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11

The use of cotton fibers as reinforcements


in composites
S. K. BA J PA I and G. M A RY, Government Model
Science College (Autonomous), India and
N. C H A N D, Advanced Materials and Processes Research
Institute (AMPRI) (CSIR), India

DOI: 10.1533/9781782421276.3.320

Abstract: This chapter discusses the properties of cotton fibers, and their
use as a reinforcement phase in a number of polymer composites.
Factors affecting the mechanical, and other, properties of the composites
are detailed with reference to relevant studies, and the use of
compatibilizers and their means of introduction into the composites are
discussed. Particular reference is made to the biomedical uses of
polymer/cotton fiber composites, requiring further the introduction of
antimicrobial agents, and the chapter ends with a summary of the
required properties of polymer/cotton fiber composites for medical
application.

Key words: cotton fibers, acrylamide, N-vinyl-2-pyrrolidone, acrylic acid,


grafting, chitosan, alginate, silver nanoparticles, FTIR, mechanical
properties, SEM, antibacterial action.

11.1 Introduction
Cotton is the most widely used natural textile fiber in the world today. We
use it every day, for example in the clothes we wear or the furniture in our
homes. Cotton is comfortable to wear, easy to care for, and durable. It is
also an important cash crop for many countries such as China, India and
the United States. Cotton has been an important fiber since its cultivation
in the United States by colonists in the sixteenth century. Cotton has since
spread to more than 80 countries and makes up 56% of all fibers used for
clothing and home furnishings in the United States. The US alone produces
3.8 million tons of cotton a year and consumes 1.7 million tons a year [1].
Cotton can be identified by visual inspection, burn tests, microscopy and
solubility tests.

11.2 Physical properties of cotton fibers


11.2.1 Fiber length
Length is the most important attribute of cotton fiber. Fiber length is
described [2] as ‘the average length of the longer one-half of the fibers

320
© 2015 Elsevier Ltd
Cotton fibers as reinforcements in composites 321

Table 11.1 Classification of upland cotton based on


length of cotton fiber

Upper half mean length (inches) Quality

Below 0.99 Short


0.99–1.10 Medium
1.11–1.26 Long
Above 1.26 Extra long

Table 11.2 Length uniformity vs uniformity index

Length uniformity Uniformity index (%)

Very high >85


High 83–85
Intermediate 80–82
Low 77–79
Very low <77

(upper half mean length)’. This measure is taken by scanning a ‘beard’ of


parallel fibers through a sensing region. The beard is formed from the fibers
taken from the sample, clasped in a holding clamp and combed to align the
fibers. Typical lengths of upland cottons might range from 0.79 to 1.36
inches, as shown in Table 11.1.
Length uniformity or uniformity ratio is determined as ‘a ratio between
the mean length and the upper half mean length of the fibers and is expressed
as a percentage’ [2]. Typical comparisons are illustrated in Table 11.2. A low
uniformity index indicates that there might be a high content of short fibers,
which lowers the quality of a textile product.

11.2.2 Fiber strength


Fiber strength is measured in grams per denier. It is determined as the force
necessary to break the beard of fibers clamped in two sets of jaws 1/8 inch
apart [2]. Typical tensile levels are illustrated in Table 11.3. The breaking
strength of cotton is about 3.0–4.9 g/denier, and the breaking elongation is
about 8–10% [3].

11.2.3 Micronaire
Micronaire measurements reflect fiber fineness and maturity. A constant
mass (2.34 grams) of cotton fibers is compressed into a space of known
322 Biofiber Reinforcement in Composite Materials

Table 11.3 Fiber strength in grams per denier

Degree of strength Fiber strength (g/denier)

Very strong >31


Strong 29–30
Average 26–28
Intermediate 24–25
Weak <23

Table 11.4 Micronaire measurement

Cotton range Micronaire reading

Premium 3.7–4.2
Base range 4.3–4.9
Discount range >5.0

volume, and air permeability measurements of this compressed sample are


taken. These are indicative of micronaire values (Table 11.4).

11.2.4 Color
The color of cotton samples is determined by two parameters: the degree
of reflectance (Rd) and the yellowness (+b). Degree of reflectance shows
the brightness of the sample, and yellowness depicts the degree of cotton
pigmentation. The appropriate area located in a Nickerson–Hunter cotton
colorimeter diagram represents each color code. The color of the fibers is
affected by climatic conditions, impact of insects and fungi, type of soil,
storage conditions, etc. There are five recognized groups of color: white,
gray, spotted, tinged, and yellow stained. As the color of cotton deteriorates
the processability of the fibers decreases.
Work at the University of Tennessee has led to color measurement using
both a spectrometer CIE-based average color measurement and a color
uniformity measurement using image analysis to improve the accuracy and
provide additional measurement for color grading [4]. The investigators
have developed a two-color grading system using neural networks.

11.2.5 Trash
A trash measurement describes the amount of non-lint materials such as
parts of the cotton plant in the fiber. Trash content is assessed from scanning
Cotton fibers as reinforcements in composites 323

the cotton sample surface with a video camera and calculating the percentage
of the surface area occupied by trash particles. The values of trash content
should be within the range from 0 to 1.6%. Trash content is highly correlated
to the leaf grade of the sample.

11.3 Chemical and other properties of cotton fibers


Cotton is a natural cellulosic fiber and swells in a high-humidity environment,
in water and in concentrated solutions of certain acids, salts and bases. The
swelling effect is usually attributed to the sorption of highly hydrated
ions. The moisture regain for cotton is about 7.1–8.5% and the moisture
absorption is 7–8% [3].
Cotton is attacked by hot dilute or cold concentrated acid solutions.
Acid hydrolysis of cellulose produces hydro-celluloses. The fibers show
excellent resistance to alkalis. There are a few other solvents that
will dissolve cotton completely, although included among them is a
copper complex of cuprammonium hydroxide and cupriethylenediamine
(Schweitzer’s reagent [5]). Cotton degradation is usually attributed to
oxidation, hydrolysis or both. Oxidation of cellulose can lead to two types
of oxycellulose [6], depending on the environment in which the oxidation
takes place.
Cotton fibers show double refraction when observed in polarized light.
Even though various effects can be observed, second-order yellow and
second-order blue are characteristic colors of cellulosic fibers [7]. A typical
birefringence value, as shown in the table of physical properties, is 0.047.
Cotton fibers are very prone to attack by certain microorganisms, insects
and fungi that cause functional, hygienic and aesthetic difficulties. Their
tendency to promote bacterial growth is due to their moisture absorption
tendency which provides a good environment in which microbes can
develop.

11.4 Cultivation of and quality issues affecting


cotton fibers
Prior to seed planting, the ground is plowed and divided into seed rows.
Next the seeds, which have a size of about 0.5 cm, are inserted into the soil
with a mechanical planter. Irrigation causes the seed to germinate.
Cotton is grown in large monocultures and is therefore susceptible to
pests. After bloom the cotton balls become visible, each containing up to
25 seeds. After about eight weeks these balls tear open and the cotton
emerges and harvesting can begin.
When harvesting the plants are sprayed with defoliant beforehand to
minimize contamination with leaves and the freshly picked cotton is pressed
324 Biofiber Reinforcement in Composite Materials

into large modules. The cotton gin mechanically separates the fibers from
the seed and turns it into ginned cotton, which is also called lint. The lint is
pressed into large bales and transported to the textile mill. At the mill, the
bales are picked apart and cleaned again before being fed into a
carding-machine.
At this point, the fibers are laid side by side and made into an untwisted
rope called a sliver. A spinning frame turns these slivers into yarn. In the
next step, the yarn is dyed and looms are used to weave it into ready-to-use
fabrics.
One method of analyzing individual fibers is to develop an optical sensing
tool that can be used to characterize single cotton fiber quality (Thomasson
et al., [8]). Should cotton producers and processors employ the same method
of characterizing cotton fiber quality, this would maximize the efficiency of
the manufacture of cotton products.
Variations in the quality of cotton fibers exist between different areas of
a cotton field, from plant to plant, and even within the same plant. Moreover,
the quality of fibers on a single seed may vary in length, shape, thickness
and maturity as described in Jost [9]. By studying individual cotton fibers
from different parts of a seed, different plants and different locations on a
field, it may be possible to determine the causes of the variation in cotton
fiber quality (Cui et al., [10]).

11.5 Processing of cotton fibers as reinforcements


in composites
Cotton fibers are a good candidate for biomedical applications and in this
chapter we describe some of the strategies that have been adopted to
develop fiber/polymer composites and polymer-attached fibers for
biomedical applications, with particular reference to antimicrobial efficacy.
Synthetic and natural polymers can be attached to the cotton cellulosic
backbone to yield polymer-grafted fibers. The following are examples of
graft co-polymerization of vinyl monomers and natural polymers onto
cotton cellulose:

• Grafting of monomer acrylamide (AAm) and N-vinyl-2-pyrrolidone


(VP) on to cotton fibers
• Graft co-polymerization of acrylic acid onto cotton fibers
• Covalent attachment of biopolymer chitosan onto cotton fibers
• Preparation of calcium alginate attached cotton fibers.

The basic mechanism involved in graft co-polymerization onto a substrate


is illustrated in Fig. 11.1. The initiator reacts with the appropriate functional
groups of the substrate molecules to produce free radicals. Monomers then
Cotton fibers as reinforcements in composites 325

Graft polymer

Monomer unit
Initiator

Growth Polymer brush

11.1 Grafting mechanism.

NH4+ O + O– O– + O
N N
Cellulose fiber O
O O–– Ceric
base polymer + +3 O O– N
N O Ce

ammonium
O C
O– nitrate
Initiator O– + +
N N +
O O– O– O NH4
Step-I
NH4+ O + O– O– + O O
N N
O O H2C O CH2 O
OO – – Ceric H2C CH
N
+
O Ce+3
– O– N + + N
+
O C ions NH2
O– O– Acrylamide H2 C CO
+ + N N
N N + H H
O

O O– O NH4 H2C CH2
N.N' methylene
Fibers with free radicals N-vinyl-2-pyrrolidone
bis acrylamide
Crosslinker
Grafting

N
O H2N
m O n
Co-polymer
poly(AAm-co-N-vinyl-2-pyrrolidone)-grafted cotton fibers
Step-II

11.2 Grafting procedure.

attach to the free radical sites, forming macro-radicals. The build-up of


monomer units in this manner is known as graft co-polymerization.

11.5.1 Grafting of AAm and VP onto cotton fibers


Cotton fibers, when treated with ceric ammonium nitrate, generate free
radicals via proton abstraction. The free radicals are then treated with
the monomers AAm and VP which attached to these active sites, thus
forming graft chains of poly(AAm-co-VP) copolymer onto cotton cellulose
fibers [11]. This is illustrated in Fig. 11.2.
326 Biofiber Reinforcement in Composite Materials

1800 1600 1400

11.3 FTIR spectral analysis to confirm specific bindings [11].

Zinc ions are loaded into these polymer-grafted cotton (PGC) fibers by
equilibrating an appropriate quantity of dry grafted fibers in an aqueous
solution of Zn(II) ions. When the fibers come into contact with the aqueous
medium, the grafted polymer network absorbs the solution. The zinc ions
within the swollen polymer network may react with the oxygen atom in the
carbonyl group of vinyl-pyrrolidone.
A comparison of FTIR spectra of Zn(II)-loaded PGC fibers with that of
plain PGC fibers usually gives valuable information about the mode of
attachment. It was observed that the peak appearing at 1705 cm−1 for CO
group of N-vinyl-2-pyrrolidone in PGC fibers was shifted to 1633 cm−1 in
Zn(II)-loaded PGC fibers (as shown in Fig. 11.3). This indicates the binding
of Zn(II) with oxygen of the CO group of VP in Zn(II)-loaded grafted
fibers.

11.5.2 Graft co-polymerization of acrylic acid onto cotton


fibers and loading of gentamycin sulphate into
composite fibers
An acidic monomer such as acrylic acid (AAc) can be grafted onto cellulose
in order to load cationic antibiotic drugs such as gentamycin sulphate. These
cationic drugs undergo ion-exchange with free H+ ions present in the grafted
polymer network which result from the ionization of −COOH groups of
monomer AAc [12].
The percent grafting (PG) is calculated using the following expression:

Wg − W0
PG = × 100
W0
Cotton fibers as reinforcements in composites 327

+
Cellulose fibers Ce4+ + HA Ce3+ + H + A* Cell-OH + A* Cell-O* + HA

+
Cell-OH + Ce4+ Cell-O* + Ce3+ + H

Cell-O* + CH2 = CH *
Cell-O – CH2 = CH
Cell-O*
Acrylic Acid COOH COOH
PAAc - grafted fibers

11.4 Polyacrylic acid grafted cotton fibers [12].

where W0 = weight of cotton fibers before grafting procedure and Wg =


weight of grafted cotton fibers or weight of cotton fibers after grafting
procedure.
Figure 11.4 illustrates the grafting procedure of monomer acrylic acid
onto cotton cellulose.
A brief protocol of procedure is as follows. Pre-weighed cotton fibers are
placed in 10 ml of 20 mM CAN for 30 min, blotted with tissue paper to
remove extra CAN, and then immersed in 25 ml of a solution containing
pre-weighed quantities of monomer AAc and crosslinker MB. After the
grafting reaction is over, each substrate is equilibrated in distilled water to
remove unreacted salts. Finally, the grafted fibers are put in 50% methanol
solution to remove any homopolymer formed [13] and placed at 40°C in a
dust free chamber until the fibers are completely dry.
Poly(acrylic acid) grafted fibers can be readily loaded with Zn(II) ions
by equilibration. Gentamycin sulphate (GS) is a water-soluble drug with a
solubility of approximately 50 mg per ml H2O. In aqueous medium it is
present in the form of a cation:

G.SO4  G ++ + SO4−−

The poly (acrylic acid)-grafted fibers have carboxylic groups attached


along the polyacrylic acid-grafted chains with free or counter H+ ions:

fibers − COOH  fibers − COO− + H +


328 Biofiber Reinforcement in Composite Materials

CH2OH
O
O OH O Cellulose

OH
+ HIO4

CH2OH
O
O O O O Cellulose dialdehyde
C C
H OH
Chi-NH2

CH2OH
O
O O O Chitosan attached cellulose (CAC)
CH
C
N H
NH2 n NH2
HO

HO O HO O HO
O O O
HO
CH2OH CH2OH CH2OH

11.5 Chitosan-attached cotton cellulose fibers.

When grafted fibers are placed in an aqueous solution of the drug


gentamycin sulphate, ion-exchange occurs between the counter H+ ions
attached along the fibers and the G++ ions present in the aqueous solution:

COO– ·H+ COO–


+ G+ ·SO4– – G+ + + 2H+ + SO4– – …
COO– ·H+ COO–

These fibers release G++ ions into a release medium and perform antibacterial
action against antimicrobial infections.

11.5.3 Covalent attachment of biopolymer chitosan on to


cotton fibers followed by loading of copper ions
The covalent attachment of a polymer onto the backbone of cotton cellulose
fiber can also be achieved by oxidizing the cotton cellulose using an
appropriate oxidant such as periodic acid to produce cellulose dialdehyde.
These dialdehyde groups can be attached to a suitable polymer containing
NH2 groups via a coupling reaction. An example of such attachment is
illustrated in Fig. 11.5.
Cotton fibers as reinforcements in composites 329

(a) (b)

11.6 (a) Plain cotton fibers; (b) Cu(II) ion-bound chitosan-attached


fibers [14].

The biopolymer chitosan exhibits antibacterial action against a number


of microorganisms such as E. coli; however, in order to enhance its
antibacterial action the chitosan-attached cotton fibers can be further
modified by attachment of some strong antibacterial agent. For example,
Cu(II) ions can be attached to the chitosan chains as Cu(II) has a strong
tendency to bind with the NH2 groups. Cu(II)-loaded chitosan-attached
cotton cellulose fibers exhibit biocidal action against microorganisms. A
photograph of plain and Cu(II)-loaded chitosan-attached cotton cellulose
fibers is given in Fig. 11.6. These Cu(II) ions are released from the fibers
when they are brought in contact with physiological fluid [14].

11.5.4 Preparation of calcium alginate-attached cotton


fibers containing Cu nanoparticles
Bajpai and Thomas [15] attached chitosan macromolecular chains onto the
cellulose cotton backbone via oxidation to cellulose dialdehyde by periodic
acid, and the resulting cellulose dialdehyde was coupled with the chitosan
chains with elimination of water. Placing the chitosan-attached cellulose
fibers into an aqueous AgNO3 solution allows Ag(I) ions to bind with the
amino groups of the chitosan macromolecular chains. These Ag(I)-attached
fibers are then reduced with sodium citrate to yield Ag nanoparticle-loaded
chitosan-attached cotton cellulose fibers, as illustrated in Fig. 11.7.
These fabrics can be used for antibacterial applications wherever needed.
The optical images of plain, chitosan-attached and Ag-loaded fabrics are
shown in Fig. 11.8.
CH2OH CH2OH
CH2OH CH2OH
O O O
Cellulosic O OH
O
OH O O OH O
OH O
Cellulose
O CH HC CH HC
chains OH OH
Oxidation O O O O dialdehyde
by NalO4
(a) Cotton fabric

CH2OH CH2OH
CH2OH CH2OH O O
O O O OH OH O
O OH O CH HC O CH HC
OH
Cellulose CH HC O CH HC O O N O NH2
dialdehyde O O O O Coupling N H2 n OH Chitosan
with HO
OH O CH OH
O
O
HO O
O
HO chain
2 CH2OH CH2OH
(b) chitosan

CH2OH CH2OH CH2OH CH2OH


O O O
O O OH O
O OH OH O OH O
CH HC O CH HC CH HC CH HC Ag
+ Chelation of
O + O N O
O O
N H2 n
N O NH2
OH Ag –N–H n N–H OH Ag to chitosan
HO O HO O HO Reaction + HO O HO O HO chains
OH O CH OH O O Ag –O O CH OH O
CH2OH
O
CH2OH
2 CH2OH CH2OH with 2

AgNO3
(c)

CH2OH CH2OH CH2OH CH2OH


O O O O
O OH OH O O OH OH O
O + CH HC O
CH HC CH HC Ag CH HC
O+ O N O O O N O Silver
Ag –N–H n N–H OH –N–H n N–H OH
Reduction nanoparticles
+ HO O HO O HO HO O HO O HO
Ag –O O CH OH O
CH2OH
O
CH2OH with citrate –O O CH OH O
CH2OH
O
CH2OH
2 2

(d)

11.7 Matrix form of nanosilver-loaded fabric [15].


Cotton fibers as reinforcements in composites 331

(a) (b) (c)

11.8 (a) Plain fabric; (b) chitosan-attached fabric; (c) nanosilver-loaded


fabric.

β-(1-4)-D-Mannuronic Acid α-(1-4)-L-Guluronic Acid


O
M O –
OOC G
OH
COO– OH
O
O O

O O OH
HO 1
4 1 O
4

11.9 Structure of alginate.

The main drawback with the techniques described above is the loss
of mechanical strength of the fibers due to cleavage of the C2–C3
bond, limiting their applications where high mechanical strength is
required.
An alternative approach in which the mechanical strength of the
fibers is not compromised involves absorption of a biopolymer sodium
alginate into the ultra-fine pores of the cotton fibers, followed by
ionotropic gelation of alginate using divalent Cu(II) ions to produce
copper alginate/cellulose composite fibers. Here, the role of the Cu(II)
is not only to crosslink the alginate chains but also to impart antibacterial
properties to the resulting composite fibers [16] (see Fig. 11.9). This
procedure is illustrated in Fig. 11.10 and the resulting fibers are shown
in Fig. 11.11.
332 Biofiber Reinforcement in Composite Materials

Immersion in
sodium alginate

Cotton fiber Cotton fiber with alginate


(a) adsorbed on the surface

Cu(II) solution

Cotton fiber with alginate Cotton fibers with copper


adsorbed on the surface alginate on the surface
(b)
Key: Cotton fiber Alginate molecule
Egg box structure Cu(II) ion
of alginate chains

11.10 (a) Sorption of alginate chains into cotton cellulose fibers;


(b) crosslinking of alginate chains by Cu(II) ions thus forming ‘egg-
box’ cavities.

11.6 Assessing the antibacterial activity of


biomedical composites reinforced with
composite cotton fibers
Cotton fiber composites can exhibit antibacterial activity against bacteria,
viruses, fungi, etc., on introduction of appropriate antimicrobial agents.
These fibers/fabrics can be used as burn and wound dressing materials, and
for other purposes in the biomedical fields. Figure 11.12, for example,
compares the antibacterial action of Zn(II) ion loaded polymer-grafted
fibers with polymer-grafted fibers as the control. It is clear that there is
appreciable inhibition in the bacterial growth in the Petri plate supplemented
with Zn(II) loaded fibers. Similar results are obtained with cellulose fibers
loaded with alternative agents (see Figs 11.13–11.16).
Cotton fibers as reinforcements in composites 333

(a) (b) (c)

11.11 Photographs showing (a) plain cotton cellulose fibers;


(b) copper alginate–cotton cellulose (CACC) fibers; (c) nanocopper-
loaded alginate–cotton cellulose composite fibers.

(a) (b)

11.12 Photographs showing bacterial growth in the plates:


(a) containing poly(acrylamide-co-vinyl pyrrolidone)-g-fibers,
and (b) poly(acrylamide-co-vinyl pyrrolidone)-grafted-fibers
containing Zn(II) ions.

11.7 Assessing the mechanical properties of


biomedical and other composites reinforced
with cotton fibers
Cotton fibers have also been incorporated into a polymer matrix as the
reinforcement phase, yielding improved mechanical properties. In work by
Way et al. [17], PLA composites with up to 25% w/w cotton linter (CL)
loadings or up to 50% w/w maple wood fiber (WF) loadings were prepared
by melt blending. The presence of the fibers in the PLA matrix was shown
by TGA tests to improve the thermal stability of all of the PLA composites.
334 Biofiber Reinforcement in Composite Materials

(a)

(b) (c)

11.13 Antibacterial activity of drug-loaded grafted fibers: (a) plain


fiber; (b) 2% drug-loaded fiber; (c) 4% drug-loaded fiber.

(a) (b) (c)

11.14 Biocidal action of (a) plain cellulose fibers; (b) chitosan-bounded


copper attached cotton fibers (CBCAC)(2) and (c) CBCAC(4) fibers
against E. coli as studied by the zone-inhibition method (the number
in parentheses denotes the percent (w/v) concentration of aqueous
solutions of Cu(II) ions used for loading).
Cotton fibers as reinforcements in composites 335

(a) (b) (c)

11.15 Biocidal action of (a) plain fibers; (b) CACC(2) and (c) CACC(4)
fibers against E. coli as studied by the zone inhibition method (the
number in parentheses denotes the percent (w/v) concentration of
aqueous solutions of Cu(II) ions used for loading).

1.2 cm 1.5 cm

(a) (b) (c)

11.16 Photographs showing the inhibition zone of (a) plain cotton


fabric disc; (b) chitosan-attached cotton fabric disc; (c) nanosilver-
loaded 1% chitosan-attached fabric disc.

In contrast to many other natural fiber-reinforced thermoplastic composites,


where the improvement in stiffness markedly reduces the toughness, the
PLA CL and PLA WF composites offer excellent improvements in both
stiffness (with increases of up to 51 and 98% in tensile modulus as well as
56 and 123% in flexural modulus respectively) and toughness (up to 72 and
56% increase in notched impact strength respectively). DMA results
indicated that the mechanical loss factor (tan d) was decreased, suggesting
better damping capabilities were achieved with the composites.
Because of the biodegradability of poly(lactic acid), it is the most
frequently studied polymer for biomedical applications in last two decades,
and attempts have been made, from time to time, to strengthen this polymer
by incorporating suitable strengthening agents. The cotton stalks bast fiber
is a new kind of natural cellulose fiber and it possesses properties similar
to those of flax fibers. PLA is a class of biodegradable matrix material. As
flax fibers can be reinforced and then compounded with PLA, cotton stalks
bast fibers as reinforced materials and PLA as matrix can be used to make
336 Biofiber Reinforcement in Composite Materials

a kind of green and biodegradable composite in the experiment. With this


basic idea, Wu et al. [18] have recently reported results of their research
based on cotton stalk bast fibers reinforced polylactic acid biodegradable
composites. The composites were prepared by mixing, molding and cold
forming. An orthogonal experiment table including length of the fibers,
mass fraction of PLA, molding temperature and molding pressure was
devised. The tensile strength, flexural strength and impact strength were
then tested and the analysis of range and variance was carried out. The
optimal processing condition was obtained as follows: length of the fibers
was 6 mm, mass fraction of PLA was 75%, and molding temperature was
175°C and molding pressure was 12 MPa. The result showed that the cotton
stalks bast fibers reinforced PLA biodegradable composites had good
mechanical properties. Through this study, waste cotton stalks basts were
turned into useful resources and provided a kind of environmentally-
friendly composite.
Nowadays, polyurethane (PU) foams are used extensively as cushion
materials because of their superior physical properties (e.g., high tensile
strength, abrasion and tear resistance, low temperature flexibility, oil and
solvent resistance, printability) and high versatility [19]. With the increasing
quantity of PU wastes, the recycling of PU has become an urgent and
important task. Waste cotton fabric (WCF), which is derived from used
clothes and surplus from textile industries, represents another type
of environmental problem. Nowadays, most WCF is land filled or
incinerated [20].
The PLA composites were also subjected to a composting environment
in which increases in the onset of biodegradation were observed with
increasing fiber content. This is due to the fact that the fibers are more
readily mineralized than the PLA matrix. Conversely, after 90 days, the
PLA with the lowest fiber content exhibited the highest degree of
degradation due to mineralization of the matrix phase.
Wang et al. [21] undertook preparation of thermoplastic composites from
reclaimed polyurethane (PU) foam and waste cotton fabric (WCF) with the
aim of providing a cost-effective technology for recycling the two polymers.
An activated WCF ultra-fine powder was successfully prepared through a
mechano-chemical route and was used as a reinforcement to enhance the
melt processability and mechanical properties of reclaimed PU foam. The
relatively strong shearing and compression forces exerted by the pan mill
destroyed the hydrogen bonds of the WCF cellulose and released reactive
hydroxyl groups, which were beneficial to the interfacial cohesion between
the WCF and the PU matrix and the mechanical properties of the PU/WCF
composites were thus significantly improved. Similar results have been
obtained using poly(ethylene tetraphthalate) PET/cotton composites (see
Fig. 11.17).
Cotton fibers as reinforcements in composites 337

11.17 SEM micrograph of the tensile fracture surface of polyester–


cotton–kapok fabric composite [23].

(a) (b)

11.18 SEM images of the WCF powders (a) before and (b) after 40
cycles of pan milling [22].

The heat shrinkage of the composites sharply decreased with increasing


pretreated WCF content (Fig. 11.18). In this study, the mechano-chemically
activated WCF was used as a low-cost but effective functional additive for
the enhancement of the melt processability and mechanical properties of
reclaimed PU foam (Zou et al., [22]).
Plastic/fiber composites are widely used in many industries including the
aircraft, automobile, leisure, electronic, and medical sectors. The potential
advantages of natural fibers, aside from their environmental benefits, include
the abundance of raw materials from renewable resources, and low cost.
Furthermore, it is possible to obtain a higher loading of natural fibers in
plastic/fiber composites than in conventional inorganic fillers because of the
non-abrasive nature of the former.
338 Biofiber Reinforcement in Composite Materials

In a work by Kim et al. [24] the mechanical properties of polypropylene


(PP)/natural fiber composites were studied. For the natural fiber component
of the composites, cotton fiber was compared with wood fiber. The effect of
the melt index of PP on the mechanical properties of the composites was
also investigated. In order to improve the poor interfacial interaction
between the hydrophilic natural fibers and the hydrophobic matrix
PP, maleic anhydride (MAH) grafted PP (PP-g-MAH) was used as a
compatibilizer. The tensile strength of the PP/wood fiber composites was
found to decrease with increasing wt% of the wood fibers, whereas that of
the PP/cotton fiber composites showed higher tensile strength with the
addition of 20 to 30 wt% cotton fiber due to entanglement.
The use of PP-g-MAH was helpful in increasing the tensile and flexural
strengths of the PP/cotton fiber and PP/wood fiber composites, due to the
increased interaction between the fiber and PP matrixes. Similarly, Kapok/
cotton fabric has also been used as reinforcement for conventional
polypropylene and maleic anhydride polypropylene resins [25].Treating the
reinforcement with acetic anhydride and sodium hydroxide strengthens the
fabric (fibers).
Many efforts have been made to develop biodegradable materials based
on starch due to the environmental problems arising from petroleum-
derived plastics. Due to its low cost and availability as a renewable resource,
starch has been widely researched as an important raw material for
packaging, agricultural and biomedical applications. In recent work [26]
modification of thermoplastic rice starch (TPRS) was carried out using
cotton fiber or low-density polyethylene (LDPE). It was found that the
TPRS/cotton fiber and the TPRS/LDPE composites exhibited improved
mechanical properties and lower water uptake. Use of maleic anhydride
grafted-polyethylene (MAPE) and vinyl trimethoxysilane (VTMS) as
compatibilizers in the TPRS/LDPE composite improved the tensile
properties but slightly increased water absorption. The compatibilizers also
reduced phase separation in the TPRS/LDPE composites (see Fig. 11.19).
In a recent study, Navin Chand et al. [27] found that nano cellulose fibers
present in sisal fiber have been separated. The other components present
in sisal fiber such as lignin, pectin and wax were removed in the process.
These separated nano cellulose fibers were reinforced in some olefins
namely low-density polyethylene (LDPE), linear low-density polyethylene
(LLDPE) and polypropylene (PP) by the melt mixing technique.
Cellulose fibers obtained from various natural resources have also been
utilized for reinforcement of polymers. For example, separated nanocellulose
fibers derived from sisal were used to reinforce a number of olefins, namely
low-density polyethylene (LDPE), linear low-density polyethylene
(LLDPE) and polypropylene (PP) using the melt mixing technique. The
mechanical properties of the composites exhibit improved strength up to
Cotton fibers as reinforcements in composites 339

Ester linkage
Starch Starch

O O Chain entanglement O O

O C C O O C C O

CH2 CH LDPE CH2 CH2

CH CH

MAPE

11.19 Schematic diagram of interaction in TPRS/LDPE/MAPE.

(a) (b)

11.20 Optical micrographs of (a) neat PBS and (b) CSBF/PBS (20/80)
composite.

certain loading of nanofibers in the LDPE and LLDPE cases, whilst the PP
composites showed a reduction in strength with increased fiber content.
In recent decades, researches focused on biodegradable polymers have
received more and more attention due to their promising applications and
environmental considerations. One of the biodegradable polymers is
poly(butylene succinate) (PBS) synthesized by succinic acid and butanediol,
both of which can be derived from bio-based renewable resources. In a
recent work by Tan et al. [28] biodegradable poly(butylene succinate) was
reinforced with cotton stalk bast fibers (CSBF) which had been pretreated
by the continuous steam explosion method. The non-isothermal
crystallization kinetics, crystalline structure and spherulitic morphology
of neat PBS and CSBF/PBS composites were investigated by differential
scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and
polarizing optical microscopy (POM). Moreover, the dynamic mechanical
thermal properties of neat PBS and CSBF/PBS composites were studied by
dynamic mechanical thermal analysis (DMA) (see Fig. 11.20).
340 Biofiber Reinforcement in Composite Materials

11.8 Summary
The following properties are advantageous for application of polymer/
cotton fiber composites in the medical sector:
• The fibers should possess reasonably good water absorption in order to
absorb the exudates released from wounds. This can be achieved by
introducing a hydrophilic polymer by means of grafting or some other
technique. Synthetic polymers such as sodium acrylate or natural
polymers such as starch or sodium alginate are possible candidates in
this respect.
• The fibers should have good mechanical strength after attachment of
the polymer and loading of the antibacterial agent. This is usually
achieved by soaking the fibers in an aqueous solution of monomer/
polymer.

11.9 References
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