Class 5 - Structure of Cotton

Structure of Cotton Fiber -part 2
By: Dr. Rotich K. Gideon

Class 5
Contents
 Crystalline and orientation in cotton with respect
to fibre fine structure.
 Pore structure of cotton.
 Describing molecular shape of cotton fibre in
terms of different models.
5/8/2020 Cotton Structure 2

Crystalline and Orientation in Cotton With Respect to Fiber
Fine Structure

Cellulose Molecule to Cotton Fiber
• Polymer system
– Linear cellulose
– Average Degree of
Polymerization:
• 6,000 to 10,000
– Functional side group:-
• OH

Cellulose Molecule to Cotton Fiber

Fibrillar Orientation
• Cotton structure comprise of:-
– ‘Cuticle’ :- outermost layer, made of wax and pectic materials.
– ‘primary wall’ :- which has a crisscross structure of cellulose microfibrils.
– ‘Secondary wall’ :- layers consisting of fibrils of pure cellulose laid down
spirally about the axis of the fiber.
• Helix angle varies for different types, varieties and strains of cotton,
and dependent on environmental growth conditions at certain
critical times in the growth cycle.
• Helix angle which cellulose fibrils make with respect to fibre axis,
frequently referred to as fibrillar orientation,
• Orientation of microfibrils progressively increases from the
outermost to the inner layers.
Transmission electron micrograph of the loose tangle of cellulose microfibrils in a

cotton fiber cell wall. (Credit to Wilton Goynes.)
• Cellulose fibrils abruptly change their sense
of orientation within individual secondary
wall layers and subsequent layers.
• Freeze fractured replicas of secondary layers
in developing cotton fibers have been shown
to contain fibrils deposited in a wavy pattern
with a definite wavelength and amplitude".
– Locations where abrupt change in
orientation of fibrils takes place are
popularly called the reversals and can be
identified as dark extinction bands along
fibers when observed undercrossed
polarized light.

• Width & length of cellulose fibrils deposited
in a cotton fiber can be determine by:-
– Small-angle X-ray scattering,
– Wide-angle line broadening and
– Electron microscopic techniques.
• Elementary cellulose fibrils are 3.5 nm in
width, finer elementary fibrils of < 2 nm
width have also been claimed in native
cellulose.
• There is a differences in the microfibrillar
widths:-
– From primary and secondary walls of
cotton fibers
– From variety to variety.

Crystallinity Of Cotton

Crystallinity
 Cellulose molecules have
tendency to aggregate into
highly well-defined order
regions due to:-
 Chemical structure
 Ability to generate intra- and
intermolecular hydrogen
bonds, forces.
 These are normally known as
“crystalline regions” and
can be arranged in different
polymorphs named
• Cellulose I (Iα and Iβ), II, III (IIII
and IIIII) and IV (IVI and IVII)
Crystallinity
• Crystallinity known to influence physical Polymer system of some common fibers
and chemical behavior of cotton fibers.
• Native cellulose, irrespective of its source,
has been shown to be 60-70% crystalline
• Crystalline cellulose was detected in
developing cotton fibres during its early
stages of secondary deposition by using
X-rays.
• Most of the crystalline cellulose in mature
dried cotton hairs is confined to the
secondary growth walls.
– cellulose of primary walls is definitely
crystalline but it is that of cellulose-IV

Crystallinity
• Vanderhaart and Atalla established with solid
state NMR spectrum, that native cellulose
was a composite of two distinct crystalline
phases:- Iβ and Iα.
– Celluloses produced by primitive organisms
(bacteria, algae etc.) enriched in Iα phase
– Cellulose of higher plants (woody tissues, cotton,
ramie etc.) consists mainly of the Iβ phase
Solid State NMR spectrum
• Discovery of the crystalline dimorphism of
of cellulose Iα and Iβ
cellulose and existence of two families of native
cellulose explained the number of
inconsistencies
Crystallinity
• In recent X-ray and electron
diffraction studies, the space
group and the chain packing Triclinic unit cell
of the Iβ and Iα phases have
been characterized:-
– Cellulose Iα has a triclinic unit
cell containing one chain,
– Cellulose Iβ has a monoclinic
unit cell containing two parallel Monoclinic unit cell
chains

Crystallinity
Crystal structures
• Unit-cell dimensions of
cellulose-I crystal
– Unit cell dimensions
• a= 8.35 A,
• b= 10.3 A,
• c= 7.9 A and
• monoclinic angle ~ = 84°.
– This crystal is generally a
monoclinic and of space
group P 2

The relationship between the unit cells of monoclinic cellulose Iß and triclinic cellulose Ia

Methods for measuring crystalline forms and crystallinity of
cellulose
• X-ray diffraction
• Solid state Nuclear Magnetic Most applied
methods, generally
Resonance (NMR) spectroscopy
regarded as the most
specifically: cross-polarization magic
reliable
angle spinning (CP-MAS) 13C NMR
• Electron diffraction
• Neutron scattering
• IR spectroscopy
• Raman spectroscopy

Crystallinity of cotton fibers
• Earliest quantitative studies carried out by Mark, Kratky and Sekora, Hermans
and Weidinger.
– These early determinations of crystallinity were based on
"absolute'' methods by measuring scattered intensity fractions of
crystalline I and amorphous I, on photographic films.
• Crystallinity index introduced by Wakelin et al.
– using
• A highly crystalline hydrolyzed cotton cellulose as crystalline standard and
• A ball-milled cotton as the amorphous standard.
– This approach cannot be easily adapted in routine procedures since
they are time consuming and require standard materials.
Crystallinity of cotton fibers
• Techniques developed to measure empirical crystallinity index (CI) of native
cotton (cellulose I ). For example:-
– Segal et al (1959) developed a simple equation from X-ray diffraction (XRD),
i.e., ratio of crystalline cellulose intensity (It–Ia) to total intensity (It) at
22.7◦2θ, where Ia is the intensity of amorphous cellulose at 18◦2θ.
– O’Connor et al. (1958) used infrared (IR) spectroscopy by assigning
absorption band 1429 cm−1 to crystalline & 893 cm−1to amorphous region.
– Atalla & Vanderhart (1999) used solid state nuclear magnetic resonance
(NMR): 86–92 ppm assigned to crystalline cellulose and 81–84 ppm assigned
to disordered cellulose
– Liu et al. (2011 & 2012) developed three-IR absorption band algorithm, using
the ratio of (I708− I800)/(I730− I800), where708 and 730 cm−1represent relative
amounts of Iβ and Iα crystal forms, respectively.

X-ray diffraction (XRD) analysis
Example of XRD graph
• X-ray diffractometer is
used to get the XRD
pattern
• Crystalline index (CI)
which is the percentage
obtained by correlating
crystalline &
amorphous areas
5/8/2020 1st Yr FST - Natural fibers 20

How to calculate Crystalline index (CI)
• Peaks related to the
crystallographic planes.
• CI calculated using the expression
(2) as 47.15%, where H22.85and
H18.5are the height of the peaks at
22.85◦ and 18.5◦, respectively.
(2)
H18.5 - diffraction intensity 18.5◦ related to the

amorphous fraction
H22.85 - diffraction intensity 22.85◦ crystalline fraction.
5/8/2020 1st Yr FST - Natural fibers 21

Pore Structure Of Cotton

• Cotton fiber is hydrophilic and porous.
– Upon immersion in liquid water, cotton fiber swells and its internal
pores fill with water.
– Pure cotton holds a substantial percentage of its dry weight in water
• Pores accessible to water molecules are not necessarily accessible to
chemical agents.
– Chemical modification is required to impart many desired properties to
cotton fabric.
• Including color, permanent press, flame resistance, soil release, and
antimicrobial properties to name a few.
– Thus, a knowledge of cotton’s accessibility under water-swollen
conditions to dyes and other chemical agents of various sizes is
required for better control of the various chemical treatments applied
to cotton textiles.

• Accessibilities of cotton fibers have been
measured by solute exclusion.
– Both static techniques, glass column
chromatography and liquid
chromatography have been used.
– Series of water-soluble molecules of
increasing size are used as molecular
probes or ‘‘feeler gauges.’’
– Molecules used as probes must penetrate
the cellulose under investigation and not
be absorbed on the cellulosic surfaces.
– These include sugars of low molecular
weight, ethylene glycols, glymes, and
dextrans.
• Static measurement is based on addition of a water-
swollen cellulose to a solution of molecular probe.
– Water in pores accessible to solute dilutes solution.
• In the chromatographic techniques,
– either glass or standard liquid chromatography
columns were packed with cellulose in various forms.
– Elution volumes of molecular probes used
determined.
– Data is generally plotted as internal volume accessible
to individual solutes against their molecular sizes.
– Degree to which the internal volume has been
expanded or contracted is deduced.
Changes in Internal Pore Volume
Cellulose has been evaluated in the
forms of:-
 Decrystallized, ball-milled cotton,
chopped cotton, cotton batting, and
whole fabric.
These techniques have been used to
clarify the effects of:-
Variety , temperature, scouring–
bleaching , caustic mercerization ,
liquid ammonia treatment, cross-
linking with different agents under
varying conditions , dyeability, and
treatment with cellulases ,on the
cotton.

Describing Molecular Shape Of Cotton Fiber In
Terms Of Different Models

Model representations of fiber fine structure
• Models tended to divide into three broad types:-
• 'two-phase',
• 'continuous structure',
• 'intermediate'.
• (a) Two-phase models.

– Assumed that fibers consisted of an amalgamation of
hard, discrete and perfectly crystalline micelles
embedded in a matrix of noncrystalline (amorphous)
polymer,
– A major characteristic of this structural view was the
existence of two distinct phases, i.e. the crystals (or
micelles) and the non-crystalline polymer

(i)The fringed micelle concept.
– Because of deformation and molecular
length, the micellar theory of fibre
structure was disputed.
– Abitz and co-workers suggested that
individual molecules might pass
alternately through several micelles, and
through several intervening regions
– A major advantage of this model was that
it provided the structural continuity Individual chain molecule may
which was absent from those proposed pass alternately through ordered
earlier and disordered regions.

(ii) The fringed fibril concept.
– Hearle (1958) proposed a two-phase
structure that chains could be expected to
enter or leave a crystal at essentially any
position along its length.
– His view of the structure of a fibre
incorporated continuous 'fringed fibrils',
– This model had the advantage that it could
be applied to fibres which various
techniques revealed to possess long,
chains may enter or
needle-like features ('fibrils') as distinct
leave crystallites at
from approximately cuboidal micelles. any surface location.

(iii) Chain folding.
– More recent views of fibre structure
included the notion of chain molecules
folding back and forth on themselves.
– Keller (1957) proposed that the chains
must fold.
– The inclusion of the phenomenon in fibre
structure models was therefore a logical
progression; there are, for example,
modified fringed micelle and fringed fibril
forms which incorporate chain folding. chain folding: (a) folding in a
– Keller (1963) presents an excellent account polymer single crystal; (b)
of contemporary ideas regarding fringed fibril model
crystallinity in high polymers. incorporating some chain
folding.
(b) Continuous structure models.
• Staudinger (1932) believed that (i) Paracrystals.
 In perfect crystal, lattice spacing is precise
the molecules of high polymers
& exactly constant throughout the crystal.
would organize themselves However, suppose there is a small, random
into a single large, imperfect variation in the lattice spacing
crystal as opposed to separate The notion of order and disorder co-
small, and essentially perfect, existing is preserved, but without the need
ones. to invoke two distinct phases.
short-range order is
preserved, but
Arrangement of molecules in a long-range order
large, but imperfect, fibre crystal lost.

(c) Intermediate views.
(i) Defects.
– Fibre crystals (whether of the fringed
micelle type or not) are now thought
to contain defects analogous to
Structural disorder
those observed in other materials associated with the
such as metals — vacancies, imperfect packing of
impurities, dislocations, and so on. various-sized rods
– Among other things, defects are
thought to be responsible for plastic
deformation processes in many
crystalline fibres, since they impart
mobility to the lattice.

(c) Intermediate views.
(ii) Assembly of crystalline fibrils.
– Structural disorder need not arise from the presence of a true
amorphous material, nor even from imperfections within
crystals.
– A collection of otherwise perfect crystals would appear
disordered if they themselves were imperfectly arranged.
– Discontinuities, and possibly voids, at the crystal boundaries,
distributed over the bulk of the material, can give rise to
many of the features associated with disorder, such as the
diffuse scattering and broadening observed in X-ray
diffraction experiments on fibres.
Structure parameters

Structure parameters
• In applying knowledge of structure to the elucidation of
mechanical and other fibre properties, a more concrete
description is needed.
• For example,
– Reliable prediction of the tensile behavior of a fibre possessing a
specific structural architecture requires hard numerical data
rather than vague pictorial notions.
• Hearle and co-workers (Morton and Hearle, 1975; Hearle, 1977) devised a
scheme whereby fibre structure would be described in terms
of certain quantitative parameters.
Quantitative Parameters
1. Degree of order.
– Expresses fraction of material considered to exist in an ordered
state within the fibre structure.
– In the case of a solid polymer, the perfect crystal represents the
most efficient chain-packing arrangement possible, and the
highest density.
– On the other hand, the imperfect packing of the amorphous
chains leads to a lower density.
– Density is therefore a good indicator of the degree of order, and
is typically used as a basis for the scale upon which degree of
order is measured.

2. Degree of localization of order.
• The two-phase and continuous structure models discussed earlier
represent extreme views; in the former there is a clearly denned
ordered phase, whereas in the latter there is no such concept, and
the 'order' is deemed to permeate the entire structure in a rather
diffuse way.
• One could regard these two extremes as denning two fixed points
on a scale of localization of order'.
• Experimentally, this parameter is more difficult to deal with than the
degree of order, although it can be estimated from crystal size
measurements using, say, X-ray diffraction techniques.

3. Length: width ratio of ordered units.
– The average aspect ratio of the ordered units, specifically
with respect to the fibre direction.
– For example,
• Units could be cuboidal micelles with similar width and length.
• Alternatively, they might be long fibrils, or thin, flat lamellae.
– The measurement scale for this parameter could run from
zero for infinitely thin lamellae, to infinity for infinitely long
fibrils.
• Micelles would have a value around unity.
– This third parameter may also be estimated from various
diffraction techniques.

4. Degree of orientation of ordered units.
– Structures defined by varying degrees of orientation of the ordered
units.
– Orientation has a profound influence on most fibre properties, but
notably on mechanical properties such as modulus, strength and
extensibility.
– Estimated by using a variety of analytical techniques, including wide-
angle X-ray diffraction (WAXD) and vibrational spectroscopy.
5. Size of ordered units.
– The size of the ordered units determines the overall scale of the
structure, and is effectively a measure of its fineness or coarseness.
– It is thus analogous to the 'magnification' of the structure, and is quite
distinct from the length: width ratio.
– Any of the structures discussed so far could be imagined to exist with a
wide range of sizes.
6. Molecular extent.
– It is analogous to fibre extent in
slivers or yarns, and may apply to
either ordered or disordered chains,
or to some average over all the
molecules within the structure .
– The measurement scale for this
parameter would range from near
zero for a tightly coiled molecule, to
unity for a fully-extended one.
– The distinction between extent and
orientation must be preserved.
– It is possible to combine high
orientation and low extent on the
one hand, or low orientation and
high extent on the other. Definition of molecular extent.
7. Shape of ordered units.
– Most models say little about precise shape of
ordered units, either laterally, or when viewed in
cross-section.
– They tend to be assigned a vague cuboidal shape.
– However, certain aspects of fibre behavior will be
sensitive to whether units have, for example,
cylindrical, rectangular, or lozenge-shaped profiles.
– lozenge-shaped profiles may be appropriate in melt-
spun fibres, where the normal to the chain-fold
surface may be regularly inclined to the fibre axis.
• Such features may lead to the possibility of Structural inhomogeneities
inter lamellar shear within the structure of a coupled with skewed crystals
fibre loaded in tension. may increase shear effects

8. Relative orientation of disordered and
ordered material
– A well developed fibre would feature
equally high levels of amorphous and
crystalline chain orientation.
– However, there will be cases where the
ordered units are themselves well
oriented, but the amorphous chain
segments are essentially isotropic
• Such a combination can arise when
an initially highly-drawn melt-spun
fibre, say, is heat treated at a
temperature above its glass
transition, enabling the amorphous Combination of oriented ordered
regions to relax, and shrinkage to and unoriented disordered phases
take place.
9. Packing pattern of ordered units.
– The way in which the ordered units
themselves aggregate will play a role in the
overall fibre structure.
– Whereas a random lateral arrangement might
yield a uniformly distributed coarse-grain
structure, more regular stacking could
produce a 'pseudofibrillar' effect
– These two structures could be expected to
have differing influences on, for example, the
(a) random stacking;
mechanics of fracture in tension.
(b) regular stacking;
– A further level of detail is the extent of (c) staggered stacking
staggering of the stacks
10. Degree of linking between ordered units.
– Models emphasize the continuity and cohesion
provided by having individual molecules pass
alternately through ordered and disordered
regions.
– However, not every chain emerging from one
crystalline surface will enter another;
• Some will terminate in intervening space
between crystallites;
• others may re-enter same crystal, forming
loops;
• yet others may terminate within crystallites.
• These chain segments will contribute nothing
towards overall load-bearing capacity.
– Effective Chains are known as 'tie molecules'. Different types of chain segments
• Some may be stretched tightly between associated with the crystal-
crystallites, and it is these that will bear the amorphous boundary.
initial stress when the structure is loaded.
END

Class 5 - Structure of Cotton

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Class 5 - Structure of Cotton

Uploaded by

Copyright:

Available Formats

Structure of Cotton Fiber -part 2

By: Dr. Rotich K. Gideon

5/8/2020 Cotton Structure 2

5/8/2020 Cotton Structure 3

5/8/2020 Cotton Structure 4

5/8/2020 Cotton Structure 5

Transmission electron micrograph of the loose tangle of cellulose microfibrils in a

5/8/2020 Cotton Structure 8

5/8/2020 Cotton Structure 9

5/8/2020 Cotton Structure 10

5/8/2020 Cotton Structure 12

5/8/2020 Cotton Structure 14

5/8/2020 Cotton Structure 15

5/8/2020 Cotton Structure 16

5/8/2020 Cotton Structure 17

5/8/2020 Cotton Structure 19

5/8/2020 1st Yr FST - Natural fibers 20

H18.5 - diffraction intensity 18.5◦ related to the

5/8/2020 1st Yr FST - Natural fibers 21

5/8/2020 Cotton Structure 22

5/8/2020 Cotton Structure 23

5/8/2020 Cotton Structure 26

5/8/2020 Cotton Structure 27

• (a) Two-phase models.

5/8/2020 Cotton Structure 28

5/8/2020 Cotton Structure 29

5/8/2020 Cotton Structure 30

5/8/2020 Cotton Structure 32

5/8/2020 Cotton Structure 33

5/8/2020 Cotton Structure 35

5/8/2020 Cotton Structure 37

5/8/2020 Cotton Structure 38

5/8/2020 Cotton Structure 39

5/8/2020 Cotton Structure 42

5/8/2020 Cotton Structure 46

You might also like