Spectroscopic Characterization of Multilayered Functional Protective Polymers via Surface Modification with Organic Polymers against Highly Toxic Chemicals

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Chapter 7
Spectroscopic Characterization of Multilayered
Functional Protective Polymers via Surface Modification
with Organic Polymers against Highly Toxic Chemicals
Peter P. Ndibewu, Prince Ngobeni, Tina E. Lefakane and Taki E. Netshiozwi
Additional information is available at the end of the chapter
http://dx.doi.org/10.5772/62154
Abstract
Recent advances in biopolymers, including functional biomaterials for the manufacture
of personal protective garments (PPGs) or equipment (PPE) have dramatically improved
their efficiency and performance. Good and acceptable permeation characteristics, me‐
chanical strength and durability are common attributes of these materials simultaneously
without compromise for their cost-effectiveness and manufacturability. The comprehen‐
sive characterization of these materials and specimens’ three-dimensionality with the en‐
deavor to obtain the highest resistance to highly toxic agents such as nuclear, chemical
and biological warfare agents is the must fulfilling aim in today’s global interest in con‐
tinuous development in this area.
Because energy absorption component seems to be important in considering quality the
requirements related to the application of most protective materials (e.g. clothing), spec‐
troscopy would seem to be the cornerstone to be considered for most analytical purposes
to supplement the qualitative and quantitative assessment of polymeric materials. The
major techniques worth mentioning include: scanning electron microscopy coupled to X-
ray dispersive spectroscopy (SEM/EDS), atomic force microscopy (AFM), scattering-type
near-field optical microscopy, scanning tunneling microscopy (STM), attenuated total re‐
flectance Fourier transform spectroscopy (ATR-FT-IR), infrared spectroscopic ellipsome‐
try, nano-FTIR absorption spectroscopy, near-field optical microscopy, and infrared
vibrational nano-spectrosocopy. This chapter will discuss the importance of a particularly
important natural polymer (cellulose) containing acetyl groups to form modifiable bio‐
polymers (e.g. cellulose acetate polymers), doped to yield multi-layered functional pro‐
tective materials (MFPMs) or composites (MFPCs). The ultimate aim seeks to provide
critical insights into understanding the enhancement of their permeation characteristics
against exposure to toxic industrial chemicals, including chlorine which is currently be‐
ing used as a chemical warfare agent of choice in the Syrian conflict. MFPMs or MFPCs
are a group of materials made from a combination of fiber or polymers together with
varying amounts of additives possessing tailored physical and mechanical properties.
Many of these materials should not only be durable but also must provide cost-competi‐
© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution,
and reproduction in any medium, provided the original work is properly cited.

tive products in the manufacturability of personal protective garments (PPGs). The key
advantages and disadvantages of available protective materials manufactured with syn‐
thetic polymers compared to biopolymeric ones based on the objective of achieving the
highest quality, maximum protection, or both are presented. The chapter will also explain
the fundamental differences of each material- and how biopolymers can potentially affect
their design and the outcome of use. The challenges related to the cost and characteriza‐
tion for the purpose of facilitating correlation of different physical properties and mor‐
phological heterogeneities will be presented. The need for advanced characterization and
analytical tools (such as spectroscopy and microscopy) shall be dealt with. This should
pave the way in the critical understanding of how better permeation studies can be ach‐
ieved from suitable biopolymer--based personal protective garments (PPGs). The reutili‐
zation of waste materials in the production of multilayered functional protective
materials (MFPMs) or composites (MFPCs) have advantages to the economy, environ‐
ment, and technology. The synthesis of targeted multi-layered metal-organic doped poly‐
mers via surface modification can be achieved in well planned experiments to yield
products of acceptable permeation studies for industry use in the manufacture of PPGs
and hence boost the third generation economy. The simple biopolymer preparation yet
robust with intuitive practical applications in the industry will explore a strong scientific
elucidation of mechanisms to explain or achieve the desired properties while overcoming
the boundary of expensive needs for the development of the industry.
Keywords: Polymers, cellulose, functionalization, multilayer, personal protective gar‐
ments, toxic chemicals, characterization, spectroscopy , microscopy
1. Introduction
According to Wang et al. [1], it has been documented that a fast depletion rate of non-renewable
energy and environmental pollution caused by synthetic or petroleum-based polymers has
motivated the utilization of naturally occurring polymers leading to the creation of a wide
range of new materials with interesting physicochemical, mechanical and morphological
characteristics. Cellulose [2] forms the structural component of the cell walls of plants and is
by far the most abundant natural polymer (polysaccharide) on earth. Cellulose provides many
manufactured products, including paper and paper products, rayon, linen, and cellulose
nitrate (a constituent of nail polish). This natural abundance offers cellulose an attractive
attention due to its renewability, wide availability, low cost, biocompatibility and biodegrad‐
ability [1]. Cellulose acetate and rayon are known examples with many day-to-day applications
ranging from thin-films to regenerated cellulose for particular usage such in packaging
materials, e.g. cellophane. Rayon is the most important regenerated natural fiber [3], produced
from cellulose derived from wood pulp. Cellulose acetate [4] has been widely produced from
processed wood pulp (Figure 1) dictating the current market source with intense research
focused on various other renewable materials as feedstock [5-7].
Cellulose can also be degraded with NaOH followed by carbon disulfide reaction to form
cellulose xanthate and regenerated through precipitation in an acid medium- and then cold
drawn to form spinnerette fibers for specific usage. Regenerated cellulose materials endowed
with different functions and properties have been designed and fabricated in different forms,
Recent Advances in Biopolymers
146

such as filaments, films/membranes, microspheres/beads, hydrogels/aerogels and bioplastics,
for various applications and use in day-to-day demands. In this regard, the process of
regeneration follows a physical process resulting in a number of novel regenerated cellulose
materials employed for wide applications in textiles, packaging, biomedicine, water treatment,
optical/electrical devices and agriculture and food materials. The ‘ease-of-car’ properties such
as crease resistance can be imparted to cellulose by various cross—linking agents [3]. The most
common are di-(N-hydroxymethyl) ureas. In the presence of Lewis acid, these reagents bridge
hydroxy groups on adjacent polycellulose chains as shown in reaction scheme 1.
Scheme 1. Bridging of hydroxy groups on adjacent polycellulose chains [3].
However, many processes have been developed to improve the fiber characteristics of
cellulose. For example, treatment with strong aqueous NaOH (mercerization) alters the
strength, surface character, and dyebility of cellulose during manufacturing.
Another interesting research area that expands its scope of development mainly in the fields
of tissue engineering for many years is in the processing of organic-inorganic hybrids and
photoactive polymer nanocomposites. In this area, processing strategies with very strong
scientific interest and several applications in the nanocomposites field are based on the
development of interpenetrating networks and sol–gel processed materials [9-16]. Other
processing strategies of polymer nanocomposites that should be mentioned here include the
microwave-assisted processes [17, 18], frontal polymerization [19-24] and processing of foams
[25, 26] and aerogels [27-29]. In all these processes, the presence of nanofillers and the inter‐
action with the matrix represent again relevant factors for the processing behavior and the
final properties of the nanocomposites obtained, which can be exploited in the manufacture
of protective polymeric materials such as personal protective garments (PPGs).
Amidst all these recent advances in biopolymers, including functional biomaterials, their
usage for the manufacture of personal protective garments (PPGs) or equipment (PPE) have
dramatically improved their efficiency and performance. Thus from the research point of view,
Figure 1. Reaction scheme for the synthesis of cellulose acetate - a modified natural polymer [8].
Spectroscopic Characterization of Multilayered Functional Protective Polymers via Surface Modification with Organic...
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generating wide impact and benefits of the regenerated cellulose materials to the society. Good
and acceptable permeation characteristics, mechanical strength, and durability are common
attributes of these materials simultaneously without compromise for their cost-effectiveness
and manufacturability. The comprehensive characterization of these materials and specimens
three-dimensionality with the endeavor to obtain highest resistance to highly toxic agents such
as nuclear, chemical and biological warfare agents is the must fulfilling aim in today’s global
interest in the continuous development in this area.
The reutilization of waste materials in the production of multilayered functional protective
materials (MFPMs) or composites (MFPCs) has advantages to the economy, environment, and
technology. The synthesis of targeted multi-layered metal-organic doped polymers via surface
modification can be achieved in well planned experiments to yield products of acceptable
permeation studies for industry use in the manufacture of PPGs and hence boost the third
generation economy. The simple biopolymer preparation yet robust with intuitive practical
applications in the industry will explore a strong scientific elucidation of mechanisms to
explain or achieve the desired properties while overcoming the boundary of expensive needs
for the development of the industry. Apart from the ‘green’ methodologies of material
processing and the resultant properties and functions, with emphasis on the regenerated
cellulose materials and the composite materials, this chapter also emphasizes other composite
blending procedures. Wang et al. [1] reported that the latter processes followed new intensive
developments resulting in environment-friendly biopolymerization steps. This avoided
consuming chemicals because most of the agents (solvents, coagulants, etc.) may be recycled
and reused, with no accompanying chemical reaction. These authors pointed out that regen‐
erated cellulose varies in different shapes, such as powder, fibers, films, hydrogels, and
spheres, especially the applications of ‘green’ cellulose solvents in dissolution and regenera‐
tion, leading to sustainable development, environmental preservation and energy conserva‐
tions.
Although new polymers have been developed from complex polymeric blends, generally
through multilayered linkages, for the purpose of improving their surface function and
performance, their molecular self-assembly has proportionately led to very complex organic
and inorganic molecular interactions at even nanoscales [30]. Hence, the understanding and
control of such materials during the manufacturability of protective equipment, including
personal protective garments (PPGs) have been impeded by difficulties in their characteriza‐
tion using conventional analytical techniques [31]. Various state-of-the-art spectroscopic and
hyphenated techniques are currently available for both qualitative and qualitative character‐
izations of polymeric protective materials (PPMs) to directly resolve nanoscale morphology
and associated intermolecular interactions for the systematic control of functionality in
multicomponent systems and manufacturability. These include, but not limited to techniques
such as:
1. Scanning electron microscopy coupled to X-ray dispersive spectroscopy (SEM/EDS) for
surface imaging [32-35] and structural elucidation.
2. Atomic force microscopy (AFM) [36] and scattering-type near-field optical microscopy
[37, 38] for nanoscale morphology and nanoscale-resolved subsurface imaging.
Recent Advances in Biopolymers
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3. Scanning tunneling microscopy (STM) [39] for associated intermolecular interactions.
4. Attenuated total reflectance Fourier transform spectroscopy (ATR-FT-IR) [40, 41].
5. Infrared spectroscopic ellipsometry [42] and nano-FTIR absorption spectroscopy [43, 44]
for apertureless near-field optical microscopy [45, 46], and infrared vibrational nanospec‐
trosocopy [47].
This chapter fundamentally addresses these challenges by first overviewing the chemistry of
an important natural polymer, cellulose, critically discussing the potential of its use to form
modifiable biopolymers (e.g. cellulose acetate polymers), doped to yield multi-layered
functional protective materials (MFPMs) or composites (MFPCs). The mention of regenerated
cellulose processing is being made. The ultimate aim of the chapter seeks to provide critical
insights into understanding the acetylation mechanisms for the enhancement of their perme‐
ation characteristics against exposure to toxic industrial chemicals, including chlorine which
is currently being used as a chemical warfare agent of choice in the Syrian conflict. MFPMs or
MFPCs are a group of materials made from a combination of fibers or polymers together with
varying amounts of additives possessing tailored physical and mechanical properties. Many
of these materials should not only be durable but must provide cost-competitive products in
the manufacturability of personal protective garments (PPGs). The key advantages and
disadvantages of available protective materials manufactured with synthetic polymers
compared to biopolymeric ones based on the objective of achieving the highest quality,
maximum protection, or both are presented. The chapter will also explain the fundamental
differences of each material and how biopolymers can potentially affect their design and the
outcome of use. The challenges related to the cost and characterization for the purpose of
facilitating correlation of different physical properties and morphological heterogeneities are
presented. This should pave the way in the critical understanding of how better permeation
studies can be achieved from suitable cellulosic biopolymer--based personal protective
garments (PPGs).
2. Overview of natural polymer chemistry
2.1. Natural polymers
Polymers are large molecules constructed by the repetitive bonding of many smaller molecules
called monomers (or monomer residues) [48]. Although synthetic polymers appear in many
forms that are familiar to the consumer, biopolymers constitute all living organisms [7].
Biopolymers are responsible for the structural and functional chemistry of all plants and
animals. The polymeric sugars, known as polysaccharides, are an important component of the
cell membranes of plants. The chemical formula of this type of sugar is illustrated in Figure 2b.
Wool is a fibrous insoluble animal protein known as keratin. In its natural form, it has an α-
keratin structure and is a classic example of the protein α-helix. A variety of groups that make
up a polypeptide provide many possibilities for inter- and intramolecular interactions.
Hydrogen bonding, steric repulsions, van der Waals attraction, and solvation contribute to the
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
(b)



(a)


Figure 2. (a) Hierarchical structure from plant to cellulose chains, Adapted from Peponi et al. (2014). (b) A strand of
cellulose (Nelson and Cox, 2013).
Recent Advances in Biopolymers
150

three-dimensional conformations of these types of proteins. The peptide bond (C-H) is the
major factor in determining peptide conformation (Figure 3). Rotations are most important at
the single bonds connected to the α-carbon atoms.
types of proteins. The peptide bond (C-H) is the major factor in
determining peptide conformation (Figure 3). Rotations are most
important at the single bonds connected to the α-carbon atoms.


Figure 3. A schematic representation of a protein α-helix showing possibility of rotations at the single bonds connected
to the α-carbon atoms, Adapted from [3, 51].
The reshaping of wool fibers usually involves the reductive cleavage of the disulfide bonds
and the formation of new cross-links involving disulfides or other groups. These cross-linking
modifications are used to impart permanent press to wool fabric (Scheme 2).
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Scheme 2. Cross-linking modifications to impart pressability to wool fabric.
The flexible protein structure of wool leads to fabric with excellent handling qualities. When
exposed to moisture and heat, the tendency to shrink creates a problem. However, blends of
wool and synthetic fibers are currently the most effective approach to shrink-resistant “wool”
fabrics.
Pure pulp from cotton (Figure 4), with the scientific name as Gossypium herbaceum spp. [52] is
widely available in the arid regions of the world, particularly Africa. This natural polymer is
very rich in α-cellulose consisting of 95 – 98% [53]. Cellulose is the most widely available
biopolymer in this class (cotton) and accounts for approximately 50 % of total linear β-1,4-
polyglucoside exhibiting a strong fibre structure that is quite versatile [54]. Cotton fibers are
also cross-linked for crease resistance by using epichlorohydrin (3-chloropropylene oxide) or
the diepoxide of butadiene. Cotton fabrics retain their strength whether wet or dry. They have
excellent wearability and are pleasing in appearance and to the touch. However, the resistance
of these fibers against toxic chemicals can be possibly improved through surface modifications.
Figure 4. A photograph of fiber from the G. herbaceum species represents the purest natural form of cellulose, contain‐
ing more than 90% of this polysaccharide [55].
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Cellulosic fibers from natural protein (silk) are most widely spread out in southern Africa, and
elsewhere [56]. Silk is a fibrous protein produced by insects, including those from sources such
as the common Bombyx mori or the wild Antheraea pernyi and Antheraea assama. The “pleated
sheet” structure of silk fibroin (Figure 5) has a repeating sequence of glycine at every other
position with alanine or serine in between. The sheet sections interact through dispersion
forces.
Figure 5. A schematic representation of silk fibroin, Adapted from [57].
The polymer chains tightly pack together in pleated sheet conformations that result in a strong
fiber. Interestingly, silk fabric does not have good wear resistance, and because of its high price
it is luxury fabric. All these fibrous materials can be very good basic raw biomaterials for
manufacturing cellulose acetate biopolymers. The cocoons of various silkworms (moth larvae),
after appropriate chemical treatment, provide the fibroin used for most silk fabric. More than
70 % of the average composition of fibroin is due to the small amino acids glycine, alanine,
and serine.
Cotton is not the only source of cellulose polymers but just one of the available sources. Non-
wood bioresources has always constituted an enormous supply potential for cellulosic
biopolymers for centuries [58] and would continue to be potentially so [59] should exploitation
follow sustainable principles. A polymeric form of glucosamine known as chitin is a major
component of the exoskeleton (shell) of many insects [3].
2.2. Cellulosic biomaterials
Cellulose, (C6H10O5)n is an organic compound (polysaccharide) with the chemical structure
presented in Figures 6A and B. This molecule is the major chemical component of the cell wall
fiber, contributing to 40 % - 45 % of the wood’s dry weight [60]. This polysaccharide is
composed of linear chains of β(1 → 4) D-glucose units held together by ß-1,4-glycosidic bonds
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(Figure 7). In bleached kraft pulps prepared from native wood, there is possibly a degree of
polymerization from 10,000 to 1,000 units [61]. The D-anhydroglucopyranose unit is endowed
with hydroxyl (-OH) groups at positions C2, C3, and C6. These groups are capable of undergoing
the typical reactions known for primary and secondary alcohols [62].
Figure 6. Molecular structure of cellulose (A): Chain of several hundred to more than 10,000 β(1 → 4) linked D-glu‐
cose units [60, 63], (B): polymeric polysaccharide [54].
On one hand, cellulose exhibits a strong tendency to form intra- and inter-molecular hydrogen
bonds via the hydroxyl groups as shown in Figure 7. On the other hand, the linear cellulose
chains tend to stiffen the entire straight chain, thus, promoting aggregation into a crystalline
structure that gives the cellulose molecule a multitude of partially crystalline fiber structures
and morphologies [60].
Figure 7. Cellulose, a 1,4’-O-(β-D-glucopyranoside) polymer, Adapted from [2, 48].
A schematic representation of a strand of cellulose (conformation Iα) showing the hydrogen
bonds (thin lines) within and between cellulose molecules [50] is illustrated in Figure 8.
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Figure 8. A schematic representation of a strand of cellulose (conformation Iα) showing the hydrogen bonds (thin lines)
within and between cellulose molecules [50].
This readily bioavailable resource thus offers a great potential for continuously applied
polymer research because, as already mentioned, it is the most abundant organic chemical on
earth. It is reported in the literature [64] that more than 50% of the carbon in plant occurs in
the cellulose support structure of stems and leaves; wood is largely cellulose, and cotton is
more than 90% cellulose. It is worth mentioning that the great strength of wood is due largely
to the H bonds between cellulose chains [57]. Cellulose is composed of long unbranched chains
from 100 to 10,000 glucose molecules. Groups of these chains, held together by the hydrogen
bonding between – OH groups on adjacent chains, are twisted into rope-like structures that
make cellulose tough and fibrous [64]. Note that the absorbent properties of cotton and paper
towels are due to capillary action and formation of hydrogen bonds between water molecules
and –OH groups on cellulose chains.
2.3. Cellulose polymers
Cellulose acetate (Figure 9) is one of the oldest man-made macromolecules used extensively
in the textile and polymer industries [63]. It has an inherent advantage in that the starting
material, cellulose (Figure 7), is a renewable natural resource [66] widely produced from
processed wood pulp (Figure 2a) dictating the current market source with intense research
focused on various other renewable materials as feedstock [5-7].
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Figure 9. Cellulose acetate molecule [4].
Cellulose acetate is currently being used in fiber or film processing; however, it has been
reported [67] to have high glass transition temperature which limits its thermal processing.
Current applications of cellulose acetate include textiles, cigarette tow, lacquers, cellulose
films, and in food packaging [68, 69]. Because it is nontoxic, it possesses a great potential to be
used in new blends for the manufacture of a variety of biomaterials with very high potential
eco-friendly characteristics. An example of such application(s) is in the manufacture of
protective materials, e.g. personal protective garments. Cellulose acetate is broadly classified
into two types:- cellulose diacetate and cellulose triacetate with acetyl values of approximately
55% (degree of substitution: 2.4) and 61% (degree of substitution: 2.9), respectively [67]. This
type of biopolymer, sourced from a variety of renewable materials could undoubtedly
revolutionize the polymer industry in just the near future owing to its versatility in chemical
modification for better physicochemical qualities.
Cellulose acetate gives fabrics a silk-like appearance [8] (Figure 8) and it can be blended easily
with fibers from other materials, providing room for the manipulation of the physico-chemical
properties for improvement via surface modification with organic polymers and/or metal-
organic supramolecules. Its texture is soft and cool against the skin, is naturally absorptive and
breathable, has good drape and is excellent at combating static cling [70]. Cellulose acetate is
also frequently used for linings in suits or coats, for formal wear including wedding gowns [71].
Two conventional acetylation techniques have successfully been employed in the fibrous and
solution processes [65] to fully acetylate purified plant-derived cellulose-based mechanical
pulp. The reaction media for acetylating pulp by the fibrous process consist of xylenes, acetic
anhydride, and H2SO4. Xylene acts as a non-solvent, diluent. Cellulose acetate is isolated from
the remainder of the acetylated components by differential solubility in dichloromethane/
methanol (9:1,v/v) [65].
Through this approach, it is possible to modify cellulosic fiber using raw materials that contain
acetyl groups capable of forming cellulose acetate polymers. Such raw materials used in the
manufacture of these types of biopolymers are usually acetic acid and acetic anhydride. Acetic
acid is one of the simplest organic acids; a main component of vinegar can be prepared
naturally or synthetically from chemical processes. Acetic anhydride is produced by combin‐
ing two acetic acid molecules with the removal of a water molecule. Thereafter, it follows a
comprehensive evaluation by measuring key physicochemical parameters characterizing the
polymer and some chemical/instrumental analyses are also conducted to complement the
physicochemical measurements in the evaluation protocol.
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Thus, the biopolymer preparation protocol is simple (Fig. 10) and entails that cellulosic fibre,
acetic acid, and acetic anhydride should be mixed together and reacted to form cellulose acetate
polymers. This process is aided by the addition of a small amount of H2SO4 which is subse‐
quently neutralized during processing. The unique properties [8, 72] of the biopolymer
(cellulose acetate) enable a great variety of end-use applications to be investigated in a number
of permeation studies against selected Industrial toxic material, nuclear, biological and
chemical agents.
O
OH
OH
OH
CH
2
OH
O
OH
OH
CH
2
OH
O
OH
OH
OH
CH
2
O
H
OO
O
OAc
OAc
OSO
3
H
CH
2
OAc
O
OAc
OSO
3
H
CH
2
OAc
O
OAc
OAc
OSO
3
H
CH
2
OAc
OO
Acetic anhydried/ H
2
SO
4
Ice bath
O
OH
OAc
OH
CH
2
OAc
O
OAc
OH
CH
2
OAc
O
OAc
OAc
OH
CH
2
OAc
OO
Hydrolysis
Acetic acid + H
2
O
n
n
n
Cellulose
Cellulose acetate
Figure 10. A simple preparation protocol of cellulose acetate polymer [73].
2.4. Biopolymers and crystallinity
A particular polymer is not made up of a single molecular species but is a mixture of macro‐
molecules with similar structures and molecular weights that exhibit some average charac‐
teristic properties. The monomer-polymer term has probably been erred since time
immemorial before humans employed it to such an advantage today. Biological macromole‐
cules are nothing more than condensation polymers created by nature’s reaction chemistry
and improved through evolution [57]. Remarkably, these molecules are today’s greatest proof
of the versatility of carbon and its kingdom of atomic partners. Polymers, therefore, do not
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crystallize in exactly the same way that “pure” compounds do. The packing of identical
molecules required to form precise crystal structures is only partially attained. Yet some
polymers have many of the physical characteristics of crystals said to be crystalline. For
example, long segments of linear polymer chains are oriented in a regular manner with respect
to another. Such crystalline regions of a polymer are referred to as crystallites [74]. Structurally,
amorphous and noncrystalline regions lie between the crystallites and constitute defects in the
crystalline structure [72].
Biopolymers that have polar functional groups show considerable tendency to be crystalline.
This would seem a positive character that favors surface modification to meet specific
demands, for example, to create “creuse” blends with considerable resistance to nuclear,
chemical and biological warfare agents. During processing and manufacturability, orientation
can be aided by alignment of dipoles on different chains. Another good example is proteins,
constituting a group of the many natural polymers that can crystallize because of their regular
helical structure. In this regard, the order imposed by hydrogen bonds is further inducement
to malleable crystallinity. Because polar groups are not, however, a necessary prerequisite to
crystallization, crystalline polyethylene and polypropylene can be prepared interlayered with
biopolymer to yield a desired strength and wearability. The van der Waals interactions
between the long hydrocarbon chains provide sufficient total attractive energy to account for
the high degree of regularity within the polymers. Sight should not be lost, though, that
irregularities such as branch points, comonomer units, and cross-links lead to amorphous
polymers. In other words, crystalline polymers usually are relatively strong and nonelastic
and have characteristic melting points, such as synthetic fibers (e.g. nylon and Dacron).
Because amorphous polymers do not have true melting points but instead have glass transition
temperatures at which the rigid and glasslike material becomes a viscous liquid as the
temperature is raised, multilayered surface modifications via organic or biopolymers can be
envisaged to enhance the functional protective properties.
Each type of protein has its own amino acid composition, specific number and proportion of
the different amino acids. The forces responsible for protein shapes (varying from long rods
to undulating sheets, baskets with deep crevices to Y-shaped blobs) are the same bonding and
intermolecular forces that operate for all molecules in nature. The –SH ends of two cysteine R
groups often form an –S-S- bond, a covalent disulfide bridge that brings distant parts of the
chain together as clearly illustrated in Figure 11 [57].
Polar and ionic R groups usually protrude into the aqueous fluid, interacting with water
through ionic-dipole forces and H bonds: sometimes securing the chain’s bends through an
acid (-COO-) R group lying near a basic (-NH3+) one to form an electrostatic salt bridge. This
allows for an enormous potential for multilayer intercalation with other functional organic
biomaterials to obtain desirable characteristics and qualities. The helical and sheet-like
segments, thus, arise from H H bonds between the C=O of one peptide bond and the N-H of
another. Other H bonds act to keep distant portions of the chain near each other. Nonpolar R
groups usually congregate through dispersion forces within the protein interior. As such,
fibrous proteins have relatively simple amino acid compositions and structures shaped like
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158

extended helices or sheets. These are key components of hair, wool, skin, and connective tissue
materials that require strength and flexibility.
Finally but not the least, spatial configurations (Scheme 3(a)) of polymer molecules have a
critical effect upon the physical properties of the polymer. The structure of natural rubber is
an example to illustrate this. In this case, three spatial arrangements can result from polymer‐
ization process:
1. Atactic, in which the configurations are random along the polymer chain.
2. Isotactic, in which the configurations at each chiral center are identical.
3. Syndiotactic, in which the configurations at each chiral center alternate.
If the polypropylene stereoisomers have been prepared, the regular structures of the isotactic
and syndiotactic polymers lead to hard crystalline materials. The random repeating configu‐
rations along the atactic polymer chain result in soft, amorphous, elastic material.
Figure 11. Schematic depiction of the forces operating in many fibrous proteins, Adapted from [57].
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.
C
HCH3
CH2
C
CH2
C
CH2
C
.
HCH3HH
CH3
CH3
(a) Atactic
.
C
HCH3
CH2
C
CH2
C
CH2
C
.
HCH3CH3HCH3
H
(b) Isotactic
.
C
HCH3
CH2
C
CH2
C
CH2
C
.
CH3HCH3CH3H
H
(c) Syndiotactic
Scheme 3: Configurations of polypropylene: (a): atactic, (b):
isotactic, and (c): syndiotactic [3].
Further processing using biopolymer copolymerization under well-
monitored conditions could further improve not only the resistance of
Scheme 3. Configurations of polypropylene: (a): atactic, (b): isotactic, and (c): syndiotactic [3].
Further processing using biopolymer copolymerization under well- monitored conditions
could further improve not only the resistance of such polymers against both toxic industrial
and chemical agents but also may not create great wearability and manufacturability.
3. Polyelectrolytic polymers
3.1. Polymeric Ionic Liquids (PILs)
Polyelectrolytes constitute a class of polymers with repeating units bearing an electrolyte
group. The main moieties of polyelectrolytes are polycations and polyanions. In an aqueous
medium, these groups are susceptible to dissociate yielding charged polymers. As such,
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polyelectrolyte properties are similar to both electrolytes in the form of salts and usual high
molecular weight polymeric compounds. Thus, polyelectrolytes are sometimes called poly‐
salts (Figure 12). However, theoretical approaches [75-77] to describing the statistical proper‐
ties of these charged macromolecules differ profoundly from those of both their electrically
neutral and synthetic counterparts [78], while technological and industrial fields exploit their
unique properties for a wide range of applications.
Figure 12. Example of a polyelectrolyte molecule, a molecule in which a substantial portion of the constitutional units
has ionizable or ionic groups, or both [77]. The chemical structures of two synthetic polyelectrolytes: To the left is
poly(sodium styrene sulfonate) (PSS), and to the right is polyacrylic acid (PAA).
As illustrated in Figure 12, PSS is a 'strong' polyelectrolyte (fully charged in solution), whereas
PAA is a 'weak' polyelectrolyte (partially charged). Like polymers, their solutions are often
viscous. Charged molecular chains, commonly present in soft matter systems, play a funda‐
mental role in determining the structure, stability and the interactions of various molecular
assemblies. Both natural and synthetic polyelectrolytes are used in a variety of industries. The
good examples to be discussed in this chapter are those of natural polyelectrolytes (e.g. liquid
cellulose). For instance, polypeptides (already discussed in Section 2.4), glycosaminoglycans,
and DNA are good examples of natural polyelectrolytes.
The main factor strongly affecting the physical properties of polyelectrolyte solutions is the
degree of charging. The dissociation of polyelectrolytes would release counter-ions directly
affecting the solution's ionic strength and the Debye length. Consequentially, other properties
such as electrical conductivity are affected.
If a polyelectrolyte completely dissociates in solution with reasonable pH values yields, it is
referred to as very ‘strong’. In contrast, polyelectrolytes that partially dissociate at immediate
pH with a dissociation constant (pKa or pKb) in the range of ~2 to ~10 are termed ‘weak’.
Electrochemically, it can be seen that, weak polyelectrolytes are not always fully charged in
solution. Moreover, their fractional charge can be modified by changing the solution pH,
counterion concentration, or the ionic strength. These properties have been exploited in several
industrial applications. The introduction of new ionic moieties, cations and anions, extend the
properties and classical applications of the polyelectrolytes. Ndibewu et al. [79] used two
locally available ionic polyelectrolytes (PP1 and PP2) to study the polymeric cementation
mechanistic types on two South African subgrade soils (black cotton soil: BCS and reddish
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chert soil: RCS) during soil composite pavement compaction processes. The compositional
physicochemical properties (pH and electrical conductivity, mS) of the two polyelectrolytes
measured by preparing a 0.03% (v/v) solution at ambient temperature are presented for
illustration in Table 1.
Ionic-lignosulfonate based
polyelectrolytes
(Stabilizers)
pH Conductivity
(mS)
Turbidity
(NTU)
Total Dissolved
Solutes
(TDS in mg/L)
PP1 4.31±0.02 1.016±0.017 0.58±0.03 0.51±0.03
PP2 3.85±0.01 0.400±0.052 1.57±0.03 0.21±0.01
Table 1. Compositional chemical-physical properties of the enzyme-based formulations measured by preparing a
0.03% (v/v) solution at ambient temperature
In this study, the authors were able to access (via infrared synchrotron light spectroscopy and
micro-imaging spectroscopy) the strength enhancement properties (plasticity index) affected
by the use of the polyelectrolytes. Although, it wasn’t possible for them to describe the exact
mechanisms through which polyelectrolytes achieved this kind of polyelectrolytic polymeric-
enhanced surface networking, new molecular and complex bonding rearrangements were
prominent in more performing microcrystalline formations (Figure 13), demonstrating the
polymer character of this important group of natural polyelectrolytes.
PILs have many applications, mostly related to modifying flow and stability properties of
aqueous solutions and gels. For instance, they can be used to destabilize a colloidal suspension
and to initiate flocculation (precipitation). These properties, if so well desirably monitored, can
yield very interesting sought properties obtained from blends with their synthetic counter‐
parts.
Mecerreyes [78] in his review article has discussed the two main approaches for synthesizing
ionic liquids (Figure 14) or polyelectrolytes, named polymeric ionic liquids (PILs) in analogy
to their monomeric constituents. This author listed a few examples herein included: cations
such as imidazolium, pyridinium, and pyrrolidonium and anions such as hexafluorophos‐
phate, triflates, and amidotriflates. These new liquid macromolecules are now giving rise to a
new family of functional polymers with particular properties and new applications. The first
part of this chapter has focused on the renewable sources of these PILs while synthetic aspects
of PILs and the main aspects related to their physico-chemical properties are being discussed.
There are a few technological applications of these polymers, namely: polymer electrolytes
used in electrochemical devices, use as building blocks in materials science, nanocomposites,
gas membranes, innovative anion-sensitive materials and smart surfaces. There are also a
countless set of applications in different fields such as energy, environment, optoelectronics,
analytical chemistry, biotechnology and catalysis. It would be interesting to explore other
possibilities targeting their synthesis and blends in the manufacture of personal protective
materials.
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The potential use of PILs in blends or complex composites of new clothing with high resistance
against nuclear, chemical and biological agents is because PILs can potentially impart a surface
charge to neutral particles, enabling them to be dispersed in aqueous solution or mixtures
(superplasticizer). Elsewhere, they are often used as thickeners, emulsifiers, conditioners,
clarifying agents, and even drag reducers. They are used in water treatment and for oil
recovery. Many soaps, shampoos, and cosmetics incorporate polyelectrolytes. Some of the
polyelectrolytes that appear on food labels are pectin, carrageenan, alginates, and carboxy‐
methyl cellulose. All but the last are of natural origin. Finally, they are used in a variety of
protective or surface coating components, e.g. cement.
PILS are also being investigated for biochemical and medical applications exploiting the high
solubility characteristics. For example, much research currently focuses on using biocompat‐

Figure 13: SEM micrographs of (a) black soil composite specimen
(BCS), (b) stabilized with PP1 (BCS-PP1) or (c) stabilized with PP2
(BCS-PP2) and (d) red chert soil composite specimen (RCS), (e)
stabilized with PP2 (RCS-PP1) or (f) stabilized with PP2 (RCS-PP2)
[79].

PILs have many applications, mostly related to modifying flow and
stability properties of aqueous solutions and gels. For instance, they
RCS BCS
Figure 13. SEM micrographs of (a) black soil composite specimen (BCS), (b) stabilized with PP1 (BCS-PP1) or (c) stabi‐
lized with PP2 (BCS-PP2) and (d) red chert soil composite specimen (RCS), (e) stabilized with PP2 (RCS-PP1) or (f)
stabilized with PP2 (RCS-PP2) [79].
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ible polyelectrolytes for applications in: implant coatings, controlled-drug release, and many
other applications. Recently, the biocompatibility and biodegradability of macroporous
materials composed of polyelectrolyte complexes have been described in which the material
is presented to exhibit excellent proliferation of mammalian cells [81]. Perhaps, the approach
to incorporate PILs into synthetic polymer blends for desired properties and characteristics
could exploit the recent processing strategies of polyelectrolyte multilayers (PEMs) utilized in
the formation of new types of materials for fuel cells. These thin films are prepared using a
technique known as the layer-by-layer (LbL) deposition. In the technique, a suitable charged
growth substrate is dipped back and forth between dilute polyelectrolyte solution baths that
are positively and negatively charged. The mechanism of polyelectrolyte deposition during
which the surface are reversibly charged is adsorption. This allows for a gradual but controlled
Figure 14. Typical chemical structures of polymeric ionic liquids [80].
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build-up of electrostatically cross-linked films of polycation-polyanion layers. This procedure
sounds feasible in creating intercalated layers in cellulose-based polymeric protective gar‐
ments of any controlled thickness to stop the penetration of toxic or chemical agents. The
advantage is that thickness control of such films down to single-nanometer scale maybe
possible. LbL films can also be constructed by substituting charged species such as nanopar‐
ticles or clay platelets [82] in place of or in addition to one of the polyelectrolytes. LbL
deposition has also been accomplished using hydrogen bonding instead of electrostatics.
Another interesting avenue to explore in this regard could be polyelectrolyte adsorption.
The main benefits of using water-based processes in PILs-cellulose-based garment manufac‐
turing would be reasonably less costs, the utilization of particular chemical properties of the
film for further modification, such as the synthesis of inner surface metal-organic, nanoparti‐
cles, or porosity phase transitions to create anti-reflective coatings, chemical shutters, and
superhydrophobic surface coatings with environmental benefits to biodegrade.
As illustrated in Figure 14, Mecerreyes [80] has also reported that PILs present some of the
unique properties of ILs (ionic conductivity, thermal stability, tuneable solution properties and
chemical stability) together with the intrinsic polymer properties that are unique. This
uniqueness is premised on the ground that most PILs are not soluble in water but in polar
organic solvents. This is in contrary to classic polyelectrolytes, usually water soluble while
dissociating in aqueous solutions and making the polymers charged to form polysalts. This is
due to the hydrophobic character of the counter-ion and the reduced columbic interactions.
Thus, the preparation of inorganic–organic nanocomposites/polymeric blends offer a potential
route for producing functional materials that combine the best features of inorganics (e.g.
improved mechanical strength, thermal stability) with the properties of PILs.
4. Functional protective materials
4.1. Functional polymers
Because the relatively high persistence length of the cellulose molecular chain conformation
and their close packing through numerous hydrogen bonds have made the dissolution of
cellulose - a difficult process, the development of new polymeric compounds (e.g. regenerated
cellulose) using environment-friendly low-cost solvents for cellulose regeneration is essential
for the successful utilization of the cellulose as a component of polymeric materials with a wide
applications including the use in the manufacture of protective materials such as PPGs.
Regenerated celluloses have drawn attention owing to their ease to be fabricated. Also, they
are biocompatible and biodegradable while thermal and chemically stable.
It should be noticed, though that there is still some persistence difficulty in dissolving this
natural polymer thus widening the field of current research into using them in preparing
“green” solvents for further polymerization processes.
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The different solvents used in the preparation of regenerated cellulose confer to the regener‐
ated newer functional properties (physicochemical and mechanical). These solvents have been
extensively discussed elsewhere by Wang et al. [1]. It is worth mentioning a few of these
solvents here including: N-methylmorpholine-N-oxide (NMMO), LiCl/N, N-dimethylaceta‐
mide (LiCl/DMAc), NaOH aqueous solution, alkali/urea, NaOH/thiourea aqueous solution,
and tetra butyl ammonium fluoride/dimethyl sulfoxide system.
5. Toxic industrial chemicals and their potential use by terrorists
5.1. Toxic industrial chemicals
The industrial revolution brought prosperity and improved quality of humankind, along with
it the use of chemicals and complex technologies. As a result, industrial chemicals are produced
in large quantities, transported and stored for making petroleum, textiles, plastics, fertilizers,
pesticides, herbicides and other products for peaceful use [84]. Some of these chemicals such
phosgene are utilized for making isocyanates, perfumes and fumigants; cyanogen chloride for
making herbicides, dyes and vitamins; and hydrogen cyanide for making plastics, pesticides
and sanitizers. Phosgene and cyanogen chloride were used during World War II as chemical
weapons. These served to illustrate that some of these industrial chemicals are toxic. According
to some researchers [84-86], a substance is toxic if it has a median lethal concentration (LC50)
in air of more than 200 parts per million (ppm) but not more than 20 mg/L of mist, fume or
dust when administered by continuous inhalation for 1 hour (or less, if death occurs within 1
hour) to rats weighing between 200 and 300 g. It should be noted that the toxic effects of
chemical, biological, radiological, nuclear, explosive and other toxic industrial chemicals
(TICs) are dose dependent and depends on the mode of exposure such as inhalation through
the lungs, ingestion, injection through puncture and absorption through skin.
Interestingly, a substantial use of chemicals is essential to meet the social and economic goals
of the world community,, and today's best practice demonstrates that chemicals are used
widely in a cost-effective manner and with a certain degree of safety. However, past events
such as the 1984 accidental release of methyl isocyanate in Bhopal, India, resulted in 3 000
deaths [87] and according to Sohrabji [88], it contaminated underground water within a 3.5
km radius around the affected industrial buildings. The recent Tianjin hazardous chemical
storage facility explosions [89] on the 23 August 2015 resulted in 123 people confirmed to have
died and another 50 reported to be missing and most of them being fire fighters. This incident
has demonstrated that more work need to be done, to ensure the environmentally sound
management of toxic chemicals within the principles of sustainable development. According
to the United Nations Environment Programme (UNEP) Agenda 21 [90], there are two
challenges, particularly in developing countries, which are: (a) a lack of sufficient scientific
information for the assessment of risks associated with the use and storage of a large number
of chemicals, and (b) a lack of resources for the assessment of chemicals for which data are
available. However, countries such as Germany, Switzerland and China [91], in partnership
with the International Co-operation and Assistance Division of the Organisation for the
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Prohibition of Chemical Weapon Convention (OPCW) are addressing some of these challeng‐
es. They are developing and implementing program such as ‘Promoting Chemical Safety
Management Training’ [92] and the internship program in organic chemistry, respectively,
which are aimed at developing skills of personnel from developing countries.
In the current political situation, many governments of the world are afraid that if some of
these toxic industrial chemicals fall on the hands of terrorist, or deliberately released, they may
have some serious effects on the exposed individuals. A detailed list of toxic industrial
chemicals was compiled by International Task Force 25: 1998 Industrial Chemicals Final Report
1998 [93]. As an example, chlorine is commonly used in water treatment facilities, and paper
and cloth manufacturing industries and it is often transported by road. According to the United
Nations Security Council, Report No. S/2007/314, insurgents in Iraqi have increasingly used
chlorine in improvised devices for the purpose of harming unprotected people. Historically,
chlorine was used by Germans in 1915 [94, 95] against the British forces, and it was released
against the military in Iraq in 2007. Furthermore, chlorine has attracted some attention in both
the Syria and Iraqi conflicts, where the parties involved are accusing each other of using
chlorine gas as a chemical weapon [94].
5.2. Chemical and biological warfare agents
Chemical warfare agents (CWAs) are chemical substances, whether gaseous, liquid or solid,
which are used because of their direct toxic effects on humans, animals or plants. In military
operations, CWAs are intended to kill, seriously injure, or incapacitate the victims and are
particularly effective because of their extremely high toxicity [85, 97]. They have been classified
into nerve, blister or vesicants, choking or lachrymators, blood, tear, vomiting and incapaci‐
tating agents [98] based on mode of their effect on humans [99].
Dr Gerhard Schrader of I.G Farben in Germany discovered the nerve agents in the 1936 [100].
The first nerve agent to be discovered was Tabun, followed by Sarin and Soman, their chemical
structures are shown in figure 15.
Figure 15. Selected nerve chemical warfare agents.
More ominously, governments such as those of Germany, Britain, the United States, the former
U.S.S.R and Japan invested in the development of delivery system technology comprising
artillery shells, unguided gas rockets and the Mark 116 ‘Weteye‘ air- dropped gas bombs [101].
The Chemical Weapon Convention (CWC) prohibits the development, production, stockpil‐
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ing, and use of chemical weapons, except for the purpose not prohibited by the CWC such as
industrial, agricultural, pharmaceutical and other peaceful purpose [102].
The most widely published chemical terror incident involving nerve agent Sarin occurred in
Japan [103]. A Japanese religious doomsday sect used Sarin against unprotected people in
Matsumoto resulting in the death of seven people [104]. Sarin was again used in terror attack
by the same religious sect on 20 March 1995 Tokyo subway resulting in approximately 5 500
people seeking medical attention [105, 106]. Unfortunately, the first responders also become
victims. Seemingly, the terror attack with CWAs seems to be an on-going activity in Syria,
where multiple incidents involving Sarin gas were reported and some investigated by the
OPCW [107-109]. The most disturbing threat according to Almemar [96] is the increasing
amount of evidence of chlorine gas attacks, by the Islamic State of Iraq and Syria (ISIS) in Iraq
and Syria against Kurdish Peshmerga.
Biological warfare agents refer to the military or terrorist employment of microbial or other
biological agents such as bacteria, viruses, fungi and toxins to intend or inflict death, temporary
incapacitation or permanent harm in humans, animals and plants [110]. This is important in
case of filoviruses, Marburg and Ebola; both these agents pose a serious threat as lethal
pathogens and their use by terrorist will results in fear and panic [111]. Contemporary
biological warfare has its roots in World War I and the post-war era. According to Guillemin
[110], the German military spy agents mounted an international sabotage by infecting horses
and mules that were being shipped to Britain and France with glanders and anthrax from
neutral nations such as the United States, Norway, Spain and Romania. This resulted in entire
shiploads of animals being sick and killed. After the tragic terror events of 11 September 2001
in the United States, an unknown perpetrator mailed four letters containing Anthrax spores
to unsuspecting victims in Florida, New York and two senators in Washington DC [112]. As a
result, 5 of the victims eventually died of inhalation of anthrax wheras 17 others who contracted
a cutaneous form of the diseases were successfully treated [112].
Similar to chemical agents, governments around the world are worried that if some of the
biological agents, such as anthrax, small pox, plague, tularemia, Ebola, Marburg and others,
may find their way into the hands of terrorists, such attack may cause a huge economic loss
[113]. According to Aken and Hammond [114], the members of the Japanese cult, Aum
Shinrikyo reportedly tried unsuccessfully to get their hands on Ebola virus during an outbreak
of the diseases in the Democratic Republic of Congo (formally known as Zaire) in the early
1990s. They attempted using a complex published method for cultivating polio; however, only
highly trained experts would be able to master the technique [114]. Thus, with the current
developments in biotechnology, there is a possibility that in the near future, such groups or
interested states could theoretically, cultivate viruses in the laboratory [115].
In conclusion, perhaps the human suffering and economic impacts resulting from biological
agents were recently illustrated in West African countries (Guinea, Liberia, Sierra Leone,
Senegal and Nigeria) with the outbreak of Ebola in March 2014. As of 2 October 2014, according
to the World Health Organisation (WHO) [116], 7157 of Ebola infections and 3330 deaths were
suspected, with only 3953 infections that were positively confirmed by laboratory results.
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5.3. Protection against biochemical warfare agents
The two incidents namely: terror attack in Tokyo subway and the Ebola outbreak in West
African countries have demonstrated the importance of protecting the first responders and
health workers. In the Tokyo subway incident, it was reported [117] that the first group of
responders and health-care workers involved in the initial response were not wearing proper
personal protective equipment (PPE), and surely not knowing that a highly toxic nerve agent
was released to unsuspecting passengers. As a result, 135 of the 1364 fire department personnel
who responded to the incident experienced secondary exposure while transporting victims to
emergency facilities [118]. Lastly, some the first firefighting responders in the Tianjin series of
chemical explosions were also reported to be the victims of the secondary explosions [89].
According to Bray [111], in Africa, Ebola outbreaks resulted in a large number of infections
among health practitioners, such as doctors and nurses, mainly because of the inability to
employ proper infection control measures, such as proper use of gloves, gowns and masks.
Furthermore, people handling the deceased, conducting funerals, traditional healers, mid‐
wives, mothers, humanitarian and aid workers may also become the victims [119, 120], which
may illustrate the importance of training the above groups in the techniques of using personal
protective garments correctly.
According to DuPont [121], safe and reliable protective clothing is essential to prevent
spreading infection and protect against chemicals. They have recommended different over-
the-counter garments that are tailor-made to offer protection against biological contaminated
liquids and dust that first responders should consider.
5.4. Personal protective garments against industrial toxic chemicals
For any operation, proper protective clothing is required. However, it comes with numerous
variables to be considered such as weight, comfort, level of protection, and duration of
protection. Furthermore, it is dependent on the nature of the challenges to be encountered, for
example, CWAs or TICs. The commonly used chemical protective clothing are carbon-based
hooded suits (one- or two-piece), worn together with gloves and boots and some even wear
the carbon-based undergarments [122, 123]. Tugara et al. [124] reported that the elimination
of one or more of the ensemble components will reduce and improve weight, logistic concerns,
and cost reduction while increasing comfort. More researchers are considering alternative
materials such as membranes in the form of films, electro-spun nanofibers, super-hydrophobic
materials, fabrics and others [125, 124]. When evaluating the membranes relative to protective
clothing, the main properties to be considered for some applications, for instance, the military
would include the following: high strength, antiballistic performance, fire-retardant charac‐
teristics, vapor absorption and liquid barrier characteristics [124]. So far, the spun-bond and
melt blown non-woven materials used for protective clothing offer low cost, improved barrier
properties, impermeability to particulate matter, medium strength and comfort [124, 126, 127].
There are different types of materials used as personal protective garments (PPGs). Mostly
they are found as multilayers to provide multiple functions. The classic types of the multilay‐
ered PPGs consist of the following: (a) air-permeable materials that usually consist of a woven
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shell fabric, a layer of sorptive material (for example, activated carbon-impregnated foam or
a carbon-loaded non-woven felt), and a liner fabric. At low hydrostatic pressures, liquids can
easily penetrate permeable materials; hence the shell fabrics are usually coated with Quarpel
and other fluoro-polymers to improve liquid repellency [124, 126]; (b) semi-permeable
materials that consist of two types of membranes, the porous as well as the solution-diffusion
membranes; and (c) impermeable materials that provide better protection against TICs and
CWAs. However, because they prohibit transmission of sweat from the body to the environ‐
ment, they should be cautiously used with the appropriate microclimate cooling/heating
system (Rao, 2006; SANS 5101, 2004). Some examples of the impermeable PPGs are: 4H by the
Safety 4 Company, Tychem by DuPont [121], and CPF3 by Kappler [126,127].
Table 2. Properties of high-performance fibres used for protective clothing [128]
There has been an extensive research work conducted to improve the properties of the
materials while trying not to compromise the protection capacity. The material industry has
expanded and adventured into many alternatives that are available to meet the individu‐
al’s requirements. There are selectively permeable materials (SPMs) that have the com‐
bined properties of the impermeable and semipermeable materials; they are extremely thin,
and lightweight, and consist of flexible protective barrier materials offering resistance to
CWAs and selected TICs. Their protection mechanism is based on selective solution/
diffusion process instead of adsorption process that is used by the activated carbon materi‐
als [126, 129]. Other material types consist of self-detoxification abilities in which the agent-
reactive catalysts are incorporated to reduce the hazard by either hydrolyzing the chemical
or trapping it [124, 126].
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In general, the list of different types of PPG materials does not end here; there are many more
technologies that are also focusing on improving the protection of the PPGs. Some of these
technologies include super-repellency functions and electronic fabrics with sensors, for
example to monitor physiological parameters [125, 127]. It all depends on what functions one
chooses to focus on, ultimately for each requirement, there will be a suitable technology.
Mao [128] recently reviewed the properties of high-performance textile materials available in
the form of fiber, film, membrane and liquid (herein presented in Table 2), used for protective
clothing. These materials are reported to have exceptional mechanical, fire resistance and
chemical resistance.
6. Spectroscopy and permeation tests
6.1. Permeation tests for evaluation of chemical protective materials
Several tests for the evaluation of chemical protective materials have been evaluated [130-135].
This includes that of the mustard gas and a matrix thereof has been compiled, especially in the
textile industry [136]. However, most of the materials tested either are expensive or need
further improvement. The matrix of materials evaluated will automatically increase the chance
of developing readily available ones, also for use by civilians. The challenge remains though
in the sampling and detection systems developed so far. A variety of sampling and detection
systems have been used to meet the analytical needs of a particular testing scenario described
in detail by other authors [137, 138]. Test cell designs prescribed by standard methods have
remained basically fixed for over two decades [130, 131]. This has led to the continuous
questioning of the analytical reliability for these standard cell designs [139- 141] noticeably
with the desire for further improvement. In this regard, some authors [142] have extensively
discussed the efforts to improve current nerve guide conduits (NGCs). Their article focuses on
research to improve material selection, geometric structures, and incorporation of cells and
chemical cues. In this report, they suggested that the advanced NGC model suggested by
Hudson and Evans [143] is considered the most widely accepted based on which model the
above six major components need to be considered and integrated in an advanced NGC.
Despite all these developments, there is still a general consensus that a comprehensive
description of performance criteria for permeation test cells is lacking [144] in the literature.
This suggests that there is an urgent need to define scientifically acceptable procedures and
criteria addressing a test cell design with minimum attributes that ensure its reliability for the
evaluation of chemical protective materials. In this line of thinking, Verwolf et al. [144]
emphasized the vapor challenges as one of the more problematic than liquid permeates. These
authors state that flowing vapor streams exiting the feed side require precision in its generation
and proper monitoring of standard atmospheres of the test chemical(s). This operation is often
not an easy task. This can result in large volumes of contaminated air to be disposed of.
Furthermore, there would be the requirement of decontamination of the vapor flow path and
vent stream upon the completion of a test run. As a practical example, highly toxic compounds
such as chemical weapon agents (CWAs) could make this approach practically and economi‐
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cally not feasible or even prohibitive. Finally, the delivery of a standard vapor to the feed side
of the test material may not be taken for granted, because the transfer conduit and connectors
could interact with the analyte via sorption phenomena or via a chemical reaction, and/or
undesirable partitioning in stagnant regions.
6.2. Resistance of protective materials and spectroscopic characterization
The quality of chemical protective materials is generally judged by the breakthrough time
[145- 149]. This parameter describes the time from the beginning of the exposure until the
chemical appears on the inside of the glove [148]. As an example, the time range is from 15
minutes to more than 24 hours for different pesticides through different types of glove material
[150, 151] Furthermore, the resistance against penetration of a given toxic chemicals through
a protective material will depend on chemical-specific physico-chemical properties [128]. This
parameter is very important during manufacturability and testing or decontamination
exercise. It could be thoroughly evaluated using permeation studies [152] for various toxic
chemicals against the protective materials or personal protective garments used for this
purpose.
From most of the literature reports and published results [128], the overall outcome is that
composite materials and hybrid structures used in protective clothing and personal protection
equipment (helmet, knee protection panel, gloves, protection curtains, protection tent and
shield, etc.) would be those with unique properties, and should be highly resistant to toxic
chemicals. Continuous research should focus on the development of composite materials and
hybrid structures usually employed to provide multiple functions in addition to resistance
requirements. The results on stress–strain relationship and deformation characteristics during
development and manufacturability can no longer be over-emphasized here. This then also
places lots of emphasis on simultaneous analytical capabilities and techniques to accompany
efforts in the development of traditional protective equipment to highly desired ones such as
in the decontamination after any chemical spillage. Because the energy absorption component
seems to be important in considering the quality requirements related to the application of
most protective materials (e.g. clothing), spectroscopy would seem to be the cornerstone to be
considered for most analytical purpose. This is because qualities (aesthetic properties, clothing
comfort and human mobility) of protective materials can successfully be assessed or quanti‐
tatively evaluated employing many already discussed spectroscopic techniques in the
introduction of this chapter such as scanning electron microscopy coupled to X-ray dispersive
spectroscopy (SEM/EDS) for surface imaging and structural elucidation; atomic force micro‐
scopy (AFM) and scanning tunnelling microscopy for both morphology, and surface-resolved
property or associated intermolecular interactions; scattering-type near-field optical micro‐
scopy for nanoscale morphology and nanoscale-resolved subsurface imaging, attenuated total
reflectance Fourier transform spectroscopy (ATR-FT-IR) for functionalized surface identifica‐
tions, infrared spectroscopic ellipsometry and nano-FTIR absorption spectroscopy for aper‐
tureless near-field optical microscopy, and infrared vibrational nanospectrosocopy for
nanoscale composite network formations.
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7. General conclusion
7.1. General outlook
The general outlook is a peaceful world, free from not only hunger and poverty but wars and
natural disasters. Perhaps amongst the challenges that man must tackle to create a safer
environment is not only the need to develop new products to suit specific needs using more
sustainable technologies is his ability to solve both yesterday’s pollution that include toxic
chemicals dumps into the environment and quickly act to stop further chemical accidental
spillages. Since man is at the center of protection against nuclear and chemical attack whether
conscious or unconscious, his safety is critically important. These projects continue research
into the future focusing on developing far more performance protective materials, e.g.
polymeric materials of various composite blends with required both mechanical strength and
chemical resistance for common use and in the manufacture of personal protective equipment.
To realize this sustainable world, we are facing the emerging challenges in agriculture, forestry,
academia, government and industry. Thus, stakeholders (governments and researchers)
should find the need here to work together for the common goal. From the ‘green’ perspective,
cellulose is the most abundant natural and renewable resource, and is a prime candidate for
replacing the petroleum-based products to expand to new applications without polluting the
earth. We, as well as have indicated the inherent advantages of safety, biocompatibility and
biodegradability of cellulose owing to the fact that cellulose is intrinsically a part of plants and
animals (tunicates), and thus, a renewable biomaterial. Co-workers in their works have
demonstrated the versatility of the cellulose natural polymer. The abundance of the OH groups
endows cellulose with the affinity to inorganic/organic substances, leading to the preparation
of hybrid materials, and expanding the potential application of cellulose as a functional
material. This chapter has further expanded on the diversity and richness of regenerated
cellulose materials fabricated via physical dissolution. Numerous citations have been exploit‐
ed in putting this chapter together pointing out how in the last decades, regeneration have
been astonishing, demonstrating promising potentials in textiles, packaging, biomedicine,
water treatment, optical/electrical devices, agriculture and food fields. From one of the
literature source, the general agreement is that physical dissolution and regeneration process
are environmentally friendly by avoiding the consumption of chemicals because most of the
agents can be recycled and reused, and the nature of cellulose is retained. As a result, no
chemical reaction occurs, promising to bring another Green Revolution to the comprehensive
utilization of cellulose-like natural resources. Therefore, we herein agree to it that cellulose-
polymeric focused research impact and benefits are truly fascinating to society. This considers
the physical processes in the preparation of new materials via environment-friendly technol‐
ogies as substitution to the petroleum-based materials.
The overall outlook of functional polymers against toxic chemicals broadly discussed in this
chapter can be coined in the following problem statement ‘Explorations in cellulose (natural
polymer) as a renewable resource may improve the world to be greener and more sustainable
in the future, particularly in terms of functional polymers processing (e.g. usage in PPGs and
PPE against toxic chemicals) if current efforts encourage further investigations of cellulose-
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based materials; that will increase a deeper understanding of the new mechanisms involved
in the cellulose dissolution, regeneration and blends tunable with various applications owing
to improved mechanical strength and physicochemical properties’. To achieve these goals, a
spectroscopic and microscopic approach that combines newly developed simple to advanced
hyphenated techniques will surely provide an efficient tool to supplement the existing ones
for the assessment of structural integrity and durability of polymeric materials; and to
determine differences between designs and manufacture deficiencies towards improvement.
Sample preparation may affect the quality of results and their interpretation thus, higher-
quality results and reliability will depend on the quality and appropriate sample preparation
techniques. An understanding of the impact of sample preparation on the results is vital.
7.2. Conclusion and future perspectives
This chapter started with an overview of natural polymer chemistry with focus on cellu‐
lose and cellulose acetate. Polyelectrolytic materials, a typical class of polymeric ionic liquids
(PILs), have been discussed to stimulate interest in the cellulose polymers and regenerated
cellulose. It is herein shown how modified/functionalized cellulose employing ‘green’
procedures and strategies owe a great potential in producing new polymeric materials with
improved mechanical strength and physicochemical properties against toxic chemical
penetration. A subsection has dealt with toxic industrial chemicals and their potential treat
in terrorism or bioterrorism. In this section, emphasis has been placed on the resistance of
current protective materials to deal with this dreadful threat to world peace and develop‐
ment. Before providing an overview of the authors’ outlook on the cellulose polymers and
future research perspectives; key analytical features to supplement the understanding of both
structural and morphological integrity and the mechanisms imparting enhanced manufactur‐
ability/wearability are briefly discussed.
With no intention to claim for any exhaustive review, the chapter has attempted to provide a
broad vision on the importance of natural polymers (e.g. cellulose), their regeneration via
‘green’ routes, processing, blends via multilayering strategies that have been accomplished to
date, to stimulate the increasing interests in cellulose research and development. Advantages
and disadvantages co-exist, no matter what technologies one invents; however, it is worth
noting that the novel “green” cellulose solvents as well as the physical dissolution/regeneration
techniques open up a completely new avenue to create novel enticing materials with desired
properties and functions. The current challenge to effectively deal with any incident of toxic
chemical spillage while protecting the recue agents, as well as preventing environmental
disasters constituted the backbone of motivations to undertake this project of writing this
chapter.
In view of the literature sources reviewed in this chapter, further explorations in cellulose-
based polymeric research could give a full perspective view of the preparation of the envi‐
ronment-friendly cellulose materials and their potential use in personal protective garments
(PPGs) against nuclear and chemical agents. New cellulose functionalized materials or
regenerated solvents modified for specific properties could also add hope to decontamination
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exercises when dealing with cases of usage of chemical war agents’. On a final note, informa‐
tion provided in this chapter is far from being conclusive, but simply a calling for more research
interest and creativity into making the world a more peaceful environment if the clean-up of
toxic chemicals or decontamination of nuclear and chemical agents were dealt with effectively
using appropriate protective materials and clothing.
7.3. Recommendations
This chapter has limitations, and we apologize for any during readership. We humbly realize
that not all that the audiences would expect could be provided in such a short chapter. The
first conclusive recommendation would be further readership through the exhaustive list of
references and citations. Second, research should continue to provide in the nearest future a
validated permeation test cell(s) for many known toxic industrial chemicals and/or specific
nuclear and chemical agents of immediate treats to mankind. Moreover, research is encour‐
aged in the creation of new cellulose-based polymeric materials modified with organic/
synthetic counterparts to acquire the most desired characteristics for a wider use in protective
materials in general, and for use in the manufacture of personal protective garments (PPGs)
against toxic chemicals in particular. Testing of current materials should be done in ambient
temperatures to assess the impact of environmental factors such as humidity and air velocity
on their permeation breakthrough rates, as well as penetration resistance for specific chemicals.
Experimental challenges during permeation studies lie in the difficulty to determine exactly
the start of the chemical breakthrough. This is because of factors such as variations in the
temperature settings, the evaporation of the agent exposed and the chemical bonding and
interlocking within the material that interferes with the detection of breakthrough [136]. In
some types of materials, the permeation time is directly proportional to the material thickness,
whereas in some, the permeation time depends on the composition of the material. For
example: aluminum foil and activated carbon cloth are materials that can be used for the
manufacture of personal protective clothing and whose permeation time would depend much
on their chemical or physical composition. In view of the above, it is highly recommended to
use non-toxic chemicals for initial testing and experiments before an attempt to simulate ‘real’
situation experimental designs. Of interest would be a need to compile a world compendium
of existing polymers prepared and tested or investigated under set conditions to serve future
research purpose. A deeper understanding of the new or old mechanisms involved in the
cellulose dissolution and regeneration/processing will not only make the regenerated cellulose
materials more functional, but also more reproducible in view of their particular applications
in this particular example.
The development of new analytical capabilities, as well as new method development is
encouraged to explore the nano- and macrostructure of polymer integrity and durability.
This could be specific, starting with cellulose-based polymers or regenerated solvents. There
should be an increasing interest for investigations of the renewable resources with ‘limit‐
less’ abundance or which can be non-competitively produced. Nanostructured polymers and
nanocomposites have been gaining popularity in the last two decades due to their exciting
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bulk and surface properties. Indeed, nanocomposites based on polymeric matrices could yield
new properties of particular interest. A number of new nanoparticles with extraordinary
properties have encouraged the enlargement of the polymer markets. To name a few, carbon
nanotubes, graphenes, as well as nanoclays, nanocellulose, metals and ceramics have created
new and exciting possibilities. Unfortunately, the successful development of these new
materials would strongly depend on the scale-up of reliable processing technologies.
Organic–inorganic hybrids are also an interesting research area since many years mainly in
the fields of tissue engineering and photoactive polymer nanocomposites. This area can be
explored for the development of new interpenetrating networks through sol–gel processes.
Current industry trends in the processing of polymers focus on traditional synthetic polymers
with only targeted composite blends or nanocomposites using some particular techniques and
approaches, proprietary to industries. The modernization of processing infrastructures at
transformation companies must be encouraged to involve research, including fundamental
research, as well as collaborative research between industry-based research and development
(R & D). Technical efforts are dedicated to the modification and updating of the current
equipment and real innovations in new polymer creation and processing strategies are relevant
in conquering most challenges raised in this chapter and elsewhere.
Acknowledgements
We are indebted to the Tshwane University of Technology for their financial support to this
endeavor, courtesy of the Executive Dean of the Faculty of Science. T. E. Lefakane acknowl‐
edges Protechnik Laboratories, a Division of Armscor SOC Ltd, a division of the South African
National Defence Research and Development Board, whose financial support granted to the
mentioned author has permitted extensive laboratory investigations that generated interest‐
ing results upon which valuable insights into drafting this chapter have been partly sourced.
Author details
Peter P. Ndibewu1*, Prince Ngobeni1, Tina E. Lefakane2 and Taki E. Netshiozwi2
*Address all correspondence to: NdibewuP@tut.ac.za
1 Tshwane University of Technology, Department of Chemistry, Arcadia Campus, Pretoria,
Republic of South Africa
2 Protechnik Laboratories, Pretoria, Republic of South Africa
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