers or other synthetic
fibers can be added to the slurry [139, 140]. The use of
active agents, with controlled weight percentage and size,
promotes uniform 3-D distribution of adsorbent materials
within the web structure [127, 129, 134, 138]. It is recommended not to use chemically functionalized particles
as the nature of the aqueous process could render chemically unstable adsorbent materials inoperative [83].
Wet-laid nonwoven media are capable of uniform
immobilization of adsorbent particles sized 180 microns.
Preferably, the weight percentage of particles smaller than
10 microns should not exceed 15 % of the total composite
medium weight [134137]. When using fibrillated fibers,
more adsorbent particles can be immobilized; this is due to
mechanical interlocking action of fibrillated fibers [135
137, 139]. However, denser structures are associated with
higher pressure drops [59, 83].
Common fiber size used in a wetlay process is about
0.78 denier (1035 microns in diameter) with lengths
ranging 536 mm [129]. However, if employing fibrillated
fibers, the fibrillated fibers should be less than a micron in
diameter, preferably from 50 to 400 nm, and 125 mm
long [127, 134, 138]. Weight percentage of fibrillated fibers
should be 1020 % of the final composite structure [129,
135137]. To improve the performance, ACF with lengths
ranging 510 mm can be added to the slurry in weight
percentages similar to that of AC particles.
The most competitive advantage of the wetlay process is
the absence of adhesives or melt fusing compared to the
previous techniques, resulting in not-shielded pore structure of the adsorbents [133, 139]. Production time tends to
be as short as that of papermaking processes and the

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J Mater Sci (2016) 51:41734200

absence of various chemicals promotes the environmental


issues [130]. However, following disadvantages are associated with this process:
(a)
(b)

(c)

The energy price is high since water is being moved


around in the whole system [25, 27];
There is no actual physical or chemical binding
between the web and adsorbents, so the structure is
vulnerable to dusting [59]; and
The process is not compatible with most of MOF
materials because of their hydro-sensitivity and
hydro-degradability [141147].

Direct growth on the substrate


Implementation and technology
In general, this method involves the synthesis of MOFs in
the presence of final substrate that is usually pre-functionalized. Two general approaches are in situ growth and
secondary or seeded (also called layer-by-layer [148])
growth. The in situ growth refers to immersion of prefunctionalized substrate in the growth solution. However,
in the seeded growth method, the substrate already has the
preattached seed crystals when immersed in the growth
solution [149152]. The latter stepwise formation method
is popular for preparation of mixed-ligand or pillaredlayered MOF materials. The seeded growth method is
used for zeolite membranes and yields highly oriented
growth on the substrate [153]. Modifications of the substrate prior to growth process result in improved heterogeneous nucleation of MOFs and stronger interfacial
bonding between the native substrate and MOFs [150,
152, 154, 155].
Among the non-polymeric support materials, the most
commonly used are a-alumina [148, 150, 154158], TiO2
[150], silica, porous alumina, graphite [148, 159], zeolites,
carbon [159], and porous potassium hexatitanate disks
[158]. Although these inorganic membranes are rather
solvent-insensitive, thermally stable, and selective, they
suffer from low flexibility/breathability, brittleness, and
thermal expansion [159, 160]. Polymeric nonwoven substrates, however, offer greater flexibility [148, 159] and
breathability. This makes nonwovens a great option for
protective clothing, filtration, and gas separation applications [161, 162]. MOFs have a great potential of anchoring
and growing directly on polymeric substrates [150] due to
their organicinorganic hybrid nature. Fibers that have
been used as the support for direct growth of MOFs include
silk [148], cellulose [152, 163], polyester and wool [161].
Polymeric membrane supports include polymetylmethaacrylate, polyimides, Matrimids, and polysulfone
[159].

J Mater Sci (2016) 51:41734200

Centrone et al. synthesized MIL-47 directly on electrospun polyacrylonitrile (PAN) substrates via microwave
irradiation. PAN solution was electrospun, collected on an
aluminum foil, and folded and heat-pressed for enhanced
mechanical strength. The substrate was then placed in a
vial that contained the precursor solution of MIL-47 to be
irradiated in a microwave for 5 s to 30 min. Finally, the
MOF-coated PAN substrate was removed from the solution, rinsed and dried for characterization. The produced
substrate was found to be a proper medium for filtration
applications [164].
Pinto et al. reported the attachment of HKUST-1 to PAN
electrospun nanofibers (see Electrospinning section).
The electrospun PAN substrate was firstly reacted with
copper acetate for 2 h and then the BTC solution was
added drop-wise to the reaction solution for the in situ
growth [165].
Fan et al. prepared a macroporous SiO2 wafer with a
thickness of 2 mm as the supporting scaffold for ZIF-8/PVP
(Polyvinylpyrrolidone) composite nonwoven web. Next,
they post-synthesized a secondary seeded growth of ZIF-8
on the prepared SiO2/ZIF-8/PVP support [166]. The produced nonwoven composite webs and the secondary-synthesized membrane are shown in Figs. 4 and 5, respectively.
In situ growth of ZIF-8 materials on flexible nylon
membranes was also done using contra-diffusion method in

4181

the work of Yao et al. The two synthesis solutions were


separated by a porous nylon membrane. The growth and
crystallization occurred and developed on both sides due to
favorable interactions between organic ligands of MOFs
and polymers [167]. Figure 6 shows the schematic of
contra-diffusion method and SEM image of the produced
film.
In another study, Kuesgens et al. synthesized HKUST-1
in the presence of two kinds of pulp fibers, Kraft-processed
and ChemoThermoMechanical pulp fibers (CTMP). The
main difference between these two kinds of pulp fibers is
the residual content of lignin after their production processing, with CTMP being less delignified. To synthesize,
they solved trimesic acid in ethanol (EtOH)/DMF and then
mixed it with an aqueous solution of Cu(NO3)2.2.5 H2O.
Afterward, 1 gram of pulp fibers was added to the solution
and the solution was stirred for 15 min. The slurry was
gradually heated to 85 C and kept at this temperature for
24 h. By filtering and washing the product with EtOH/H2O,
the filtrate turned clear and blue fibers appeared. The fibers
were briefly dried in air and activated at 160 C for 18 h
[163].
The direct growth and in situ synthesis of HKUST-1
nanostructures on negatively charged silk fibers [148],
unmodified and anionically modified cellulose fibers [165],
modified anionic woven cotton fabric [152, 165], and

Fig. 4 SEM images of the ZIF-8/PVP composite fibers electrospun from methanol solutions of 12 wt% PVP and different seed concentrations:
a 6 wt%, b 8 wt%, c 10 wt% and d 12 wt%. Reprinted from [166] with permission from Royal Society of Chemistry

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J Mater Sci (2016) 51:41734200

Fig. 5 Cross section view of the ZIF-8 membrane. Reprinted from [166] with permission from Royal Society of Chemistry

Fig. 6 Contra-diffusion method and SEM image of the produced


film: a Diffusion cell for ZIF-8 film preparation; b Schematic
formation of ZIF-8 films on both sides of the nylon support via
contra-diffusion of Zn2 ? and Hmim (2-methylimidazolate) through

the pores of the nylon support; c SEM image of the cross section of
the ZIF-8 film prepared at room temperature for 72 h at the zincnitrate solution side. Reprinted from [167] with permission from
Royal Society of Chemistry

polyvinylamine (PVA)-modified woven polyester fabric


[161] have also been reported in the literature. The possibility of synthesizing and direct growth of HKUST-1 on
such pre-functionalized substrates is due to the presence of
carboxyl groups on both the substrates and the synthesis
solution [148, 152, 161, 163].
Direct growth of MOFs on ceramic [168], polyetherimide [169], porous alumina [170] hollow fibers, and
etched stainless steel fibers [171, 172] is also reported.
More interesting is the in situ direct growth of MOFs in the
presence of microporous AC [173], carbon nanofibers
[174], single walled carbon nano-tubes (SWCNT) [175,
176], carbon nanotube buckypapers (CNTBP) [177], and
multi-walled carbon nanotubes (MWCNT) [178180], with
the main goal of improving hydrogen storage capacity.
The concept of (self) growth is also reported for carbonbased hybrid adsorbents, with no MOFs [181]. Szczypta
et al. improved the catalytic, separation, and storage
properties ACF by self-growth of CNT on them [182]. In
another study, self-template growth of TiO2 on carbon
fibers was reported to increase the photocatalytic activity of
the resulted hybrid carbon mat [183]. Zhou et al. reported a
higher electrical conductivity by Chemical Vapor Deposition (CVD) of CNT and carbon nano-fibers on PAC [181].

Characteristics and considerations

123

Taking advantage of hydroxyl and carboxylic groups on


cellulosic materials, they have been used as host media for
embedding, immobilization, and growth of different
nanoparticles [152, 184190]. Most of the literature that
studied the in situ growth of MOFs on textile substrates,
specifically nonwoven media, is about synthesis of
HKUST-1 on carboxyl-containing fibrous substrates [164].
The conversion of nitrile to carboxylic acid group is a
necessity for the growth of MOFs on electrospun PAN
nonwovens [48].
For instance, Kuesgens et al. found that the higher lignin
content in CTMP pulp fibers results in higher degree of
coverage by HKUST-1 based on the inherent affinity of
lignin towards HKUST-1 crystals [163]. Pretreatment is
not required if there is an inherent binding between the two
components, like the binding between copper dimer and
wool protein [161]. Hence, the presence of some kind of
chemical pretreatment on the fibrous nonwoven substrate,
or an inherent affinity between the components, is a
necessity for attachment of MOFs to the substrate. Ensuring the proper chemical attachment of MOFs materials to
fibers is confirmed by FTIR and/or XPS analyses [165].

J Mater Sci (2016) 51:41734200

The current focus of direct growth is on the fabrication


of defect-free MOFs with controlled interface between the
MOFs and interstitial gaps within the growing support
[177]. Therefore, the controlled pore size within nonwoven
structures is a vital matter of concern for processing of
highly interconnected and freestanding MOFs hybrid
structures [177, 191].
In general, such media are characterized by efficient
adherence of MOFs to the substrate, regular distribution of
functional particles on the substrate [161, 163], extended
shelf life, and mechanical stability of the hybrid media
[152, 161]. In situ growth of MOFs on nonwoven media is
advantageous since the porous structure of adsorbent is not
shielded at all, corresponding to no loss of SSA. The total
accessible surface area of individual fibers within the
substrate determines the 3D uniformity of particles
attachment [161] and the particle loading capacity. However, the crystallization and growth of MOFs follow an
anisotropic fashion owing to the available space between
the fibers and the 3D surface of each fiber. Therefore,
chemical compatibility and basic structural properties of
the nonwoven web are important [161, 164].
Although the synthesis and incorporation of the adsorbent component take place at the same time, the main
disadvantage of this method is its low throughput. Microwave irradiation [164] or ultrasound [148] synthesis techniques can enhance the production time; however,
industrial-scale production of such media is not feasible.
CoForming
Implementation and technology
Coform nonwoven webs are composite meltblown substrates that contain at least one additional-functional
material, e.g., AC fibers/particles, pulp, super absorbent
polymers (SAP). The technology was first introduced/patented by Kimberly-Clark Corporation where
fiberized wood pulp was added to meltblown webs to
increase the absorbency of the nonwoven [192].
Coforming is the introduction of functional component
to meltblown stream(s) during the formation of meltblown
web, e.g., blowing the particle/pulp into tacky meltblown
filament stream [95, 193196]. Coform nonwoven webs
containing SAP have been widely used in diapers and
wipes [195, 197, 198].
There are two general ways to create such structures: (1)
providing a single stream of thermoplastic material to form
the web and introducing the functional particles of interest
to this stream; (2) providing two streams of meltblown
filaments and introducing the adsorbent component at the
convergence point of streams (impingement zone). Subsequently, the composite stream is deposited onto a

4183

perforated forming surface (drum or belt). Negative pressure is provided under the forming surface, and the solidified composite web is collected in the form of rolls [90,
198, 199].
Different devices are used to create, convey and introduce the stream of functional materials to filaments. These
include picker roll and gas stream (common for AC particles) [199], carding system and airflow (common for
ACF) [82], fluidized bed sprays [79, 95, 200], and particle
shakers and compressed air [200].
Several configurations of coform process have been
reported, most of which concern with the location and
temperature at which adsorbent materials and meltblown
stream(s) meet each other. Adsorbent particles are introduced from a feeding hopper to maintain a continuous
incorporation [60]. In practice, particles are introduced to
meltblown web stream at distances either far or close from
the die nozzle [95, 198]. In addition, particles can have
different temperatures adjusted according to the thermal
properties of web material and particles thermal properties
[60, 95, 194]. Based on the configuration, particles are
mechanically entrapped within the meltblown web and/or
thermally bonded to the filaments [198]. Coformed webs
have minimal dusting. Laminating the hybrid web (in
Lamination section) with two or more spunbond nonwoven webs can further minimize dusting and enhance the
mechanical properties [21, 79, 194, 198, 201203].
Figure 7 demonstrates a configuration of a coform line
where ACF is introduced to a single meltblown stream
using a carding system coupled with airflow. ACF diameter
was between 10 and 20 microns and their length was about
one inch [82].
Characteristics and considerations
Coform technology can be viewed from two standpoints,
web formation process and particle introduction/incorporation step. The processing parameters and techniques for
the web formation are well described in the literature and
are not the focus of this review [2527, 204212]. The
following section focuses on the particle introduction/incorporation stage of coform process.
The most important parameter is the distance and
location of the functional-component dispensing device
relative to the meltblown die(s). This is important since not
only can it change the velocity of particles at convergence
point [82, 198], but also the filaments could be either tacky
or non-tacky when particles hit them, depending on the
polymer thermal properties [60].
Tackiness of filaments has profound effects on the
mechanism by which particles are attached to filaments.
Particles would thermally bond to tacky fibers and the
resulted meltblown web would mechanically entrap the

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J Mater Sci (2016) 51:41734200

Fig. 7 Equipment for forming the meltblown/ACF composite. Reprinted from [82] with permission from the society for the Advancement of
Material and Process Engineering (SAMPE)

particles, i.e., desired immobilization [195, 198, 199].


Otherwise, if fibers are completely solidified and nontacky, the functional component is only mechanically
entrapped within the web, at the contact points of microfibers [95, 193].
If particles are introduced to the web far from the die
nozzle, three types of placements will be developed. A
portion of the particles is in point contact with partially
tacky fibers; some are mechanically entangled within the
meltblown web interstices. The rest neither are in sufficient
point contact nor mechanically entangled, resulting in
fugitive particles (dusting) [60].
Particles can be introduced into the meltblown stream as
the melt passes the die, when fibers are not fully consolidated [60, 194]. In this case, more binding and contact will
be possible between the particles and fibers; however, the
fiber stream and attenuation process are adversely affected
by the particle insertion stream. Consequently, properties
of the final meltblown structure and constituent fibers will
diminish drastically.
Alternatively, in the case of heat-stable materials, the
functional component is heated up to a temperature that
approximates the temperature of fibers at die nozzle. (Heatstable particles are any particles whose chemical, physical
or other properties do not undergo substantial changes upon
heating and the particle integrity/functionality would be
maintained.) In this case, they are introduced into the fiber
stream far from the nozzle where the web is partially
formed and sufficiently stable. Partial penetration of the

123

heated particles into the meltblown web renders a stable,


non-dusting, composite web and leaves the non-penetrated
surface of the particles available for adsorption [95, 194,
213, 214].
The velocities of meltblown filaments and particle
streams and the difference between them are two other
process parameters that should be controlled [195]. If the
velocity of filament stream(s) at impingement zone is
higher than that of the particles stream, the distribution of
the adsorbent component is substantially homogenous
within the nonwoven web. The higher speed of filaments
stream(s), promotes enhanced turbulent mixing of adsorbent particles, resulting in a consistent uniform particle
distribution. However, higher speed of particle stream
yields a gradient incorporation of particles within the
nonwoven web [198, 199].
Huang et al. found three important processing parameters that could control the incorporation process and ACFs
uniformity within the coform structure. (1) ACFs should
have enough kinetic energy to be able to overcome the
resistance of airflow and enter the fiber stream; (2) the
kinetic energy of ACFs should be low enough so that the
filament stream can arrest ACFs; and (3) the airflow must
be adjusted to provide a uniform introduction of ACF to the
meltblown web [82].
Convergence point is designed and located at the closest
distance to the collecting surface to inhibit and minimize
the dispersion of coform structure [195]. In addition, the
relative angle of meltblown die(s) and dispenser influences

J Mater Sci (2016) 51:41734200

the texture and extent of intermingling of the coform web


[199].
Loading percentage of the functional component can be
from 10 to 90 % by weight of the composite coform.
Loading percentage depends on the thermoplastic polymer
properties and its crystallization rate, fiber diameter, and
particle size [194, 195, 198200].
One of the limitations of current filter media, as opposed
to glass microfiber filters, is their large fiber diameter
range. Large fiber diameter determines both the particleloading capacity and the filtration performance. The average diameter of meltblown fibers is less than 10 microns
[198], analogous to high available surface area for adsorbent component to adhere. The smaller the meltblown
microfibers are, the more contact points between the
functional particles and fibers [95, 193, 200]. Size of the
particles can be 4005 microns [194, 200]. Larger size of
particles compared to microfibers enhances the mechanical
entrapment of adsorbent component, measurable by shaking tests [200].
Since the strength of meltblown webs is relatively low,
an optimum basis weight should be adopted to promote
structural integrity [90]. Furthermore, the mechanical performance of meltblown core structure can be enhanced by
sandwiching it between high surface area lightweight
spunbond layers that have higher strength. The composite
web is calendared afterwards to fix the layers and particles
[21, 29, 79].
In general, coform process is a high-throughput inexpensive method to produce composite webs. This is mainly
due to the simultaneous production of the web and particle
incorporation. In addition, attachment mechanism of particles to fibers can control the surface area loss.
Electrospinning
Implementation and Technology
There are three main techniques that lead to the formation
of nanofibers, namely meltblowing, multicomponent
spunbonding, and electrospinning [124, 215217], with the
latter yielding the finest fibers [218222]. Electrospinning
technique, during its first years of development, was primarily concerned with production of polymeric nanofibers
and complex nonwoven structures. During the last few
years, electrospinning was investigated as a novel technique for production of nanoparticle-polymer composite
nanofibers [223229] and organicinorganic molecular
sieve nanofibers [230]. The process involves using an
electric field to draw the fiber-forming polymer solution
[220] to afford a nonwoven web structure composing of
fibers with diameters down to few nanometers [218221,
231]. The resulted electrospun mats have shown great

4185

potentials for clean energy and water filtration applications


[232, 233].
In a typical process, for instance, according to the target
fiber diameter, the right amount of PAN is dissolved in
N,N-dimethylformamide (DMF) [216, 234239]; in hybrid
structures the functional material of interest is added to the
solution too [228, 234, 240242]. Applying the optimal
voltage to the solution [238], nanofibers are electrospun
and collected on the target substrate [243]. In laboratory
scale, the polymer solution is loaded into a syringe and
drawn from its needle tip. In industrial scale, the polymer
solution is drawn either from multiple pins [244] or from a
roller-like electrode rotating in the solution bath [245].
To produce composite nanofibers, the polymer solution
is mixed/loaded with the subject functional particles and
then electrospun [216, 217, 239, 246, 247]. The resulting
deposited nonwoven structure offers an excellent bed for
immobilization of nanoparticles, used in filtration [217,
248]. This is in view of the following facts: (1) sufficient
substrate flexibility; (2) coexistence of high SSA
nanoparticles and nanofibers; (3) optimal distribution of
nanoparticles in the electrospinning solution, thereby in the
final composite structure [217]; and (4) almost full accessibility to adsorbents pores due to the very small fiber
diameters relative to the adsorbent particle size [249].
Electrospinning solution precursors are from a vast
variety of polymers, both synthetic and natural [229, 237].
However, polymers with high carbon yields, such as pitch
[222, 250, 251] and PAN [235, 238, 252254], are
preferable for the formation of electrospun activated carbon nonwoven substrates.
In general, to produce a high-SSA activated carbon
nonwoven substrate, the electrospun web undergoes a set
of high-temperature transformational post-processes
including stabilization, carbonization, and physical/chemical activation [222, 235, 237, 239, 252, 255257]. Based
on the precursor component materials, the collected web is
stabilized (for 0.58 h at 200350 C), carbonized (for
0.58 h at 6001100 C), and subsequently activated (for
0.52 h at 6502200 C) [237]. The activation process
aims at the formation of pores. In physical activation, pores
are formed due to the thermal degradation and removal of
the activating agent at high temperatures [257260],
whereas, in chemical activation, pyrolysis of the chemical
agent and surface etching occur at lower temperatures [8,
14, 261]. The activation results in ultrafine porous AC
nanofibers that are self-assembled into the shape of a
nonwoven substrate for a variety of applications [234, 239,
251, 255, 262266]. The high SSA and micropore volume
of AC electrospun nanofibers enable applications in high
capacitance electrical double-layer capacitors [239, 240,
242, 267273], Li-ion battery separators [237, 240, 266,
274276], storage of drugs [263] and hydrogen [256, 277

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4186

279], sensors [236, 251], catalysts [262], and adsorbents


[265, 280284].
Additionally, to further develop the surface area and
functional sites on porous electrospun AC nanofibers, coelectrospinning has shown great potentials [237, 259, 260,
285]. Compared to the conventional electrospinning systems, the co-electrospinning solution comprises two
immiscible polymers with miscible solvents. The mixed
solution is electrospun using a coaxial spinneret into coresheath or islands-in-the-sea composite nanofibers. Subsequently, the core component is dissolved or pyrolyzed to
yield a high-SSA hollow porous-activated-electrospun
carbon nanofiber [257, 259261].
Although most of the studies regarding electrospun AC
nonwovens deal with the fabrication of non-hybrid structures [237], there are cases where inorganic species [225,
237, 286], SWCNT [228, 287], MWCNT [251, 288293],
and AC particles and graphite [234, 252, 294] have been
incorporated into electrospun AC substrates.
Hybrid MOF-nanofiber nonwovens, on the other hand,
are produced via mixing the pre-synthesized MOF(s) particles in the electrospinning solution. In a typical process,
MOFs crystals are synthesized separately and then dispersed uniformly in the electrospinning precursor solution
[191, 249, 295]. The MOF-containing electrospun nanofiber is then electrospun and collected on the target substrate
[243]. Some of these MOFs-containing hybrid structures
have been used as the support for secondary direct growth
(seed coating) of the mother MOF [191, 243, 296]. In the
case of subsequent secondary seed growth, the hybrid
substrate is placed in the mother-MOF synthesis reaction
media (precursor solution in the autoclave vial) and
undergone the hydrothermal/solvothermal synthesis steps
[191, 243]. Alternatively, the base hybrid substrate can be
impregnated and saturated by gradual addition (drop-bydrop) of the precursor solution, followed by solvent
removal at high temperatures, to yield the seed-coated final
substrate [296]. Hybrid MOF-nanofiber nonwovens have
been investigated for different applications such as VOC
and nitroaromatic sensors [191, 296, 297], separation and
gas purification [191, 243, 249, 295], catalysis [243], and
multicolor light-emitting devices [298].
The first attempt to use electrospinning solution as the
polymer carrier for MOF materials was by Rose et al.
[249]. They studied three polymersolvent systems (polystyrene (PS)-tetrahydrofurane (THF), PVP-EtOH, and
PAN-DMF) and two kinds of MOFs (MIL-100(Fe) and
HKUST-1). Figure 8 shows the three different compositions of the MOF-polymer electrospun composite webs
generated.
MOFs can form nanosized assemblies in both singlephase (non-hybrid) and hybrid structures. Unlike organic
polymers that can be processed into different desired

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J Mater Sci (2016) 51:41734200

shapes, e.g., fibers and sheets, MOFs are nonprocessable


owing to the insolubility and often melting with degradation [299]. However, recently, one-dimensional formation
of MOFs was reported [300305]. The key is to, first, form
amorphous coordination polymers [299], such as precursor
solutions [306, 307] or gels [308316]. Subsequently, the
single-phase MOF nanofibers can be electrospun. Electrospinning is used to spin pure MOF nanofibers from water-/
DMF-soluble Zn-based precursor solution [48]. Lu et al.
reported that the MOF nanofiber size ranges from 60 nm to
4 microns; however, the properties of nanofibers were not
reported. The solubility of the complex, the key to the
processability, depends on inclusion capability and
hydrogen bonding interactions. This is generally achievable by introduction of BPE (4,40 -bis(pyridyl) ethylene) or
BPY (4,40 -bipyridine) linear spacer ligands in the organic
solvents [306, 307]. The production of MOFs nanofibers
based on soluble precursors suffered from bad quality [317]
and was not practically available in large-scale applications
[299, 317]; therefore, electrospinning of gel-state MOFs
complexes was considered [317]. Nickel-based MOF gel
precursor was diluted by the addition of BPY and BPE to
create a viscose solution that was electrospinnable in the
absence of organic polymeric additives. The electrospun
nanofibers were about 100 nm in diameter and showed
promising properties for field emission applications [317].
Making hybrid adsorptive nonwoven webs is not limited
to MOFs or AC nanofibers. A variety of adsorbent materials can be electrospun into hybrid nonwovens. These
include zeolite nanofibers [230, 243, 318333] and zirconia/PVP [165] composite electrospun nanofiber
nonwovens.
It is worthy of attention that the similar hybridization
concept has been applied to composite nanofibers made
with the Forcespinning technology. Rotational movement
of the spinneret applies centrifugal and hydrostatic forces
to the mixed solution to initiate a liquid material jet. Jiang
et al. reported improved electrochemical properties in
force-spun tin-containing carbon nanofibers [334].
Characteristics and considerations
In general, electrospinning is a simple efficient method to
produce ultrafine high-surface-area fibers from a wide
variety of polymers. The nanofibers can be easily functionalized and their compositional and morphological
properties can be controlled by the choice of material(s) and process parameters [166, 217, 226, 227, 230,
274]. However, the process is low throughput, expensive,
and the emission of hazardous solvents and fiber non-uniformity are some of the challenges [215, 237, 335, 336].
The right choice of precursor-solvent system and the
optimal process parameters (such as applied voltage [237

J Mater Sci (2016) 51:41734200

4187

Fig. 8 Images (a, c) and SEM micrographs (b, d, e, f) from


electrospun MOF/fiber composites: a HKUST-1/PS fibers in relation
to a human hair, b HKUST-1 crystal on a PS fiber analog to a pearl
necklace, c homogeneous MIL-100(Fe)/PVP layer on polypropylene

non-woven, d MIL-100(Fe) particle in PVP fiber web, e, f HKUST-1


particles (BASF) in PAN fibers on a PAN non-woven (large substrate
fibers in background). Reprinted from [249] with permission from
John Wiley and Sons

239], TCD (tip to collector distance), solution flow rate


[237, 239], and spinneret diameter [237]) are critical factors. Physical and chemical nature of the precursor-solvent
system determines the boiling point of solvent [237, 299],
the electrical conductivity of solution [236, 237, 263], and

solution concentration [166, 217, 226, 227, 230, 237, 239,


274]. The latter is influenced by the viscosity and surface
tension of precursor-solvent and influences the morphology
and diameter of electrospun nanofibers [216, 237, 239,
299]. Lower diameter of nanofibers can contribute to

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4188

stabilization time, number of cross-junction points, substrate flexibility, SSA, pore volume, and pore accessibility.
Higher SSA, pore volume, and pore accessibility are the
keys to higher capacitance, catalytic performance,
adsorption, and selective ion adsorption [236, 237, 241,
242, 268, 273, 281283].
With regard to electrospun AC nanofibers, there are three
pore development mechanisms, namely breaking, exfoliation, and expansion; the latter yields the desired fibrous
porous structure [239]. Furthermore, pore size and uniformity of AC nanofibers are significantly affected by the size
and dispersion of activating agent [237, 258, 291, 294].
In the case of hybrid AC nanofibers, the ultimate
objective of hybridization is enhancing the pore formation
and improving the conductivity of final structure [240, 242,
267, 271, 272, 291]. Pore formation takes place during the
activation process based on different shrinkageexpansion
coefficients of the nanofiber components [228, 234, 251,
287294]. Moreover, the superior performance of electrospun AC nanofibers over its non-fibrous counterparts, i.e.,
PAC and GAC, is attributed to their high SSA, porous, and
fibrous morphology [241, 256, 282, 296].
AC nanofibers are inherently porous and high-surfacearea, so the added component in hybrid AC nanofibers is
not deemed to function as the adsorption sites. The functionality of the added component is to enhance the pore
formation process. Therefore, high loading percentage
of the functional component is not the sought-after processing parameter. Loading percentage of the functional
component ranges between 0 and 4 wt% [287] to 10 wt%
of the composite substrate [289]. Ju et al. found optimal
loading percentage at 3 wt% to reach uniform distribution,
without agglomeration [291]. Haji et al. reported that the
surface of hybrid SWCNT-AC nanofibers turned rough by
adding more than 5 wt% SWCNT [228].
Mechanical-physical properties of electrospun nonwoven web structure, such as flexibility and strength, depend
on the nature of the precursor materials and processing
conditions. Electrospun carbon fibers are too brittle and do
not have sufficient flexibility which is required for a textile
substrate, used per se in filtration application [250, 253,
337]. CNTs have high available interaction surface area
and they have been reported to reduce the brittleness of AC
nanofibers [237, 261, 281, 282, 291].
Loading percentage and loss of surface area for MOFnanofiber hybrid nonwovens are based on different objectives. In this case, high-SSA MOFs are the prime adsorptive sites; hence, higher loadings and minimal loss of the
SSA are sought-after. Hybrid MOF-nanofiber structures
can be electrospun with initial loadings of 3 wt% [296] to
5 wt% [191]; subsequently, secondary seed coating can be
done to increase the loading percentage.

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J Mater Sci (2016) 51:41734200

Rose et al. found that the maximal loading of


HKUST-1 in PS/THF was 40 %. Two possible reasons
were (1) the significant difference in polarity between
the non-polar PS and polar HKUST-1, and (2) the small
difference between particle size and fiber diameter. They
could increase the MOFs loading up to 80 % by using
PVP as the carrier polymer. This web suffered from two
important setbacks: (a) very low mechanical stability and
(b) immediate dissolution of the web upon contacting
small amounts of water. The solubility of the web cannot
be reduced by chemical cross-linking since MOFs offer
low chemical stability. Hence, they chose a PAN/DMF
solution and kept the loading at to 80 %; this web did
not suffer from water solubility. In this case, since the
loading was 80 % and the accessible MOF fraction was
78 %, they concluded that no pore blockage happens
[249]. Furthermore, Ostermann et al. reported that in the
56 wt%-loaded ZIF-8@PVP electrospun nanofibers, the
accessible ZIF fraction was 55.1 wt%. This corresponded to almost full accessibility and zero pore
blockage [295].
In conclusion, beside the advantages of electrospinning
[296], the low throughput, low fiber diameter uniformity,
and the environmental hazards inhibit the industrial
application of electrospinning [215, 237, 335, 336].

Other
MOF paper sheets
Tailoring and engineering the structure of cellulosic paper
sheets offer a suitable pliable structure. Their structure can
adopt different geometries based on the desired production
design. In addition, by choosing different pulp qualities or
use of additives one can render the structure thick, permeable, hydrophilic, and/or rigid. These highly flexible
design parameters afford paper-like bed structures for
MOFs. MOF particles can be introduced into the paper
sheet by adding fillers and/or pigments in paper forming
technology [13]. For example, HKUST-1 powder was
added to pulp slurry and introduced into paper sheets by the
Rapid Kothen sheet mold process. Figure 9 shows an
SEM image of the MOF-containing paper sheets.
It was observed that the slurry mixing approach yields
reasonably entrapped MOF composites. However,
HKUST-1 crystals were inhomogeneously distributed on
the MOF-containing paper sheets. The average content of
MOF particles ranged between 6.5 and 14.6 wt%, which is
fairly broad. Thereby, particle distribution homogeneity
needs improvement to make better MOF-containing paper
sheets [13, 163].

J Mater Sci (2016) 51:41734200

4189

Charged media

Fig. 9 Scanning electron micrograph of HKUST-1 paper hand


sheets. Reprinted from [163] with permission from John Wiley and
Sons

Mixed-matrix membranes containing MOFs


The term mixed-matrix membranes (MMMs) refers to
membranes manufactured from two or more matrices.
None of the matrices serves as the reinforcement component; however, each matrix material contributes specific
properties to final composite structure [338, 339]. Perez
et al. investigated Matrimid [340] as the base scaffold for
synthesis and growth of MOF-5 [341]. Matrimid 5218
(polyimide of 3,30 ,4, 0 -benzophenonetetracarboxylic dianhidride and diamino-phenylindane) was chosen because of
its attractive properties in gas selectivity, gas adsorption,
high air permeability, excellent mechanical properties, high
glass transition temperature, and high thermal stability
[342].
To prepare MMMs and MOF-5, Perez et al. prepared the
precursor solutions of both Matrimid matrix and MOF-5
and mixed them together with different weight ratios. After
bath sonication and stirring the mixed matrix, they cast it
onto a Mylar A92 film and annealed it in a vacuum oven
at 240 C for 24 h. The thickness of the final MMMs was
35 microns and the SEM images of the prepared MMMs
are shown in Fig. 10.
Air permeability of the membranes increased with
higher loading of MOF-5 and there was a great affinity
between the Matrimid matrix and MOF-5 crystals [341].
Pressure drop, flexibility, and mechanical properties of the
prepared membrane were not reported.
Additionally, successful spinning of PI - HKUST-1
blend is reported in the work of Hu et al. where they spun
the PI - HKUST-1 composite into MMM hollow fiber by
the dry/wet-spinning method [343].

One way to incorporate adsorbent materials into nonwoven


fibrous structure is by electrostatic charging. Either of the
components, i.e., nonwoven substrate or functional materials, can be charged and then brought together. The
coated substrate can then pass a thermal bonding process, such as calendaring, to fix the particles on the loaded
web [112, 344].
In the case of charged powder particles, the target
nonwoven substrate is ground and the charged powder is
sprayed onto the web based on electrostatic attraction. The
process involves the following steps: fluidization of the
powder particles, charging the powder, and spraying the
powder. The electrostatic properties of the target particles
are of prime consideration [95, 345].
Important process parameters include: (1) charge distribution uniformity, (2) structural integrity of fluidized
particles and nonwoven web, (3) electrostatic charging
voltage, (4) control over particle loss during spraying, and
(5) spraying distance, location, pressure, etc. [95, 345].
FibrolineTM is a commercially available process that
utilizes the electrostatic charging concept to incorporate
powders into fibrous substrates. The system is composed of
two face-to-face electrodes that are connected to an alternative high-tension generator. The strong alternative electric field affords a homogeneous powder distribution inside
the support. After scattering the powder onto the fibrous
support, the layer is placed between two dielectrics and
transported from one side to the other. Passed the alternative electric field, particles are accommodated within the
web. It is claimed that the process does not cause any
temperature build up in the substrate and no static electricity remains inside the material at the end of the treatment. Dielectric properties of the particles play the most
important role in this process (see Fig. 11).
The electrostatic/dielectric particle insertion process is
ecologically advantageous in the sense that no chemical/
binder agent is involved. This also promotes uncovered
accessible surface/pore on the adsorbent [95, 345].
Lamination
Lamination, sandwiching and bonding multiple layers of
material for enhanced functionality, is the most common
practice to make composite nonwoven filter media [1, 46,
346349]. Fibrous layers can be chosen from a variety of
processes, e.g., meltblown, spunbond, wetlaid, airlaid,
carded. Depending on the nonwoven formation techniqueconfiguration, layers can be laminated in-line with the
production or in a post process. Likewise, the adsorbent

123

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J Mater Sci (2016) 51:41734200

Fig. 10 SEM images of the surface (a, d, and g), cross section at low magnification (b, e, and h), and cross section at high magnification (c, f,
and i) of 10, 20, and 30 % MOF-5/Matrimid MMMs, respectively. Reprinted from [341] with permission from Elsevier

Fig. 11 Schematic process of


FibrolineTM. Reproduced from
[357]

component can either be applied in-line with the production or be formed separately beforehand and added later
[59, 138]. A variety of bonding techniques can be applied,
including: heat bonding or using hot melt adhesives, needle
punching, hydroentangling, and ultrasonic bonding [21, 26,
350352].

123

The functionality and properties of filter media can be


improved by laminating composite layers within a single
hybrid structure. However, the following processing
parameters and issues should be taken into consideration:
covered surface area of the absorbent component, structural
damage and delamination, increased pressure differential

J Mater Sci (2016) 51:41734200

through the filter depth, adhesion interference of particles


in highly loaded webs, stiffness, stability, and integrity of
the hybrid medium [21, 26, 353, 354].

General limitations of hybridization

4191

not the only reason that tight control on the particle loss is
important. For instance, in case of conductive ACs and
abrasive zirconia, the uncontrolled waste could potentially
cause damages to the machinery. In addition, emission of
solvent vapors in processes such as electrospinning should
be controlled to reduce environmental hazard [216, 336].

Surface area loss


Extra processes and cost-associated issues
The largest portion ([95 % [10, 13, 14]) of the surface area
and pore volume in adsorbent materials is from the
micropores, i.e., pores smaller than 2 nm. Based on the
pore structure, e.g., slit-shaped, V-shaped, ink-bottle or
neck-shaped, a large portion of surface area is accessible
through transitional macropores, i.e., pores larger than
50 nm [10]. Therefore, it is conceivable that blocking just a
few numbers of either of these pores would be at the
expense of losing a considerable amount of SSA and pore
volume [31, 355].
Choosing the suitable technique, one should deem that
the accessibility of the surface area and porous structure is
more important than the SSA itself. In general, the techniques in which the polymeric fiber and/or a binding agent
fuse into the adsorbent are vulnerable of masking a portion
of the pores. On the other hand, the media within which
functional particles are only mechanically entrapped are
vulnerable to dusting.
Process control
Due to the high surface free energy of the adsorbent
materials [22], they need to be uniformly distributed and
dispersed in the course of hybridization to avoid any
agglomeration [31, 159, 161, 174, 291, 298, 356]. Thus, the
functional component should be uniformly dispersed by
some means, such as sonication [174, 291, 294, 298, 356]
or magnetic stirring [152, 165, 265, 298]. Another process
control parameter that is in mutual relation with agglomeration is the loading percentage. It is reported that the
agglomeration is more likely to occur at higher loading
percentages [291]. Furthermore, higher loading percentages can adversely influence the mechanical properties of
the nonwoven, stability of the adsorbent materials on the
polymeric substrate, breathability, and stiffness of the
substrate [31, 159, 177, 237, 238].
Beside the uniform dispersion and loading percentage of
functional particles, the amount of waste and environmental threat associated with each technique should be
considered. In some processes, such as coforming, there
should be an effective control over the dispensing of the
functional materials. The most expensive component of a
hybrid adsorptive filter is the adsorbent material and waste
of these particles should be minimized. However, this is

Some of the mentioned techniques require pre-/post-processes that add up to final unit cost. For instance, to directly
grow the MOFs crystals on the substrate, some pretreatments are required that lengthen the production time and
add up to the final cost. In some cases, to provide the
hybrid nonwoven with optimal abrasion resistance and
mechanical strength, the web would undergo the lamination process [112, 194, 201, 202, 248]. Therefore, the extra
processes and their associated cost(s) should be considered
carefully before choosing a method.

Conclusions
We have reviewed the techniques to incorporate adsorbents
(activated carbons and metal-organic frameworks) in nonwoven gas filtration media. Electrospinning and direct
growth offer the highest adsorbent loading ranges and the
least surface area coverage; however, they have a very low
throughput. Wetlay process is not compatible with all
adsorbents and compounded nonwovens cannot contain
high loadings of adsorbents. Coating, thermal bonding,
lamination, and coform are high-throughput hybridization
processes. The major limitation of these techniques is the
potential coverage of adsorbent surface area. The amount
of the binding agent and the agent-particle surface interactions determine the coverage of adsorbents surface area.
The amount of molten polymer that fuses into the particles
pores determines the surface coverage in thermal bonding
and lamination processes. This amount depends on the
polymer thermal properties, adsorbent loading %, temperature, and duration of thermal processes. Coform process
offers an effective particle incorporation since the adsorbents are mechanically entrapped and partially bonded to
the fibers.
Funding This study was funded by The Nonwovens Institute (NWI)
at North Carolina State University (there was no specific grant
number).
Compliance with ethical standards
Conflict of Interest
of interest.

The authors declare that they have no conflict

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4192

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