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J Mater Sci (2016) 51:41734200

DOI 10.1007/s10853-016-9741-x


Hybrid adsorbent nonwoven structures: a review of current

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
Benot Maze
Michael C. Flickinger
Behnam Pourdeyhimi

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,

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

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,



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
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].


J Mater Sci (2016) 51:41734200

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
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
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
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


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
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



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


J Mater Sci (2016) 51:41734200

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

J Mater Sci (2016) 51:41734200


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
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



[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
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
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


J Mater Sci (2016) 51:41734200

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

J Mater Sci (2016) 51:41734200


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
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

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



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
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


J Mater Sci (2016) 51:41734200

absence of various chemicals promotes the environmental

issues [130]. However, following disadvantages are associated with this process:


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

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


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
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
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



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


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.
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


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



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


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

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.
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


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



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
MOFs can form nanosized assemblies in both singlephase (non-hybrid) and hybrid structures. Unlike organic
polymers that can be processed into different desired


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
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


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



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.


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].

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


Charged media

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

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

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
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, 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



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

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,


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


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.

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
Compliance with ethical standards
Conflict of Interest
of interest.

The authors declare that they have no conflict



1. Richards J (1995) Control of gaseous emissions: student manual,
APTI Course 415. Industrial Extension Service, College of
Engineering, North Carolina State University, Raleigh, NC
2. Rouquerol F (1999) Adsorption by powders and porous solids:
principles, methodology, and applications. Elsevier, New York
3. Yong Z, Mata V, Rodrigues A (2001) Adsorption of carbon
dioxide on chemically modified high surface area carbon-based
adsorbents at high temperature. Adsorpt J Int Adsorpt Soc
4. Zhou L (2007) Adsorption: progress in fundamental and application research: selected reports at the 4th Pacific Basin Conference on Adsorption Science and Technology: Tianjin, China,
2226 May 2006. World Scientific, Singapore; Hackensack, NJ
5. Bandosz TJ (2006) Activated carbon surfaces in environmental
remediation. Elsevier, San Diego
6. Toth J (2002) Adsorption: theory, modeling, and analysis.
Marcel Dekker, New York
7. Ruthven DM (1984) Principles of adsorption and adsorption
processes. Wiley, New York
8. Economy J, Daley M, Mangun C (1996) Activated carbon
fiberspast, present, and future. Abstr Pap Am Chem Soc
9. Yang RT (2003) Adsorbents: fundamentals and applications.
Wiley, Hoboken, NJ
10. Bansal RC (2005) Activated carbon adsorption. Taylor &
Francis, Boca Raton
11. Mueller U, Schubert M, Teich F, Puetter H, Schierle-Arndt K,
Pastre J (2006) Metal-organic frameworksprospective industrial applications. J Mater Chem 16:626636
12. Li J, Kuppler RJ, Zhou H (2009) Selective gas adsorption and
separation in metal-organic frameworks. Chem Soc Rev
13. Farrusseng D (ed) (2011) Metal-organic frameworks: applications from catalysis to gas storage. Wiley, Weinheim
14. Kwiatkowski JFE (ed) (2012) Activated carbon: classifications,
properties and applications. Nova Science Publishers, New York
15. Ferey G, Mellot-Draznieks C, Serre C, Millange F, Dutour J,
Surble S, Margiolaki I (2005) A chromium terephthalate-based
solid with unusually large pore volumes and surface area. Science 309:20402042
16. Horcajada P, Serre C, Maurin G, Ramsahye NA, Balas F, ValletRegi M, Sebban M et al (2008) Flexible porous metal-organic
frameworks for a controlled drug delivery. J Am Chem Soc
17. Koh K, Wong-Foy AG, Matzger AJ (2009) A porous coordination copolymer with over 5000 m(2)/g BET surface area.
J Am Chem Soc 131:41844185
18. Low JJ, Benin AI, Jakubczak P, Abrahamian JF, Faheem SA,
Willis RR (2009) Virtual high throughput screening confirmed
experimentally: porous coordination polymer hydration. J Am
Chem Soc 131:1583415842
19. Yan Y, Telepeni I, Yang S, Lin X, Kockelmann W, Dailly A,
Blake AJ et al (2010) Metal-organic polyhedral frameworks:
high H-2 adsorption capacities and neutron powder diffraction
studies. J Am Chem Soc 132:40924094
20. Zhou H, Long JR, Yaghi OM (2012) Introduction to metalorganic frameworks. Chem Rev 112:673674
21. Das D, Pourdeyhimi B (2014) Composite nonwoven materials:
structure, properties and applications. Woodhead Publishing,
22. Mahouche-Chergui S, Guerrouache M, Carbonnier B, Chehimi
MM (2013) Polymer-immobilized nanoparticles. Colloids Surf
Physicochem Eng Aspects 439:4368


J Mater Sci (2016) 51:41734200

23. Schlacchter J (2012) Respirator filter canister. US Patent
24. Wagner J (2001) Membrane filtration handbook (practical tips
and hints). Osmonics Inc, Minnetonka, Minnesota
25. Fuchs H, Kittelmann W, Lunenschloss J (2003) Nonwoven
fabrics. Wiley, Weinheim
26. Hutten IM (2007) Handbook of nonwoven filter media. Butterworth-Heinemann, Oxford, Burlington, MA
27. Russell SJ (2007) Handbook of nonwovens. CRC Press,
28. Billingsley BG, Jones ME (2013) Filter element utilizing shaped
particle-containing nonwoven web. US Patent 8,535,406
29. Das D, Pradhan AK, Chattopadhyay R, Singh S (2012) Composite nonwovens. Text Prog 44:184
30. Alexandre M, Dubois P (2000) Polymer-layered silicate
nanocomposites: preparation, properties and uses of a new class
of materials. Mater Sci Eng R-Rep 28:163
31. Kralik M, Corain B, Zecca M (2000) Catalysis by metal nanoparticles supported on functionalized polymers. Chem Pap 54:254264
32. Lee H, Yeo S, Jeong S (2003) Antibacterial effect of nanosized
silver colloidal solution on textile fabrics. J Mater Sci
38:21992204. doi:10.1023/A:1023736416361
33. Ray S, Okamoto M (2003) Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym
Sci 28:15391641
34. Cong H, Radosz M, Towler BF, Shen Y (2007) Polymerinorganic nanocomposite membranes for gas separation. Sep Purif
Technol 55:281291
35. Rozenberg BA, Tenne R (2008) Polymer-assisted fabrication of
nanoparticles and nanocomposites. Prog Polym Sci 33:40112
36. Zou H, Wu S, Shen J (2008) Polymer/silica nanocomposites:
preparation, characterization, properties, and applications. Chem
Rev 108:38933957
37. Cui X, Li CM, Bao H, Zheng X, Lu Z (2008) In situ fabrication
of silver nanoarrays in hyaluronan/PDDA layer-by-layer
assembled structure. J Colloid Interface Sci 327:459465
38. Spitalsky Z, Tasis D, Papagelis K, Galiotis C (2010) Carbon
nanotube-polymer composites: chemistry, processing, mechanical and electrical properties. Prog Polym Sci 35:357401
39. Chergui SM, Ledebt A, Mammeri F, Herbst F, Carbonnier B, Ben
Romdhane H, Delamar M et al (2010) Hairy carbon nanotube@nano-Pd heterostructures: design, characterization, and application
in suzuki C-C coupling reaction. Langmuir 26:1611516121
40. Fujii S, Matsuzawa S, Nakamura Y, Ohtaka A, Teratani T,
Akamatsu K, Tsuruoka T et al (2010) Synthesis and characterization of polypyrrole-palladium nanocomposite-coated latex
particles and their use as a catalyst for suzuki coupling reaction
in aqueous media. Langmuir 26:62306239
41. Mirkhalaf F, Graves JE (2012) Nanostructured electrocatalysts
immobilised on electrode surfaces and organic film templates.
Chem Pap 66:472483
42. Bandari R, Buchmeiser MR (2012) Polymeric monolith supported Pt-nanoparticles as ligand-free catalysts for olefin
hydrosilylation under batch and continuous conditions. Catal Sci
Technol 2:220226
43. Guerrouache M, Mahouche-Chergui S, Chehimi MM, Carbonnier B (2012) Site-specific immobilisation of gold nanoparticles
on a porous monolith surface by using a thiol-yne click photopatterning approach. Chem Commun 48:74867488
44. Pitakteeratham N, Hafuka A, Satoh H, Watanabe Y (2013) High
efficiency removal of phosphate from water by zirconium sulfate-surfactant micelle mesostructure immobilized on polymer
matrix. Water Res 47:35833590
45. Elkady MF, Ibrahim AM, El-Latif MMA (2011) Assessment of
the adsorption kinetics, equilibrium and thermodynamic for the

J Mater Sci (2016) 51:41734200















potential removal of reactive red dye using eggshell biocomposite beads. Desalination 278:412423
Sutherland K (2008) Filters and filtration handbook. Elsevier,
Burlington, MA
Purchas DB (2002) Handbook of filter media. Elsevier, New
DAmore A, Haghi AK (2014) Bioscience methodologies in
physical chemistry: an engineering and molecular approach. In:
DAmore A, Haghi AK, Zaikov GE, DAmore A (eds) editor of
compilation. Haghi AK, editor of compilation, Ebrary I (eds)
Formation of metal organic frameworks. Apple Academic Press,
Toronto, p 111
Sievert J (2011) Nonwovens in filtration. In: FILTECH 2011
conference proceedings, Wiesbaden, Germany
Alhakawati M, Banks C, Smallman D (2003) Evaluation of two
types of polyurethane for the immobilisation of Rhizopus oryzae
for copper uptake. Water Sci Technol 47:143150
Butler I (1999) Spunbond-meltblown technology handbook.
INDA, Association of the Nonwoven Fabrics Industry, Raleigh, NC
Fedorova N, Pourdeyhimi B (2007) High strength nylon microand nanofiber based nonwovens via spunbonding. J Appl Polym
Sci 104:34343442
Pourdeyhimi B, Sharp S (2011) High Strength, Durable Fabrics
Produced By Fibrillating Multilobal Fibers. US Patent 7,883,772
Pourdeyhimi B, Fedorova N, Sharp S (2011) Micro and nanofibers Spunbonded fabrics. US Patent 2011/0,318,986 A1
Durany A, Anantharamaiah N, Pourdeyhimi B (2009) High
surface area nonwovens via fibrillating spunbonded nonwovens
comprising Islands-in-the-Sea bicomponent filaments: structureprocess-property relationships. J Mater Sci 44:59265934.
Grove DA (2012) High dust holding capacity filter media. US
Patent 8,142,535
Ferey G (2008) Hybrid porous solids: past, present, future.
Chem Soc Rev 37:191214
Baumann NR, Hagen DF, Hansen PE, Markell CG (1994) Particle-loaded nonwoven fibrous article for separations and
purifications. US Patent 5,328,758
Sen AK (2008) Coated textiles: principles and applications.
Technomic Pub Co, Lancaster
Qian X, Zheng X, Zhang H, Kang W (2011) The method of
producing nanomaterials and melt blown nonwovens composites. Adv in Compos Pts 1 and 2 150151:667672
Carbonell RG, DeSimone JM, Novick BJ (2000) Method for
meniscus coating with liquid carbon dioxide. US Patent
Carbonell RG, DeSimone JM, Novick BJ (2002) Method for
meniscus coating with liquid carbon dioxide. US Patent
Carbonell RG, DeSimone JM, Novick BJ (2003) Method for
meniscus coating a substrate with a polymeric precursor. US
Patent 6,652,920
Burton SJ, Hammond DJ, Carbonell RG, Shen KZ, Gurgel PV,
Wiltshire-Lyerly V (2013) Prion protein binding materials and
methods of use. EP No. 1,615,992 B1
Carbonell RG, DeSimone JM, Novick BJ (2003) Apparatus for
meniscus coating with liquid carbon dioxide. US Patent
Burton SJ, Carbonell RG, Gurgel PV, Hammond DJ, Shen H,
Wiltshire-Lyerly V (2009) Prion protein binding materials and
methods of use. US Patent 7,510,848
Dallas AJ, Ding WL, Joriman JD, Zastera D, Giertz JR, Kalayci
VE, Chung HY (2014) Web comprising fine fiber and reactive,
adsorptive or absorptive particulate. US Patent 8,753,438
Khajavi R, Bahadoran MMS, Bahador A, Khosravi A (2013)
Removal of microbes and air pollutants passing through



















nonwoven polypropylene filters by activated carbon and

nanosilver colloidal layers. J Ind Text 42:219230
Quincy RB (2012) Activated carbon substrates. US Patent
8,168,852 B2
Pontius HT (1985) Cellulose fibers, synthetic fibers, activated
carbon. US Patent 4,504,290
Jeong SH, Hwang YH, Yi SC (2005) Antibacterial properties of
padded PP/PE nonwovens incorporating nano-sized silver colloids. J Mater Sci 40:54135418. doi:10.1007/s10853-005-4340-2
Chen SX, Liu JR, Zeng HM (2005) Structure and antibacterial
activity of silver-supporting activated carbon fibers. J Mater Sci
40:62236231. doi:10.1007/s10853-005-3149-3
Karacan I, Soy T (2013) Structure and properties of oxidatively
stabilized viscose rayon fibers impregnated with boric acid and
phosphoric acid prior to carbonization and activation steps.
J Mater Sci 48:20092021. doi:10.1007/s10853-012-6970-5
Singh B, Suryanarayana M, Baronia S, Rao N, Tripathi V, Lal
D, Sen A (2000) Evaluation of chemical protective clothing: a
comparative study of breakthrough times with sulphur mustard
and a simulant, 1,3-dichloropropane. Def Sci J 50:5157
Graver Technologies (2012) PLEKX filtration products. http://
Koslow EE, Walters Jr LS (2007) Composite for removing
moisture, liquid and odors with anti-microbial capability. US
Patent 7,238,403
Wei Q, Mao X, Hou D, Ye H, Huang F (2008) Characterization
of nonwoven material functionalized by sputter coating of
copper. Surf Coat Technol 202:25352539
Davis WT, Hood CC, Dever M (1995) Analysis of a thin activated carbon loaded adsorption medium. Sep Sci Technol
Dever M, Davis W, Hood C (1994) Development of an activated
carbon loaded melt blown spunbond laminate. Tappi J
Mann-Hummel (2013) Foams coated with activated carbon.
Gibson P, Schreuder-Gibson H, Rivin D (2001) Transport
properties of porous membranes based on electrospun nanofibers. Colloid Surf A-Physicochem Eng Asp 187:469481
Huang P, Peng C, Su C, Wang C (2004) A new filter media of
nonwoven composite with activated carbon fibers. J Adv Mater
Kishkovich O, Rezuke RW, Kinkead D (2006) Filters employing porous strongly acidic polymers. US Patent 7,022,164 B2
Freiherr VKH, Von BH (2007) Odour absorbing clothing and its
application. EP No 1,856,996 A1
Dyrud JF, Johnson EJ, Kinzer KE, McAllister JW, Mrozinski JS
(1990) Particle-filled microporous materials. US Patent
Coplan MJ, Lopatin G, Walton Jr JP (1985) Thermally plastifiable compositions for microporous sorbent structure. US Patent
Coplan MJ, Lopatin G, Walton Jr JP (1982) Open-celled
microporous sorbent-loaded textile fibers and films and methods
of fabricating same. US Patent 4,342,811
Leung WW (2012) Nanofiber filter facemasks and cabin filters.
US Patent 8,303,693
Dyrud JF, Krueger DL (1988) Respirator comprised of blown
bicomponent fibers. US Patent 4,729,371 A
Brochocka A, Majchrzycka K (2009) Technology for the production of bioactive melt-blown filtration materials applied to
respiratory protective devices. Fibres Text East Eur 17:9298
Turkevich LA (2005) Ferroelectric fibers and applications
therefor. US Patent 6,858,551


92. Krucinska I, Surma B, Chrzanowski M, Skrzetuska E, Puchalski
M (2013) Application of melt-blown technology for the manufacture of temperature-sensitive nonwoven fabrics composed of
polymer blends PP/PCL loaded with multiwall carbon nanotubes. J Appl Polym Sci 127:869878
93. Zhong J, Isayev AI (2015) Properties of polyetherimide/graphite
composites prepared using ultrasonic twin-screw extrusion.
J Appl Polym Sci 132:41397
94. Ghosh K, Maiti SN (1997) Melt rheological properties of silverpowder-filled polypropylene composites. Polym Plast Technol
Eng 36:703722
95. Chhaparwal S (2005) Fiber surface modification by particle
coating. M.Sc., North Caroline State University, Nonwoven
Cooperative Research Center
96. Cho JW, Paul DR (2001) Nylon 6 nanocomposites by melt
compounding. Polymer 42:10831094
97. Tung J, Gupta RK, Simon GP, Edward GH, Bhattacharya SN
(2005) Rheological and mechanical comparative study of in situ
polymerized and melt-blended nylon 6 nanocomposites. Polymer 46:1040510418
98. Wang M, Wang W, Liu T, Zhang W (2008) Melt rheological
properties of nylon 6/multi-walled carbon nanotube composites.
Compos Sci Technol 68:24982502
99. Ting C, Wang X, Huang X (2005) Effects of processing
parameters on the fiber diameter of melt blown nonwoven fabrics. Text Res J 75:7680
100. Duran D, Perincek S (2010) The effect of various production
parameters on the physical properties of polypropylene meltblown nonwovens. Ind Text 61:117123
101. Hassan MA, Yeom BY, Wilkie A, Pourdeyhimi B, Khan SA
(2013) Fabrication of nanofiber meltblown membranes and their
filtration properties. J Membr Sci 427:336344
102. Uppal R, Bhat G, Eash C, Akato K (2013) Meltblown nanofiber
media for enhanced quality factor. Fiber Polym 14:660668
103. Puch F, Hopmann C (2014) Nylon 6/multiwalled carbon nanotube composites: effect of the melt-compounding conditions
and nanotube content on the morphology, mechanical properties,
and rheology. J Appl Polym Sci 131:40893
104. Mahyoedin Y, Sahari J, Mukhtar A, Mohammad N (2011) Effect
of carbon black addition on the rheology properties of electrically conductive pp-graphite composite. Fundam Chem Eng Pts
105. Randall AM, Robertson CG (2014) Linear-nonlinear dichotomy
of the rheological response of particle-filled polymers. J Appl
Polym Sci 131:40818
106. Jeong SH, Yeo SY, Yi SC (2005) The effect of filler particle size
on the antibacterial properties of compounded polymer/silver
fibers. J Mater Sci 40:54075411. doi:10.1007/s10853-0054339-8
107. Gawish SM, Avci H, Ramadan AM, Mosleh S, Monticello R,
Breidt F, Kotek R (2012) Properties of antibacterial
polypropylene/nanometal composite fibers. J Biomater Sci
Polym Edn 23:4361
108. Radetic M (2013) Functionalization of textile materials with
silver nanoparticles. J Mater Sci 48:95107. doi:10.1007/
109. Ellison CJ, Phatak A, Giles DW, Macosko CW, Bates FS (2007)
Melt blown nanofibers: fiber diameter distributions and onset of
fiber breakup. Polymer 48:33063316
110. Nakamura T, Hasegawa S, Kato K (2005) Process and apparatus
for manufacturing fiber and fiber sheet carrying solid particles
and fiber and fiber sheet carrying solid particles. US Patent
111. Nakamura T, Hasegawa S, Kato K (2008) Process and apparatus
for manufacturing fiber and fiber sheet carrying solid particles.
US Patent 2008/0,083,369 A1


J Mater Sci (2016) 51:41734200

112. Czaplicki Z (2006) A new method and equipment for manufacturing new adsorptive materials with active carbon content.
Fibres Text Eastern Eur 14:7578
113. Permatron I (2013) Activated carbon air filter media for odor/fume
114. Dasdemir M, Maze B, Anantharamaiah N, Pourdeyhimi B
(2011) Formation of novel thermoplastic composites using
bicomponent nonwovens as a precursor. J Mater Sci
46:32693281. doi:10.1007/s10853-010-5214-9
115. Dasdemir M, Maze B, Anantharamaiah N, Pourdeyhimi B
(2012) Influence of polymer type, composition, and interface on
the structural and mechanical properties of core/sheath type
bicomponent nonwoven fibers. J Mater Sci 47:59555969.
MPER S, Moskopp M, Ouvry L,
116. Bohringer B, De RE, KA
Vodak DlH (2004) Adsorbing filter material with high adsorption capacity and low breakthrough property. EP No 1,468,732
117. Felton CD, Groeger HG, Serad GA (1996) Fibrous structures
containing immobilized particulate matter. US Patent 5,486,410 A
118. Fenton CD, Groeger HG, Serad GA (1997) Process for fibrous
structure containing immobilized particulate matter. US Patent
5,674,339 A
119. Felton CD, Gregory DH, Serad GA (2000) Process for fibrous
structure containing immobilized particulate matter. US Patent
6,024,813 A
120. Blucher Hv, Ouvry L, Kamper S, Moskopp M, Ruiter Ed,
Bohringer B (2007) Adsorption filter material with high
adsorption capacity and low breakthrough behavior. US Patent
7,160,369 B2
121. Wilfong DE, Xiao W, Thompson GJ, Sturm RC (2010) VOCabsorbing nonwoven composites. US Patent 7,825,050 B2
122. Samejima T (1979) Adsorptive nonwoven fabric comprising
fused fibers, non-fused fibers and absorptive material and
method of making same. US Patent 4,160,059
123. Groeger HG (1997) Particulate filter structure. US Patent
5,662,728 A
124. Yeom BY, Pourdeyhimi B (2011) Aerosol filtration properties of
PA6/PE islands-in-the-sea bicomponent spunbond web fibrillated by high-pressure water jets. J Mater Sci 46:57615767.
125. Koslow EE (2003) Composite filter medium and fluid filters
containing same. US Patent 6,550,622 B2
126. Fane AG, Schafer AI, Waite TD (2005) Nanofiltration : principles and applications. Elsevier, New York
127. Koslow EE (2005) Integrated paper comprising fibrillated fibers
and active particles immobilized therein. WO Patent
2005/035,866 A2
128. KX Technologies L (2011) PLEKXthe amazing filter medium.
129. Douglas AV, Morgan BD, Sprang TA (1996) Adsorbent
fibrous nonwoven composite structure. US Patent 5,571,604 A
130. Montefusco A (2005) The use of Nonwovens in air filtration.
Filtr Sep 42:3031
131. Heagle DG, Hiers JJ (1993) Blood filter and method of filtration.
US Patent 5,190,657
132. Koslow EE (2005) Microporous filter media, filtration systems
containing same, and methods of making and using. US Patent
6,959,820 B2
133. TriniTex A (2010) Activated carbon filter media. http://www.
134. KX Technologies L (2010) KXFACTfibrillated adsorbent
cellulose technology.

J Mater Sci (2016) 51:41734200

















Giglia RD, Battistelli EA (1986) Non-woven activated carbon
fabric. US Patent 4,565,727 A
Giglia RD, Battistelli E (1987) Non-woven activated carbon
fabric. EP No 0,144,553 B1
Giglia RD, Battistelli E (1990) Non-woven activated carbon
fabric. US Patent 4,904,343 A
Koslow EE (2010) Integrated paper comprising fibrillated fibers
and active particles immobilized therein. US Patent 7,655,112
Sterling Fibers (2011) CFF acrylic pulps/fibrillated fibers for
wet-laid/slurry processes.
Lorimier C, Le Coq L, Subrenat A, Le Cloirec P (2008) Indoor
air particulate filtration onto activated carbon fiber media.
J Environ Eng ASCE 134:126137
Schoenecker PM, Carson CG, Walton KS (2011) Structural
stability of Metal-Organic Frameworks under humid conditions.
Abstr Pap Am Chem Soc 242:201786
Jasuja H, Huang Y, Walton KS (2012) Adjusting the stability of
metal-organic frameworks under humid conditions by ligand
functionalization. Langmuir 28:1687416880
Jasuja H, Walton KS (2012) Effect of ligand functionalization
on the stability of DABCO based pillared MOFs under humid
conditions. Abstr Pap Am Chem Soc 243:219JX
Schoenecker PM, Carson CG, Jasuja H, Flemming CJJ, Walton
KS (2012) Effect of water adsorption on retention of structure
and surface area of metal-organic frameworks. Ind Eng Chem
Res 51:65136519
Jasuja H, Burtch NC, Huang Y, Cai Y, Walton KS (2013)
Kinetic water stability of an isostructural family of zinc-based
pillared metal-organic frameworks. Langmuir 29:633642
Han S, Huang Y, Watanabe T, Nair S, Walton KS, Sholl DS,
Carson Meredith J (2013) MOF stability and gas adsorption as a
function of exposure to water, humid air, SO2, and NO2.
Microporous Mesoporous Mater 173:8691
Jasuja H, Walton KS (2013) Effect of catenation and basicity of
pillared ligands on the water stability of MOFs. Dalton Trans
Abbasi AR, Akhbari K, Morsali A (2012) Dense coating of
surface mounted CuBTC metal-organic framework nanostructures on silk fibers, prepared by layer-by-layer method under
ultrasound irradiation with antibacterial activity. Ultrason
Sonochem 19:846852
Scherb C, Williams JJ, Hinterholzinger F, Bauer S, Stock N,
Bein T (2011) Implementing chemical functionality into oriented films of metal-organic frameworks on self-assembled
monolayers. J Mater Chem 21:1484914856
Shah M, McCarthy MC, Sachdeva S, Lee AK, Jeong H (2012)
Current status of metal-organic framework membranes for gas
separations: promises and challenges. Ind Eng Chem Res
Hu B, Fugetsu B, Yu H, Abe Y (2012) Prussian blue caged in
spongiform adsorbents using diatomite and carbon nanotubes for
elimination of cesium. J Hazard Mater 217218:8591
Pinto MdS, Augusto Sierra-Avila C, Hinestroza JP (2012) In situ
synthesis of a Cu-BTC metal-organic framework (MOF 199) onto
cellulosic fibrous substrates: cotton. Cellulose 19:17711779
Stock N, Biswas S (2012) Synthesis of metal-organic frameworks (MOFs): routes to various MOF topologies, morphologies, and composites. Chem Rev 112:933969
Shah MN, Gonzalez MA, McCarthy MC, Jeong H (2013) An
unconventional rapid synthesis of high performance metal-organic framework membranes. Langmuir ACS J Surf Colloids

155. Kwon HT, Jeong H (2013) In Situ synthesis of thin zeoliticimidazolate framework ZIF-8 membranes exhibiting exceptionally high propylene/propane separation. J Am Chem Soc
156. Liu Y, Ng Z, Khan EA, Jeong H, Ching C, Lai Z (2009) Synthesis of continuous MOF-5 membranes on porous alpha-alumina substrates. Microporous Mesoporous Mater 118:296301
157. Aguado S, Nicolas C, Moizan-Basle V, Nieto C, Amrouche H,
Bats N, Audebrand N et al (2011) Facile synthesis of an ultramicroporous MOF tubular membrane with selectivity towards
CO2. New J Chem 35:4144
158. Cao F, Zhang C, Xiao Y, Huang H, Zhang W, Liu D, Zhong C
et al (2012) Helium recovery by a Cu-BTC metal-organicframework membrane. Ind Eng Chem Res 51:1127411278
159. Nagaraju D, Bhagat DG, Banerjee R, Kharul UK (2013) In situ
growth of metal-organic frameworks on a porous ultrafiltration
membrane for gas separation. J Mater Chem A 1:88288835
160. Caro J (2011) Are MOF membranes better in gas separation than
those made of zeolites? Curr Opin Chem Eng 1:7783
161. Meilikhov M, Yusenko K, Schollmeyer E, Mayer C, Buschmann H,
Fischer RA (2011) Stepwise deposition of metal organic frameworks
on flexible synthetic polymer surfaces. Dalton Trans 40:48384841
162. Hasanzadeh M, Moghadam BH (2013) Polymer products and
chemical processes: techniques, analysis, and applications. In:
Anonymous potential applications of metal-organic frameworks
in textiles. CRC Press, p 239
163. Kuesgens P, Siegle S, Kaskel S (2009) Crystal growth of the
metal-organic framework Cu-3(BTC)(2) on the surface of pulp
fibers. Adv Eng Mater 11:9395
164. Centrone A, Yang Y, Speakman S, Bromberg L, Rutledge GC,
Hatton TA (2010) Growth of metal-organic frameworks on
polymer surfaces. J Am Chem Soc 132:1568715691
165. Pinto MdS, Avilla CAS, Hinestroza JP (2013) Metal organic
framework modified materials, methods of making and methods
of using same. US Patent 2013/0,274,087 A1
166. Fan L, Xue M, Kang Z, Li H, Qiu S (2012) Electrospinning
technology applied in zeolitic imidazolate framework membrane
synthesis. J Mater Chem 22:2527225276
167. Yao J, Dong D, Li D, He L, Xu G, Wang H (2011) Contradiffusion synthesis of ZIF-8 films on a polymer substrate. Chem
Commun 47:25592561
168. Pan Y, Wang B, Lai Z (2012) Synthesis of ceramic hollow fiber
supported zeolitic imidazolate framework-8 (ZIF-8) membranes
with high hydrogen permeability. J Membr Sci 421422:292298
169. Feng CY, Khulbe KC, Matsuura T, Ismail AF (2013) Recent
progresses in polymeric hollow fiber membrane preparation,
characterization and applications. Sep Purif Technol 111:4371
170. Xu G, Yao J, Wang K, He L, Webley PA, Chen C, Wang H
(2011) Preparation of ZIF-8 membranes supported on ceramic
hollow fibers from a concentrated synthesis gel. J Membr Sci
171. Cui X, Gu Z, Jiang D, Li Y, Wang H, Yan X (2009) In situ
hydrothermal growth of metal-organic framework 199 films on
stainless steel fibers for solid-phase microextraction of gaseous
benzene homologues. Anal Chem 81:97719777
172. Gu Z, Yang C, Chang N, Yan X (2012) Metal-organic frameworks for analytical chemistry: from sample collection to
chromatographic separation. Acc Chem Res 45:734745
173. Rallapalli PBS, Raj MC, Patil DV, Prasanth KP, Somani RS,
Bajaj HC (2013) Activated carbon @ MIL-101(Cr): a potential
metal-organic framework composite material for hydrogen
storage. Int J Energy Res 37:746753
174. Pachfule P, Balan BK, Kurungot S, Banerjee R (2012) Onedimensional confinement of a nanosized metal organic framework in carbon nanofibers for improved gas adsorption. Chem
Commun 48:20092011


175. Prasanth KP, Rallapalli P, Raj MC, Bajaj HC, Jasra RV (2011)
Enhanced hydrogen sorption in single walled carbon nanotube
incorporated MIL-101 composite metal-organic framework. Int
J Hydrogen Energy 36:75947601
176. Shi L, Liang R, Qiu J (2012) Controllable deposition of platinum nanoparticles on polyaniline-functionalized carbon nanotubes. J Mater Chem 22:1719617203
177. Dumee L, He L, Hill M, Zhu B, Duke M, Schuetz J, She F et al
(2013) Seeded growth of ZIF-8 on the surface of carbon nanotubes towards self-supporting gas separation membranes.
J Mater Chem A 1:92089214
178. Yang SJ, Choi JY, Chae HK, Cho JH, Nahm KS, Park CR
(2009) Preparation and enhanced hydrostability and hydrogen
storage capacity of CNT@MOF-5 hybrid composite. Chem
Mater 21:18931897
179. Yang SJ, Cho JH, Nahm KS, Park CR (2010) Enhanced
hydrogen storage capacity of Pt-loaded CNT@MOF-5 hybrid
composites. Int J Hydrog Energy 35:1306213067
180. Anbia M, Sheykhi S (2013) Preparation of multi-walled carbon
nanotube incorporated MIL-53-Cu composite metalorganic
framework with enhanced methane sorption. J Ind Eng Chem
181. Zhou F, Liu Q, Zhang W, Gu J, Zhu S, Zhang D (2014)
Fabrication of 3D carbon nanotube/porous carbon hybrid
materials. J Mater Sci 49:548557. doi:10.1007/s10853-0137734-6
182. Fraczek-Szczypta A, Bogun M, Blazewicz S (2009) Carbon fibers
modified with carbon nanotubes. J Mater Sci 44:47214727.
183. Teng F, Zhang G, Wang Y, Gao C, Zhang Z, Xie E (2015)
Photocatalytic properties of titania/porous carbon fibers composites prepared by self-template method. J Mater Sci
50:29212931. doi:10.1007/s10853-015-8857-8
184. Miyama T, Yonezawa Y (2004) Aggregation of photolytic gold
nanoparticles at the surface of chitosan films. Langmuir
185. de Moura MR, Mattoso LHC, Zucolotto V (2012) Development
of cellulose-based bactericidal nanocomposites containing silver
nanoparticles and their use as active food packaging. J Food Eng
186. Llorens A, Lloret E, Picouet PA, Trbojevich R, Fernandez A
(2012) Metallic-based micro and nanocomposites in food contact materials and active food packaging. Trends Food Sci
Technol 24:1929
187. Boufi S, Vilar MR, Ferraria AM, Botelho do Rego AM (2013)
In situ photochemical generation of silver and gold nanoparticles on chitosan. Colloids Surf Physicochem Eng Aspects
188. Amid H, Nosraty H, Maleki V (2010) Effects of nano-silver
finishing on the physical and mechanical properties of cotton
fabrics. In: 7th international conference-TEXSCI 2010, Liberec,
Czech Republic
189. Amid H, Nosraty H, Maleki V (2011) Experimental study on the
effects of nano-silver finishing on physical and mechanical
properties of cotton fabrics. SMARTEX-2011 World Textiles
Conference, Kafrelsheikh University, Egypt
190. Amid H, Nosraty H, Maleki V (2015) Physical and mechanical
properties of woven cotton fabrics after nanosilver finishing.
BAOJ Nanotechnol 1:001007
191. Wu Y, Li F, Liu H, Zhu W, Teng M, Jiang Y, Li W et al (2012)
Electrospun fibrous mats as skeletons to produce free-standing
MOF membranes. J Mater Chem 22:1697116978
192. Brooker RW, Cohen B, Jackson DM (1989) Active particlecontaining nonwoven material, method of formation thereof, and
uses thereof. US Patent 4,797,318


J Mater Sci (2016) 51:41734200

193. Braun DL (1976) Particle-loaded microfiber sheet product and
respirators made therefrom. US Patent 3,971,373
194. Brooker RW, Cohen B, Jackson DM (1989) Active particlecontaining nonwoven material, method of formation thereof, and
uses thereof. US Patent 4,797,318 A
195. Georger WA, Jones MF, Kopacz TJ, Zelazoski GA (1994)
Abrasion resistant fibrous nonwoven composite structure. US
Patent 5,350,624 A
196. Eian GL (1984) Reduced-stress vapor-sorptive garments. US
Patent 4,433,024
197. McCulloch WJG (1999) The history of the development of melt
blowing technology. In: Tappi nonwovens conference,
pp 109121
198. Frazier N, Harris C, Keck L (2003) Three-dimensional coform
nonwoven web. US Patent 2003/0,211,802 A1
199. Jackson DM, Schmidt MA (2009) Coform nonwoven web
formed from propylene/alpha-olefin meltblown fibers. US Patent
200. Nowicka C (2003) Composite nonwovens: the bonding durability of sorbent particles. Fibres Text East Eur 11:4649
201. Gaynor M, McManus J (2004) Spunbonded/meltblown/spunbonded laminate face mask. US Patent 2004/0,000,313 A1
202. Goddard WA (2007) Handbook of nanoscience, engineering,
and technology. CRC Press, Boca Raton, FL
203. Tascan M, Gaffney KL (2012) Effect of glass-beads on sound
insulation properties of nonwoven fabrics. J Eng Fibers Fabr
204. Boney LC, Haynes BD, Lake MB (2006) Process of making a
nonwoven web. US Patent 6,989,125
205. Fish JE, Lau JC, Haynes BD (2001) Die head assembly, apparatus, and process for meltblowing a fiberforming thermoplastic
polymer. US Patent 6,200,120
206. Haynes BD, McManus JL, Busby R (1999) Coflowing cold air
and hot air in melt blowing nozzle; prevents premature
quenching. US Patent 6,001,303
207. Haynes BD, Clark D, Lake M (2002) Breaker plate assembly for
producing bicomponent fibers in a meltblown apparatus. US
Patent 6,474,967
208. Haynes BD, Cook MC (2006) Die for producing meltblown
multicomponent fibers and meltblown nonwoven fabrics. US
Patent 7,150,616
209. Haynes BD, McManus JL, Duellman JM, Clark DF, Quincy III
RB (2003) Method of increasing the meltblown jet thermal core
length via hot air entrainment. US Patent 6,613,268
210. Haynes BD, Lake MB, Rhim H (2004) Process of and apparatus
for making a nonwoven web. US Patent 6,709,623
211. Lake M, Clark D, Haynes BD (2002) Breaker plate assembly for
producing bicomponent fibers in a meltblown apparatus. US
Patent 6,461,133
212. Mayer E, Lim HS (1989) New nonwoven microfiltration
membrane material. Fluid/Part Sep J 2:1721
213. Mitchler PA, Riddell WE, Baker CA (2002) Particle-containing
meltblown webs. US Patent 6,417,120 B1
214. Riddell WE (2002) Method of forming meltblown webs containing particles. US Patent 6,494,974 B2
215. Ward G (2005) Nanofibres: media at the nanoscale. Filtration
Sep 42:2224
216. Podgorski A, Balazy A, Gradon L (2006) Application of nanofibers to improve the filtration efficiency of the most penetrating
aerosol particles in fibrous filters. Chem Eng Sci 61:68046815
217. Greiner A, Wendorff J (2007) Electrospinning: a fascinating
method for the preparation of ultrathin fibers. Angew Chem Int
Ed 46:56705703
218. Grafe T, Graham K (2002) Polymeric nanofibers and nanofiber
webs: a new class of nonwovens. Presented at INTC 2002:

J Mater Sci (2016) 51:41734200
















International Nonwovens Technical Conference (Joint INDA

TAPPI Conference), Atlanta, Georgia
Kosmider K, Scott J (2002) Polymeric nanofibres exhibit an
enhanced air filtration performance. Filtration Sep 39:2022
Grafe T, Graham K (2003) Nanofiber webs from electrospinning. In: Nonwovens in filtrationfifth international conference, Stuttgart, Germany
Park HS, Park YO (2005) Filtration properties of electrospun
utrafine fiber webs. Korean J Chem Eng 22:165172
Park SH, Kim C, Jeong YI, Lim DY, Lee YE, Yang KS (2004)
Activation behaviors of isotropic pitch-based carbon fibers from
electrospinning and meltspinning. Synth Met 146:207212
Madhugiri S, Dalton A, Gutierrez J, Ferraris JP, Balkus KJ
(2003) Electrospun MEH-PPV/SBA-15 composite nanofibers
using a dual syringe method. J Am Chem Soc 125:1453114538
Zhan S, Chen D, Jiao X, Song Y (2007) Mesoporous TiO2/SiO2
composite nanofibers with selective photocatalytic properties.
Chem Commun 20:20432045
Wu Y, Balakrishna R, Reddy MV, Nair AS, Chowdari BVR,
Ramakrishna S (2012) Functional properties of electrospun NiO/
RuO2 composite carbon nanofibers. J Alloys Compounds
Luo CJ, Stoyanov SD, Stride E, Pelan E, Edirisinghe M (2012)
Electrospinning versus fibre production methods: from specifics
to technological convergence. Chem Soc Rev 41:47084735
Agarwal S, Greiner A, Wendorff JH (2013) Functional materials
by electrospinning of polymers. Prog Polym Sci 38:963991
Haji A, Nasouri K, Shoushtari AM, Kaflou A (2013) Reversible
hydrogen storage in electrospun composite nanofibers. In: Proceedings of the international conference nanomaterials: applications and properties
Ramakrishna S (2005) An introduction to electrospinning and
nanofibers. World Scientific, Singapore
Di J, Zhao Y, Yu J (2011) Fabrication of molecular sieve fibers
by electrospinning. J Mater Chem 21:85118520
Greiner A, Wendorff JH (2008) Functional self-assembled
nanofibers by electrospinning. Self-Assem Nanomater I Nanofibers 219:107171
Ramakrishna S, Jose R, Archana PS, Nair AS, Balamurugan R,
Venugopal J, Teo WE (2010) Science and engineering of electrospun nanofibers for advances in clean energy, water filtration,
and regenerative medicine. J Mater Sci 45:62836312. doi:10.
Kaur S, Sundarrajan S, Rana D, Sridhar R, Gopal R, Matsuura T,
Ramakrishna S (2014) Review: the characterization of electrospun nanofibrous liquid filtration membranes. J Mater Sci
49:61436159. doi:10.1007/s10853-014-8308-y
Patil SA, Chigome S, Hagerhall C, Torto N, Gorton L (2013)
Electrospun carbon nanofibers from polyacrylonitrile blended
with activated or graphitized carbonaceous materials for
improving anodic bioelectrocatalysis. Bioresour Technol
Gliscinska E, Babel K (2013) Preparation of activated carbon
fibres from electrospun polyacrylonitrile fibre mat and characterisation of their chemical and structural properties. Fibres Text
Eastern Eur 21:4247
Im JS, Kang SC, Lee S, Lee Y (2010) Improved gas sensing of
electrospun carbon fibers based on pore structure, conductivity
and surface modification. Carbon 48:25732581
Liu C, Lai K, Liu W, Yao M, Sun R (2009) Preparation of
carbon nanofibres through electrospinning and thermal treatment. Polym Int 58:13411349
Liu W, Adanur S (2010) Properties of electrospun polyacrylonitrile membranes and chemically-activated carbon nanofibers. Text Res J 80:124134

239. Im JS, Park S, Lee Y (2007) Preparation and characteristics of
electrospun activated carbon materials having meso- and
macropores. J Colloid Interface Sci 314:3237
240. He S, Chen L, Xie C, Hu H, Chen S, Hanif M, Hou H (2013)
Supercapacitors based on 3D network of activated carbon
nanowhiskers wrapped-on graphitized electrospun nanofibers.
J Power Sour 243:880886
241. Sullivan P, Moate J, Stone B, Atkinson JD, Hashisho Z, Rood
MJ (2012) Physical and chemical properties of PAN-derived
electrospun activated carbon nanofibers and their potential for
use as an adsorbent for toxic industrial chemicals. Adsorpt J Int
Adsorpt Soc 18:265274
242. Kim SY, Kim B, Yang KS, Oshida K (2012) Supercapacitive
properties of porous carbon nanofibers via the electrospinning of
metal alkoxide-graphene in polyacrylonitrile. Mater Lett
243. LiLi Fan, Ming Xue, ZiXi Kang, ShiLun Qiu (2013) Synthesis
of microporous membranes and films on various substrates by
novel electrospinning method. Sci China Chem 56:459464
244. Kim HY (2008) Electronic spinning apparatus, and a process of
preparing nonwoven fabric using the same. US Patent 7,332,050
245. Petrik S, Maly M (2009) Production nozzle-less electrospinning
nanofiber technology
246. Pourdeyhimi B, Lommel SA, Honarbakhsh S, Carbonell R,
Guenther RH (2013) Biodegradable non-woven fabric having
plant virus encapsulated actives for drug delivery. US Patent
247. Panthi G, Park S, Kim T, Chung H, Hong S, Park M, Kim H
(2015) Electrospun composite nanofibers of polyacrylonitrile
and Ag2CO3 nanoparticles for visible light photocatalysis and
antibacterial applications. J Mater Sci 50:44774485. doi:10.
248. Ramkumar S, Singh V, Lalagiri M (2011) Filtration efficiency of
the composite media prepared by meltblown and electrospun
nanofibers. In: Innovative nonwovens conference, NET, Atlanta,
249. Rose M, Boehringer B, Jolly M, Fischer R, Kaskel S (2011)
MOF processing by electrospinning for functional textiles. Adv
Eng Mater 13:356360
250. Bui N, Kim B, Yang KS, Dela Cruz ME, Ferraris JP (2009)
Activated carbon fibers from electrospinning of polyacrylonitrile/pitch blends. Carbon 47:25382539
251. Lee SK, Im JS, Kang SC, Lee S, Lee Y (2012) Effects of
improved porosity and electrical conductivity on pitch-based
carbon nanofibers for high-performance gas sensors. J Porous
Mater 19:989994
252. Lee KJ, Shiratori N, Lee GH, Miyawaki J, Mochida I, Yoon S,
Jang J (2010) Activated carbon nanofiber produced from electrospun polyacrylonitrile nanofiber as a highly efficient
formaldehyde adsorbent. Carbon 48:42484255
253. Manickam SS, Karra U, Huang L, Bui Nhu-Ngoc, Li B,
McCutcheon JR (2013) Activated carbon nanofiber anodes for
microbial fuel cells. Carbon 53:1928
254. Zhang L, Aboagye A, Kelkar A, Lai C, Fong H (2014) A review:
carbon nanofibers from electrospun polyacrylonitrile and their
applications. J Mater Sci 49:463480. doi:10.1007/s10853-0137705-y
255. Song X, Wang C, Zhang D (2009) Surface structure and
adsorption properties of ultrafine porous carbon fibers. Appl Surf
Sci 255:41594163
256. Im JS, Park S, Lee Y (2009) Superior prospect of chemically
activated electrospun carbon fibers for hydrogen storage. Mater
Res Bull 44:18711878
257. Peng M, Li D, Shen L, Chen Y, Zheng Q, Wang H (2006)
Nanoporous structured submicrometer carbon fibers prepared






















J Mater Sci (2016) 51:41734200

via solution electrospinning of polymer blends. Langmuir
Im JS, Jang J, Lee Y (2009) Synthesis and characterization of
mesoporous electrospun carbon fibers derived from silica template. J Ind Eng Chem 15:914918
Zussman E, Yarin A, Bazilevsky A, Avrahami R, Feldman M
(2006) Electrospun polyacrylonitrile/poly (methyl methacrylate)-derived turbostratic carbon micro-/nanotubes. Adv Mater
Kim C, Jeong YI, Ngoc BTN, Yang KS, Kojima M, Kim YA,
Endo M et al (2007) Synthesis and characterization of porous
carbon nanofibers with hollow cores through the thermal treatment of electrospun copolymeric nanofiber webs. Small 3:9195
Dror Y, Salalha W, Avrahami R, Zussman E, Yarin AL, Dersch
R, Greiner A et al (2007) One-step production of polymeric
microtubes by co-electrospinning. Small 3:10641073
Ghasemi M, Shahgaldi S, Ismail M, Kim BH, Yaakob Z, Wan
Daud WR (2011) Activated carbon nanofibers as an alternative
cathode catalyst to platinum in a two-chamber microbial fuel
cell. Int J Hydrogen Energy 36:1374613752
Yun J, Im JS, Lee SK, Kim H, Lee Y (2012) A selective drugrelease system consisting of surface-modified electrospun carbon fibers by oxy/fluorination. J Porous Mater 19:781789
Su C, Huang Y, Wong J, Lu C, Wang C (2012) PAN-based
carbon nanofiber absorbents prepared using electrospinning.
Fibers Polym 13:436442
Bai Y, Huang Z, Zhang Z, Kang F (2013) Improvement of the
hydrophilicity of electrospun porous carbon nanofibers by
grafting phenylsulfonic acid groups. J Colloid Interface Sci
Aykut Y, Pourdeyhimi B, Khan SA (2013) Catalytic graphitization and formation of macroporous-activated carbon nanofibers from salt-induced and H2S-treated polyacrylonitrile.
J Mater Sci 48:77837790. doi:10.1007/s10853-013-7463-x
Seo M, Park S (2009) Electrochemical characteristics of activated carbon nanofiber electrodes for supercapacitors. Mater Sci
Eng B 164:106111
Kim C, Yang KS (2003) Electrochemical properties of carbon
nanofiber web as an electrode for supercapacitor prepared by
electrospinning. Appl Phys Lett 83:12161218
Kim C, Kim JS, Kim SJ, Lee WJ, Yang KS (2004) Supercapacitors prepared from carbon nanofibers electrospun from
polybenzimidazol. J Electrochem Soc 151:A769A773
Kim C, Choi Y, Lee W, Yang K (2004) Supercapacitor performances of activated carbon fiber webs prepared by electrospinning of PMDA-ODA poly(amic acid) solutions. Electrochim
Acta 50:883887
Kim B, Bui N, Yang K, dela Cruz ME, Ferraris JP (2009)
Electrochemical properties of activated polyacrylonitrile/pitch
carbon fibers produced using electrospinning. Bull Korean
Chem Soc 30:19671972
Im JS, Woo S, Jung M, Lee Y (2008) Improved capacitance
characteristics of electrospun ACFs by pore size control and
vanadium catalyst. J Colloid Interface Sci 327:115119
Kim C (2005) Electrochemical characterization of electrospun
activated carbon nanofibres as an electrode in supercapacitors.
J Power Sour 142:382388
Miao J, Miyauchi M, Simmons TJ, Dordick JS, Linhardt RJ
(2010) Electrospinning of nanomaterials and applications in
electronic components and devices. J Nanosci Nanotechnol
Aykut Y (2012) Enhanced field electron emission from electrospun co-loaded activated porous carbon nanofibers. Acs Appl
Mater Interfaces 4:34053415
Ji L, Zhang X (2009) Generation of activated carbon nanofibers
from electrospun polyacrylonitrile-zinc chloride composites for




















use as anodes in lithium-ion batteries. Electrochem Commun

Im JS, Kwon O, Kim YH, Park S, Lee Y (2008) The effect of
embedded vanadium catalyst on activated electrospun CFs for
hydrogen storage. Microporous Mesoporous Mater 115:514521
Im JS, Park S, Kim TJ, Kim YH, Lee Y (2008) The study of
controlling pore size on electrospun carbon nanofibers for
hydrogen adsorption. J Colloid Interface Sci 318:4249
Im JS, Jung MJ, Lee Y (2009) Effects of fluorination modification on pore size controlled electrospun activated carbon
fibers for high capacity methane storage. J Colloid Interface Sci
Sullivan PD, Stone BR, Hashisho Z, Rood MJ (2007) Water
adsorption with hysteresis effect onto microporous activated
carbon fabrics. Adsorpt J Int Adsorpt Soc 13:173189
Katepalli H, Bikshapathi M, Sharma CS, Verma N, Sharma A
(2011) Synthesis of hierarchical fabrics by electrospinning of
PAN nanofibers on activated carbon microfibers for environmental remediation applications. Chem Eng J 171:11941200
Teng M, Qiao J, Li F, Bera PK (2012) Electrospun mesoporous
carbon nanofibers produced from phenolic resin and their use in
the adsorption of large dye molecules. Carbon 50:28772886
Oh G, Ju Y, Kim M, Jung H, Kim HJ, Lee W (2008) Adsorption
of toluene on carbon nanofibers prepared by electrospinning. Sci
Total Environ 393:341347
Shim WG, Kim C, Lee JW, Yun JJ, Jeong YI, Moon H, Yang
KS (2006) Adsorption characteristics of benzene on electrospunderived porous carbon nanofibers. J Appl Polym Sci
Ji L, Medford AJ, Zhang X (2009) Fabrication of carbon fibers
with nanoporous morphologies from electrospun polyacrylonitrile/poly(L-lactide) blends. J Polym Sci B Poly Phys
Ren T, Si Y, Yang J, Ding B, Yang X, Hong F, Yu J (2012)
Polyacrylonitrile/polybenzoxazine-based Fe3O4@carbon nanofibers: hierarchical porous structure and magnetic adsorption
property. J Mater Chem 22:1591915927
Ko F, Gogotsi Y, Ali A, Naguib N, Ye H, Yang GL, Li C et al
(2003) Electrospinning of continuous carbon nanotube-filled
nanofiber yarns. Adv Mater 15:11611165
Prilutsky S, Zussman E, Cohen Y (2008) The effect of embedded carbon nanotubes on the morphological evolution during the
carbonization of poly(acrylonitrile) nanofibers. Nanotechnology
Ra EJ, An KH, Kim KK, Jeong SY, Lee YH (2005) Anisotropic
electrical conductivity of MWCNT/PAN nanofiber paper. Chem
Phys Lett 413:188193
Chakrabarti K, Nambissan PMG, Mukherjee CD, Bardhan KK,
Kim C, Yang KS (2006) Positron annihilation spectroscopy of
polyacrylonitrile-based carbon fibers embedded with multi-wall
carbon nanotubes. Carbon 44:948953
Ju Y, Choi G, Jung H, Lee W (2008) Electrochemical properties
of electrospun PAN/MWCNT carbon nanofibers electrodes
coated with polypyrrole. Electrochim Acta 53:57965803
Yang KS, Kim C, Park SH, Kim JH, Lee WJ (2006) Fabrications
and electrochemical properties of activated carbon nanofibers
from electrospinning of various polymers. J Biomed Nanotechnol 2:103105
Park S, Im S, Rhee JM, Lee Y (2007) Preparation and characterization of activated carbon nanofiber webs containing multiwalled carbon nanotubes by electrospinning. Nanocompos
Nanoporous Mater 119:5558
Wang G, Dong Q, Ling Z, Pan C, Yu C, Qiu J (2012) Hierarchical activated carbon nanofiber webs with tuned structure
fabricated by electrospinning for capacitive deionization.
J Mater Chem 22:2181921823

J Mater Sci (2016) 51:41734200

295. Ostermann R, Cravillon J, Weidmann C, Wiebcke M, Smarsly
BM (2011) Metal-organic framework nanofibers via electrospinning. Chem Commun 47:442444
296. Xu Y, Wen Y, Zhu W, Wu Y, Lin C, Li G (2012) Electrospun
nanofibrous mats as skeletons to produce MOF membranes for
the detection of explosives. Mater Lett 87:2023
297. Khoshaman AH (2011) Application of electrospun thin films for
supra-molecule based gas sensors. Masters, applied science:
school of engineering science
298. de Melo EF, Santana NdC, Alves KGB, de Sa GF, de Melo CP,
Rodrigues MO, Junior SA (2013) LnMOF@ PVA nanofiber:
energy transfer and multicolor light-emitting devices. J Mater
Chem C 1:75747581
299. Leong WL, Vittal JJ (2011) One-dimensional coordination
polymers: complexity and diversity in structures, properties, and
applications. Chem Rev 111:688764
300. Carlucci L, Ciani G, Proserpio DM, Sironi A (1997) Extended
networks via hydrogen bond cross-linkages of [M(bipy)] (M =
Zn2 ? or Fe2 ?; bipy = 4,40 -bipyridyl) linear co-ordination
polymers. J Chem Soc Dalton Trans 11:18011803
301. Aoyagi M, Biradha K, Fujita M (2000) Formation of two, one,
and zero-dimensional coordination assemblies from Cd(II) ion
and 4,4 -bipyridine. Bull Chem Soc Jpn 73:13691373
302. Kim H, Lee J, Lee M (2005) Stimuli-responsive gels from
reversible coordination polymers. Angew Chem Int Ed
303. Kim J, Lee U, Koo BK (2006) One-dimensional network of
zinc(II) coordination polymer with 4,4-bipyridine (4,4-bipy).
Bull Korean Chem Soc 27:918920
304. Briceno A, Hill Y, Gonzalez T, Diaz de Delgado G (2009)
Combining hydrogen bonding and metal coordination for controlling topochemical [2 ? 2] cycloaddition from multi-component assemblies. Dalton Trans 9:16021610
305. Rajput L, Sarkar M, Biradha K (2010) Assembling one-dimensional coordination polymers into three-dimensional architectures via hydrogen bonds. J Chem Sci 122:707720
306. Lu JY, Norman C, Abboud KA, Ison A (2001) Crystal engineering of an inclusion coordination polymer with cationic
pocket-like structure and its property to form metalorganic
nanofibers. Inorg Chem Commun 4:459461
307. Lu JY, Runnels KA, Norman C (2001) A new metal-organic
polymer with large grid acentric structure created by unbalanced
inclusion species and its electrospun nanofibers. Inorg Chem
308. Lu JY, Norman C (2003) Synthesis and structure of two new
coordination polymers featuring noncentrosymmetric inclusion
of hydrogen-bonded species. Polyhedron 22:235240
309. Kuroiwa K, Shibata T, Takada A, Nemoto N, Kimizuka N
(2004) Heat-set gel-like networks of lipophilic Co(II) triazole
complexes in organic media and their thermochromic structural
transitions. J Am Chem Soc 126:20162021
310. Roubeau O, Colin A, Schmitt V, Clerac R (2004) Thermoreversible gels as magneto-optical switches. Angew Chem Int Ed
311. Andrews PC, Junk PC, Massi M, Silberstein M (2006) Gelation
of La(III) cations promoted by 5-(2-pyridyl) tetrazolate and
water. Chem Commun 31:33173319
312. Fujigaya T, Jiang D, Aida T (2007) Spin-crossover physical
gels: a quick thermoreversible response assisted by dynamic
self-organization. Chem Asian J 2:106113
313. Zhang S, Yang S, Lan J, Yang S, You J (2008) Helical nonracemic tubular coordination polymer gelators from simple
achiral molecules. Chem Commun 46:61706172
314. Leong WL, Batabyal SK, Kasapis S, Vittal JJ (2008) Fluorescent magnesium(II) coordination polymeric hydrogel. chemistry? A Eur J 14:88228829

315. Leong WL, Tam AY, Batabyal SK, Koh LW, Kasapis S, Yam
VW, Vittal JJ (2008) Fluorescence enhancement of coordination
polymeric gel. Chem Commun 31:36283630
316. Grondin P, Roubeau O, Castro M, Saadaoui H, Colin A, Clerac
R (2010) Multifunctional gels from polymeric spin-crossover
metallo-gelators. Langmuir 26:51845195
317. Batabyal SK, Peedikakkal AMP, Ramakrishna S, Sow CH, Vittal
JJ (2009) Coordination-polymeric nanofibers and their fieldemission properties. Macromol Rapid Commun 30:13561361
318. Mintova S, Valtchev V (1996) Deposition of zeolite A on
vegetal fibers. Zeolites 16:3134
319. Lee GS, Lee YJ, Choi SY, Park YS, Yoon KB (2000) Selfassembly of beta-glucosidase and D-glucose-tethering zeolite
crystals into fibrous aggregates. J Am Chem Soc 122:1215112157
320. Lee GS, Lee Y-, Ha K, Yoon KB (2001) Preparation of flexible
zeolite-tethering vegetable fibers. Adv Mater 13:14911495
321. Ke C, Yang WL, Ni Z, Wang YJ, Tang Y, Gu Y, Gao Z (2001)
Electrophoretic assembly of nanozeolites: zeolite coated fibers
and hollow zeolite fibers. Chem Commun 8:783784
322. Dong A, Wang Y, Tang Y, Ren N, Zhang Y, Yue Y, Gao Z
(2002) Zeolitic tissue through wood cell templating. Adv Mater
323. Lin JC, Dipre JT, Yates MZ (2003) Microemulsion-directed
synthesis of molecular sieve fibers. Chem Mater 15:27642773
324. Li S, Wang X, Beving D, Chen ZW, Yan YS (2004) Molecular
sieving in a nanoporous b-oriented pure-silica-zeolite MFI
monocrystal film. J Am Chem Soc 126:41224123
325. Liu BS, Tang DC, Au CT (2005) Fabrication of analcime zeolite
fibers by hydrothermal synthesis. Microporous Mesoporous
Mater 86:106111
326. Zhang J, Dong JH, Luo M, Xiao H, Murad S, Normann RA
(2005) Zeolite-fiber integrated optical chemical sensors for
detection of dissolved organics in water. Langmuir
327. Song W, Grassian VH, Larsen SC (2006) Fiber and film formation by self-assembly of colloidal silicalite-1 and copper
coated silicalite-1 nanocrystals. Microporous Mesoporous Mater
328. Srinivasan D, Rao R, Zribi A (2006) Synthesis of novel microand mesoporous zeolite nanostructures using electrospinning
techniques. J Electron Mater 35:504509
329. Cucchi I, Spano F, Giovanella U, Catellani M, Varesano A,
Calzaferri G, Botta C (2007) Fluorescent electrospun nanofibers
embedding dye-loaded zeolite crystals. Small 3:305309
330. Di J, Chen H, Wang X, Zhao Y, Jiang L, Yu J, Xu R (2008)
Fabrication of zeolite hollow fibers by coaxial electrospinning.
Chem Mater 20:35433545
331. Wang Z, Ge Q, Shao J, Yan Y (2009) High performance zeolite
LTA pervaporation membranes on ceramic hollow fibers by
dipcoating-wiping seed deposition. J Am Chem Soc
332. Liu HA, Balkus KJ Jr (2009) Novel delivery system for the
bioregulatory agent nitric oxide. Chem Mater 21:50325041
333. Vohra V, Devaux A, Dieu L, Scavia G, Catellani M, Calzaferri
G, Botta C (2009) Energy transfer in fluorescent nanofibers
embedding dye-loaded zeolite L crystals. Adv Mater
334. Jiang H, Ge Y, Fu K, Lu Y, Chen C, Zhu J, Dirican M et al
(2015) Centrifugally-spun tin-containing carbon nanofibers as
anode material for lithium-ion batteries. J Mater Sci
50:10941102. doi:10.1007/s10853-014-8666-5
335. Demir MM, Yilgor I, Yilgor E, Erman B (2002) Electrospinning
of polyurethane fibers. Polymer 43:33033309
336. Kalayci VE, Patra PK, Kim YK, Ugbolue SC, Warner SB (2005)
Charge consequences in electrospun polyacrylonitrile (PAN)
nanofibers. Polymer 46:71917200


337. Rose M, Kockrick E, Senkovska I, Kaskel S (2010) High surface
area carbide-derived carbon fibers produced by electrospinning
of polycarbosilane precursors. Carbon 48:403407
338. Amid H, Jeddi AAA, Salehi M, Dabiryan H (2011) Suitability of
tubular woven fabric as the reinforcement of composite pipes.
In: Proceedings of ATC-11, Daegu, South Korea
339. Amid H, Jeddi AAA, Salehi M, Dabiryan H, Pejman R (2015)
Investigation of circular woven composite preforms for composite pipes. AUTEX Res J. doi:10.1515/aut-2015-0036
340. Ciba Specialty Chemicals (1998) Matrimid 5218 Resins. http://
341. Perez EV, Balkus KJ Jr, Ferraris JP, Musselman IH (2009)
Mixed-matrix membranes containing MOF-5 for gas separations. J Membr Sci 328:165173
342. Nistor C, Shishatskiy S, Popa M, Nunes SP (2008) Composite
membranes with cross-linked matrimid selective layer for gas
separation. Environ Eng Manag J 7:653659
343. Hu J, Cai H, Ren H, Wei Y, Xu Z, Liu H, Hu Y (2010) Mixedmatrix membrane hollow fibers of Cu-3(BTC)(2) MOF and
polyimide for gas separation and adsorption. Ind Eng Chem Res
344. Nakao E (1986) Method of manufacturing an electret filter. US
Patent 4,592,815
345. Cohen B, Faass JK, Gipson LH, Jameson LK (2001) Method of
attaching a substantially uniform distribution of particulates to
individual exposed surfaces of a substrate. US Patent 6,294,222
346. Carbonell RG (2012) Particles embedded in a porous substrate
for removing target analyte from a sample. US Patent 8,101,425


J Mater Sci (2016) 51:41734200

347. Carbonell RG (2005) Particles embedded in a porous substrate
for removing target analyte from a sample. WO Patent
2,005,123,952 A2
348. Carbonell RG (2012) Devices and methods for removing target
agents from a sample. US Patent 8,163,563
349. Herigstad MO, Gurgel PV, Carbonell RG (2011) Transport and
binding characterization of a novel hybrid particle impregnated
membrane material for bioseparations. Biotechnol Prog 27:129139
350. Ramkumar SS (2009) Process for making chemical protective
wipes and such wipes. US Patent 7,516,525
351. Johnson J, Handy J (2003) Breathing new life into dust collection filters. Ceram Ind 153:3941
352. Fukuda T, Shimada M, Ishizaki N, Iwahori S (1980) Carbon
adsorptive filter material with layers of reinforcing non woven
fabrics needle punched. US Patent 4,181,513
353. Maltha A, Berkhout E, van der Molen L, Koerntjes M, Colbond
BV (2012) Enhanced performance of cabin air filter media with
a bicomponent spunbond nonwoven. In: 11th world filtration
congress, Graz, Austria
354. Diederich F (2011) Loaded adsorption filtera solution for
purgeable, volatile components and odours in automotive interiors?
In: FILTECH 2011 conference proceedings, Wiesbaden, Germany
355. Czaja AU, Trukhan N, Mueller U (2009) Industrial applications
of metal-organic frameworks. Chem Soc Rev 38:12841293
356. Satya AR, Subramanian S, Seeram R (2012) Functionalized
cellulose: PET polymer fibers with zeolites for detoxification
against nerve agents. J Inorg Mater 27:332336
357. Fibroline (2013) Homogeneous powder distribution inside the
support based on strong alternative electric field. http://www.