Fiber Properties TXL110

4/15/2015
TXL110
FromPolymerstoFibers
ProprietaryInformation RajivSrivastava@IITD
Why Fibers?
Fibers
Natural Man-Made (Manufactured)
Natural Synthetic Inorganic

Plants Animal Mineral (Regenerated) Polyamide Glass
Polyesters Ceramic
Cellulose Metallic
Polyacrylonitrile
Protein
Polyolefins
Polyvinyl derivatives
Asbestos
Bast leaf Seed Hair Secreted

protein
Flax Abaca Cotton Wool
Silk
Jute Pineapple Coir
Banana
ProprietaryInformation RajivSrivastava@IITD 2
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Why Fibers?
For their significantly useful properties and vast applications

Apparel: cloths etc.
Domestic: carpets, curtains, bedding etc.
Technical Textiles:
Protective textiles (bullet-proof vest)
Geotextiles (reinforcement of embankments)
Space (suits and aircraft structural components)
Medical Textiles (wound-dressing, scaffolds for tissue engineering)
Smart textiles (show reversible change in properties)
Fibers !
Hair like materials, having high aspect ratio, capable of being converted into yarns
and fabrics.
Generally have following further characteristics:
High length to diameter ratio

Strength
Flexibility
Elasticity
Moisture absorption and transmission
Dyebility
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Basic requirement to form fibers
Ensure continuity and strength along the length of fiber
Liner polymers
Long chain molecules, corresponding to long fibers that make up yarns: if the molecules or fibers are too short,
there will be loss of strength
A more or less parallel arrangement of molecules
Lateral forces to hold the molecules together and give cohesion to the structure
Some measure of molecular movement freedom to provide necessary extensibility and some openness for moisture
absorption and dye uptake
Effect of length of molecules (or fibers) on strength (a) long molecules showing cohesion (b)short molecules showing possibility of easy breakage
Basic requirement to form fibers
Characteristics of polymers influencing fiber properties
Molecular weight
Linearity
Orientation / Crystallization
Cohesion
Melting point
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Polymers Molecular Weight
High molecular weight

(long polymer molecules)
Path of break is long
(strong fiber)
Low molecular weight

(short polymer molecules)
Path of break is short
(weak fiber)
Polymers Linearity
Linear Polymer Non-linear Polymer
Linear polymers have a better chance to orient (crystallize) - fiber of satisfactory strength
and desirable properties could be obtained
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Orientation and Crystallization
Orientation
(Alignment of polymer
chains along the fiber
axis)
Organization of polymer chains in a

crystalline polymer fiber
Effect of increased orientation: Orientation also allows for greater

intermolecular forces of attraction
Increases: Strength, rigidity, gloss
Decreases: Elongation, chemical reactivity, dye absorption
Proprietary Information - Rajiv Srivastava @ IITD 9
Degree of crystallinity
More amorphous fibers are More crystalline fibers are

More absorbent Less absorbent
Weaker Stronger
More easily degraded by chemicals Less easily degraded by chemicals
More easily dyed Less easily dyed
Less rigid More rigid
Less lustrous More lustrous
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Cohesion
Intermolecular forces that provide cohesion between

the polymer chains in solid state:
Van der Waals forces Hydrogen bonds between CO-NH groups
Hydrogen bonds
Dipolar interactions
Electric dipoles in the acrylonitrile side group
Melting Point of polymer
High melting point is desirable since most textile fibers

are subjected to some form of heat treatment either
during processing or during day to day use.
High degree of crystallinity and strong intermolecular

forces of interaction are required in the polymer to
achieve high melting point.
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Starch vs. Cellulose

Starch Cellulose
Glucose form Glucose form
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ProprietaryInformation RajivSrivastava@IITD
Order and disorder in fiber structure
Percentage of disordered material in various celluloses

(on the basis of moisture uptake / density)
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Percentage accessibilities of celluloses measured by exchange of hydroxyl hydrogens for deuterium
Parameters to give reasonable specification

to fiber structure:
Degree of order
Degree of localization of order
Length / width ratio of localized units
Degree of orientation
Size of localized units
Fringed micelle structures (a) unoriented (undrawn) Molecular extent
fiber (b) oriented (drawn) fiber
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Degree of order
Mean values of some correlation function relating the position of neighboring
chains
Degree of localization of order

Measure of the spread of degree of order taken over zones a few molecule wide
Length / width ratio of localized units

More straightforward parameter, ranging from infinity (for very long
fibrils) to unity (for cubic micelles) to zero (for extensive flat sheets)
Three of many possible distributions of degree of order in a 50%

crystalline fiber (A) uniform intermediate order (B) all degrees of
Range of degrees of order of packing of molecules in a fiber order equally represented in different regions (C) mixture of highly
ordered and highly disordered regions
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Schematic representation of fibre structure in terms of three major variables
Chain orientation along fiber axis
All polymer properties are different when measured parallel to the chain axis direction versus
perpendicular to that direction (covalent bonds vs. Van de Waals or other weak interchain
bonding
Processing can deliberately or incidentally align chains in specified directions
Such alignment may results in the processed item having significantly different properties in
different directions in the item - Anisotropic
NOTE chains may be aligned and yet be completely amorphous, aligned chains are not
necessarily organized in a 3D crystalline array
In order to relate properties to orientation, whether the sample is semi-crystalline or completely
amorphous the degree of order in the sample needs to be quantified and visualized
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Chain orientation Hermans Factor
Fibres are generally used such that they are loaded along the fibre
axis thus fiber processing operations are designed to more or less
align polymer chains with fiber axis
Orientation does not imply crystallinity. Polymers can be amorphous
and yet oriented.
Herman's orientation function (f) is simply a mathematical
construction that allows us to describe the degree or extent of
orientation of the chain axis relative to some other axis of interest.
Herman's orientation function 'f' has the properties that, relative to the
direction of interest, if 'on average' the chain axis is:-
completely aligned f = 1
randomly oriented f = 0
perpendicular f = - 0.5
Polymer chains within the fiber may be organized into crystalline

and amorphous regions - the average angle between fiber axis and
chain axis may not be same in these two regions
f for chains in crystallites (fc) may be different from those in
amorphous regions (fa)
An orientation function can be used to estimate physical properties as
a function of orientation and fractional crystallinity
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Consider a perfectly crystalline (100%) sample composed Consider another 100% crystalline sample that doesnt
of chains aligned with direction of interest (fc = 1) have chains aligned with direction of interest (i.e. fc 1)
Intrinsic crystalline property difference (c) defined as If the property (P) is again measured along and
difference between property measured along the direction perpendicular to the direction of interest, the new
of interest (P) and perpendicular (P=) to it difference is given by
P - P= = c P - P= = fc (c)
Similarly, for a 100% amorphous sample, with all If another 100% amorphous sample doesnt has
chains aligned in direction of interest (fam = 1), chains aligned with direction of interest (fam 1),
the difference is now the intrinsic amorphous the new difference in property is given by
property difference (am)
P - P= = fam (am)
P - P= = am
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Consider a semi-crystalline sample, where If we assume that the property difference is linearly
fc fam 1 additive
and is fractional crystallinity P - P= = fc (c) + (1- ) fam (am)

NOTE idealized situation, crystalline/amorphous
regions have been separated and all chains in a region
are given same orientation

A very efficient way to introduce significant chain orientation in a fiber is by cold drawing (in between Tm and Tg)
If a sample draws uniformly and starts with an original length (Lx) and draws to Lx then Draw ratio (R) is
defined as Lx / Lx
If the original sample (Lx) contained unoriented chains (i.e. f = 0), then by the time this sample is drawn to 10
times its original length (i.e. Lx 10 Lx, or R 10), chain orientation in the resulting sample is such that f 1
relative to the draw direction i.e. f log R)
NOTE valid for cold drawing only. Also remember that f = 1 is the highest possible orientation that can be
produced. If R = 100 or log R = 2 and in theory f log R =2, still f = 1.
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TXL110
MoistureAbsorption
Moisture Absorption
Both axial and transverse swelling can take place
Significance Primary Factors

Comfortable Availability of Hydrophilic Groups
Easy to dye Amount of Amorphous Region
Affects dimensional stability Secondary Factors
Affects mechanical properties Humidity
Temperature
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Moisture Absorption
Availability of Hydrophilic Groups Amorphous Content
% Moisture
Amorphous Absorption (%)
at 65% RH
Cotton ~ 30 ~ 10%
Viscose ~ 40 ~ 12%
Wool ~ 70 ~ 17%
Silk ~ 35 ~ 11%
Nylon ~ 15 ~ 4%
More amorphous the fiber:

more absorbent
chemically less resistant
easier to dye
Equilibrium Absorption of Water

Humidity
Absolute Humidity (h) = mass of water in unit volume of air
Relative Humidity = (h / hs) x 100 (where hs is the absolute humidity of saturated air at same temperature)
Approach to moisture
equilibrium hysteresis
depending on whether
sample is gaining or
loosing weight
R = w/W 100
C = w/(w + W) 100 = R/(1 + R/100)
Moisture Regain (R) = (mass of absorbed water / mass of dry sample) 100
Mass of absorbed water = w
Moisture Content (C) = (mass of absorbed water / mass of wet sample) 100
Mass of dry sample = W
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Equilibrium Absorption of Water

Residual Regain
Moisture that is left in equilibrium with sample at given temperature and humidity
Permanent loss
Loss in weight due to release of substances other than water e.g. oils and waxes when sample is heated
Regain and Relative Humidity
Typical curves of regain of soda boiled cotton

against relative humidity (A) Absorption (B) Regain vs. relative humidity for various fibers
Desorption (C) Intermediate
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Effect of Temperature and Stress
Effect of temperature on absorption of cotton
Heats of Sorption
Differential Heat of Sorption (Q) (or heat of absorption)

Heat evolved when 1 g of water is absorbed by an infinite mass of material at a given moisture regain (J/g of water absorbed)
Q v = Ql + L
Where Qv is heat of sorption from water vapor and Ql is that from liquid water
L is latent heat of condensation of water in J/g at the temperature concerned
Integral heat of sorption(W) (or heat of wetting)
Heat evolved when a specimen of the material at a given regain, having a dry mass of 1 g, is completely wetted. (J/g of dry
material)
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Heats of Sorption
An integral heat of sorption defined as the heat evolved when 1 g

of dry material is raised to the given regain is used sometimes.
If we call this quantity W and let W0 be the heat of wetting from
dryness to saturation:
Variation of integral heat of sorption with regain
W = W0 - W
Theories of Moisture Absorption
(1) Effect of Hydrophilic (3) Hysteresis Molecular Explanation

Groups
Absorption of water by hydrogen bonding to hydroxyl

groups in a cellulose molecules
(2) Directly and Indirectly Attached Water
(4) Absorption in Crystalline and Amorphous Regions
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Let C = total number of water molecules/absorption site

(Eq. 1)
Ca = number of directly absorbed water molecules / absorption site
Cb = number of indirectly absorbed water molecules / absorption site
If C increase by dC, then fraction of molecules directly absorbed will (Eq. 2)

be proportional to the number of unoccupied sites
(Eq. 3)
Where q is factor of proportionality. Upon integration we obtain
(Eq. 4)
(Eq. 5)
Assuming q equal to 1 (by Peirce)
(Eq. 6)
Substitution in Eq. 1 gives
We can express C in term of regain (r) of the material, since
(Eq. 7)
Where Mw = molecular weight of water

Mo= molecular weight per absorption site = 1/3 molecular weight of glucose residue* = 54
=total mass of material/mass of absorbing (amorphous) material
(Eq. 8)
Division of regain of cotton between

two phases on Peirces Theory
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Theories of Moisture Absorption (Regain & Relative Humidity)
Indirectly attached water has greater effect on vapor pressure as it is the first to evaporate
Only a fraction (1/) of sites is effective in indirect absorption; when these are filled there is saturation
Suggested mechanism for limitation

of number of sites for indirect
absorption
(Eq. 9)
(Eq. 10)
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Eq (10) relates relative humidity with moisture absorption but a correction term should be added for evaporation
from sites with directly absorbed water that is not covered by indirectly absorbed water
The number of these sites is (1-p/p0)Ca = Ca exp(-Cb)
Assuming that they have K times the effect of indirectly attached water molecules:
or
(Eq. 11)
Substitution from Eqs. 5, 6 and 8 gives
(Eq. 12)
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Swelling
Swelling
Volume swelling related to Density and Regain
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Swelling
TXL110
TensileProperties
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Tensile Properties of Fibers
Why Tensile?
Factors determining results of tensile experiments
Material and its condition
Arrangement and dimensions of specimen
Nature and timing of the test
Instron tester
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Modulus
Slope of stress-strain curve at the origin (after removal of any crimp)
Strength at Break (Tenacity)
Force per unit linear density required to break a fiber
Expressed in g/d or g/tex (N/d or N/tex)
Elongation at Break
Amount of stretch necessary to break a fiber
Elasticity
Ability to recover after being deformed

Tensile Properties
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Work of Rupture
Ballistic Tester
Work Factor
If the fiber obeyed Hookes law, the load-elongation curve would

be a straight line and the work of rupture would be given by:
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Yield Point
Crimp
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Effect of Orientation
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Effect of Moisture
Stress-strain
plots at various
humidity levels
Effect of Temperature
Stress-strain
plots at various
temperatures
(wet fibers)
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Effect of Temperature
Stress-strain
plots at various
temperatures
(dry fibers)
Theories for Mechanical Properties
Structural Effects in Rayon Fibers
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Theories for Mechanical Properties

Effect of Orientation
Effects of orientation (a) network (b) micelles (c) fibrils
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4/15/2015

Natural Man-Made (Manufactured)

Natural Synthetic Inorganic

Bast leaf Seed Hair Secreted

For their significantly useful properties and vast applications

Generally have following further characteristics:

High length to diameter ratio

Basic requirement to form fibers

Ensure continuity and strength along the length of fiber

Basic requirement to form fibers

Characteristics of polymers influencing fiber properties

Polymers Molecular Weight

High molecular weight

Low molecular weight

Linear Polymer Non-linear Polymer

Orientation and Crystallization

Organization of polymer chains in a

Effect of increased orientation: Orientation also allows for greater

Proprietary Information - Rajiv Srivastava @ IITD 9

More amorphous fibers are More crystalline fibers are

Intermolecular forces that provide cohesion between

Melting Point of polymer

High melting point is desirable since most textile fibers

High degree of crystallinity and strong intermolecular

Starch vs. Cellulose

Glucose form Glucose form

Order and disorder in fiber structure

Percentage of disordered material in various celluloses

Order and disorder in fiber structure

Percentage accessibilities of celluloses measured by exchange of hydroxyl hydrogens for deuterium

Order and disorder in fiber structure

Parameters to give reasonable specification

Order and disorder in fiber structure

Degree of localization of order

Length / width ratio of localized units

Order and disorder in fiber structure

Three of many possible distributions of degree of order in a 50%

Order and disorder in fiber structure

Schematic representation of fibre structure in terms of three major variables

Chain orientation along fiber axis

Chain orientation Hermans Factor

Chain orientation Hermans Factor

Polymer chains within the fiber may be organized into crystalline

Chain orientation Hermans Factor

Chain orientation Hermans Factor

Chain orientation Hermans Factor

and is fractional crystallinity P - P= = fc (c) + (1- ) fam (am)

Chain orientation Hermans Factor

Both axial and transverse swelling can take place

Significance Primary Factors

Availability of Hydrophilic Groups Amorphous Content

More amorphous the fiber:

Equilibrium Absorption of Water

Equilibrium Absorption of Water

Regain and Relative Humidity

Typical curves of regain of soda boiled cotton

Effect of Temperature and Stress

Effect of temperature on absorption of cotton

Differential Heat of Sorption (Q) (or heat of absorption)

An integral heat of sorption defined as the heat evolved when 1 g

Theories of Moisture Absorption

(1) Effect of Hydrophilic (3) Hysteresis Molecular Explanation

Absorption of water by hydrogen bonding to hydroxyl

(2) Directly and Indirectly Attached Water