8/16/2012

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Modelfibre silk,Moleculararchitecture,configuration,conformation,
Molecularmodeling
amorphousandcrystallinephases,glasstransition,plasticization,
crystallization,melting,factorsaffectingTgandTm.
Basicstructureofafibre structureoffibrils.Roleofmolecular
entanglementonfibreformation.
Formationofstructureinviscoseandthermoplasticfibres(PET,Nylon,
PP,Acrylic).Methodsofinvestigatingphysicalstructureoffibres
(WAXD,DSC,FTIR,birefringence,sonicmodulus).Moisture
absorptionproperties.Rateofmoistureabsorption,Heatofsorption,
waterretentionandswelling.Theoriesofmoistureabsorption general
view,absorptionincrystallineandamorphousregions,quantitative
theories.
Theoriesofmechanicalpropertiesofnaturalandmanmadefibres,
viscoelasticbehaviour,comparisonofpropertiesofvariousfibres.Fibre
friction.Opticalproperties,Introductiontoelectricalproperties(dielectric
propertiesandstaticchargegeneration).Thermalproperties heatsetting.
1. Physical properties of Textile Fibres- Morton, Hearle
2. Hand book of Textile Fibres Gordon Cook, Vol-1,2
3 Handbook of Fibre Chemistry Lewin Pearce 3. Handbook of Fibre Chemistry- Lewin, Pearce
1.Minor 1: 25%
2.Minor 2 : 25%
3.Quiz: 5-10%
4.Major : 40%
Attendance policy:
100% attendance is required
1) Explanation
2) Downgrading
Textile fibres
Natural Manufactured
Vegetable
Bast
Fibre
Leaf
fibre
Flax
Jute
Hemp
Abaca
Pineaple
Nut
fibre
Coir
Animal
Animal Secreted
Mineral
Asbestos
Ceramic
Cotton
Hemp
Ramie
Animal
Hair
Wool
Mohair
cashmere
Secreted
Protein
Silk
Casein
Natural Fully
synthetic
Inorganic
materials
Cellulose, Viscose
Modified Cellulosic
Acetate, triacetate
Alginate, chitosan
Polyamide
Polyester
Polyacrylonitrile
Polyolefin
PVA
Glass
Ceramic
Metallic
Apparel: Cotton, Wool, Polyester, Nylon, Silk
Domestic: Carpets, Curtains & upholsteries, Bedding
Technical textiles:
Jute, Coir, hemp, sisal: stiff
PP, PE, Nylon: hydrophobic
PLA, PGA, casein, alginate: poor stability
Technical textiles:
(a) Medical Textiles : wound dressing, sutures, scaffolds for
tissue engineering
(b) High tenacity: Tire cords, Belts, Ropes, Tents, Civil
engineering, Sail cloth
(c) Protective Textiles: Bullet proof jackets, cut-resistance fabric
(d) Smart Textiles: colour change, communication & monitoring
devices, electronics etc
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Polymers are long chains of organic molecules= Macromolecules
- Built up from smaller units called monomers
Poly = many mer = unit or part
- The nature/structure of polymers was a big question in early 1900s
Colloidal aggregates
Mysterious forces
vs
Macromolecules;
small molecules held together
by covalent bonds
Huge Debate:
Hermann Staudinger, 1920s (Nobel Prize 1953)
for his discoveries in the field of macromolecular chemistry
Paul Flory (Nobel Prize 1974): tangled behavior of polymers.
Backbone
or
Main Chain
self-assembly
understanding of these structures at intermediate length scales, organization
of the polymers, properties
DNA and RNA
Proteins
A, T, G, C (4 bases) (Sugar phosphate backbone)
22 amino acids monomers
Poly(propylene)
CH
3
Repeat
Unit Degree of
Polymerization
(DP)
Side Group
(if long side
chain)
n
chain length, different side groups, chain branching,
stereoregularity, chain flexibility, cross linking.
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Silk
Made at room temperature via self- assembly
Honeybee Wasp
OtherproducersofSilk
(leastknown)
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Glycine Alanine Serine
What is a polypeptide
Polymer of a amino acids
R O R O
H2N CH C OH H2N CH C OH
R O O
H2N CH C HN CH C OH
R
Conc
(12-15%) C, D
23-30% B
Dehydration
60%- 15%
Handbook of Fibre Chemistry
Shear stress
pH
ion conc
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Fibroin Fibroin
20~30 20~30 mm
Sericin Sericin
Silk
alanine,
glycine-alanine,
glycine-alanine-serine
primary sequences and secondary structures
Silk I: unordered structure
Silk II: crystalline -sheets: contribute to the high tensile
strength of silk fibers
-turn, helical structures: provide elasticity
Secondary structures, -helix and -sheet,
have regular hydrogen-bonding patterns.
-helix -sheet
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Primarystructure
(Aminoacidsequence)

Secondarystructure
helix,sheet

T i Tertiarystructure
Threedimensionalstructureformedbyassemblyof
secondarystructures

Quaternarystructure
Structureformedbymorethanonepolypeptide
chains
Tertiary structure Quaternary structure
Bombyx mori silkworm
Silk fibroin is a high-molecular-weight block copolymer consisting of a
heavy (370 kDa) and light (26 kDa) chain, linked together by a
disulfide bond.
The heavy chain consists of alternating hydrophobic repetitive
Nephila clavipes (spider silk)
The heavy chain consists of alternating hydrophobic, repetitive
oligopeptides, separated by smaller charged and amorphous sequences.
The hydrophobic domain is rich in alanine & glycine, while the
hydrophilic spacers give the heavy chain a polyelectrolyte nature.
The sequence of light chain is less repetitive, contains high conc of
glutamic and aspartic acid residues.
Assemblying folding packing
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Silk fibers Silk film Silk gel
Silk scaffold
Supercontractionofspidersilk
Contraction leads to changes in orientation
of molecular chains due to rupture of H
bonds and conformations
deformational energy is stored in the form
of conformational entropy
recoverable disorientation of the molecular
chains in fibres oriented amorphous region.
During supercontraction, well-defined crystalline region retains
considerable order because solvent molecules cannot penetrate
it, .. at the same time the degree of orientation in the oriented
amorphous, as well as the poorly defined crystalline regions
decreases appreciably
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During supercontraction, water plasticizes silk fibers by
breaking hydrogen bonds between polymer chains,
allowing re-orientation of silk molecules to lower energy
levels. This allows the random- coil macromolecular
regions to move rapidly to more disordered, higher
entropy configurations. This movement causes length-
wise contraction of spider silk.
During drying, silk may also contract. Reformation of
hydrogen bonds results in organization of the silk
proteins.
restores shape and tension after prey capture
Recovers from slackness of the webs
Moleculararchitecture
configuration, conformation configuration,conformation
Polymer architecture
- Microstructure: how individual monomers or atoms are arranged
- Alternating v. random copolymers
- Stereochemical configurations
- Macrostructure: how the whole polymer molecule looks like
- Significant influence on properties ---> viscosity, etc.
CH
3
CH
3
n
CH
3
n
H
Conventional View
Stereogenic
Center
Gross Fibrillar structure
CH
3
n
H H
n
H
3
C
TWO distinct configurations
- These are different configurations
Configuration : fixed relative arrangements of atoms
of a molecule in space
g
- Can not be interchanged by bond rotations
- These may seem like a small difference
- Three important classes of configurations:
-Isotactic
-Syndiotactic
-Atactic
polymer
tacticity
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- Isotactic PP:
- Regular stereochemistry
-Chains can pack closely
-Highly crystalline
-Good mechanical properties
-Tough, impact resistant
-Opaque (scattering from crystalline
regions)
- Atactic PP:
- Irregular stereochemistry
-Chains cannot pack closely
-poor packing Non-crystalline -poor packing, Non-crystalline
-Completely amorphous
-Soft & waxy
- Syndiotactic PP:
- Regular stereochemistry
Regular alternation of the side
groups promotes close packing and
crystallization
-Has in between properties
-Tough and clear
Higher orientation
High DP: Longer chains make stronger polymers
Higher orientation
greater resistance
to deformation,
greater breaking
load,
lower extension to
break.
Molecular orientation /crystallinity
All polymers are not suitable as fibres
Optimum mol wt. to get mech. propts
Adequate intermolecular forces & capacity
t i t th h l l li t to orient through molecular alignment.
Spinnability
Orientation , semi crystalline
Morphology
- crystallite size
- arrangement of crystalline & amorphous regions
- fibrillar structure etc
fibril : an assembly of molecules
Structure
fine structure
inter molecular distances
inter planes distances
molecular orientation etc
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Classification according to back bone Structure:
- There are many ways to classify polymers by their structure:
- Linear
Two end groups
Contour length
B h d - Branched
More than 2 end groups
Branch Points
branching has a substantial impact on properties: Crystallization, density,
strength, Chemical activity etc.
Hyperbranched Polymers
Many, many end groups
-Very low density materials (e.g., ULDPE: ultra-low density polyethylene)
-Fillers in resin matrix, coating, additives
- Many branches, but branching in uncontrolled or random
-Many branches, but
branching is
uncontrolled or
random
H
2
N
NH
H
2
N
Hyperbranched Polymers
N
NH
N
N
NH
HN
NH
2
HN
N
H
2
N
NH
N
NH
H
2
N
N
NH
2
N
H
H
2
N
NH
2
NH
2
Poly(ethylene imine)
H
N
n
Ring-opening
polymerization of
aziridine
Dendrimers or Dendritic Polymers
-Compared to hyperbranched polymer, Dendrimers have
PERFECT branching emanating from a core
Tree-like Branching
- Every branch point has exactly three branches
-Specific number of endgroups
-Chemical detection (dye, radionucleotide, phamaceutical), drug delivery
- Globular, 3-D structure
~ 1 to 100 nm in diameter
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Ladder Polymers:
- High thermal and oxidative stability
- Must cut at least two bonds to break a chain
- Double-stranded
Crosslinked Polymers
- Branched polymers
- If the branches link to the backbones of other polymer molecules
Crosslinked or
Network Polymer
- Crosslinks can be short or long
- The material can be: - lightly crosslinked
- highly crosslinked
- Crosslinked polymers typically do not dissolve, melt, or flow
(But they may swell in certain solvents)
Structure vs. Conformation
- Polymers are rarely stretched out in solution or in the melt
- Assume a random coil conformation
- The angle between the singly bonded carbon atoms is ~109 degree
carbon atoms form a zigzag pattern in a polymer molecule.
- while maintaining the 109o angle between bonds
polymer chains can rotate around single C-C
bonds
- (double and triple bonds are very rigid).
- Random kinks and coils lead to entanglement
Isotactic PP 160 - 170 C
Syndiotactic PP 125 - 130 C
Atactic PP < 0 C
melting point = ratio of latent heat of melting to entropy
of melting
molar cohesion energy (of the whole molecule for
monomers, or per chain unit for polymers),
molecular flexibility (due to rotation around bonds),
molecular shape effects
of melting
- The summation of subtle effects and weak forces play imp
roles in properties
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Sir Norman Haworth
Nobel prize 1937
Hermann Emil Fischer
Nobel prize 1902
Nobel prize 1937
Cellobiose
impart strength and rigidity to plant cell walls,
can withstand high hydrostatic pressure gradients
Microfibrils: 36
parallel, interacting
cellulose chains.
Chitosan
Alginate
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What is a polypeptide
Polymer of a amino acids
R O R O
H2N CH C OH H2N CH C OH
R O O
H2N CH C HN CH C OH
R
Molecular interactions
in wool fibre
Nylon 66
[-(CH2)
6
-NH-CO-(CH)
4
-CO-NH-]n
PAN
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In silico Structure Prediction of
Polymers-
Molecular Modeling
Polymer Structure
Linear
Branched
Crosslinked
Structure Prediction
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Mathematical Models
Ab Initio
Semi empirical
Molecular Dynamics
Quantum Mechanics
ab initio Method
H=E
Eisenergyofthesystem
isthewavefunction
HistheHamiltonianoperator
Approximations
The Born-Oppenheimer
approximation pp
Hartree-Fock approximation
Pros & Cons
+++++
Predict structure of-
Unsynthesized species
diffi lt ( i ibl ) t i l t difficult (or impossible) to isolate
-Ve
Very large calculations
Time consuming
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Semiempirical Methods
Several approximations
Some electron interactions are
ignored
Molecular mechanics
Force Field Theory
classical Newtonian physics
experimentally derived parameters
calculate geometry as a function of steric energy
Protein Structure
Primary Structure
Secondary Structure Secondary Structure
Tertiary Structure
Quaternary Structure
Primary Structure
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Secondary Structure
Ramachandran Plot
Tertiary Structure Quaternary Structure
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Protein Structure Prediction
XRD
Homology Modeling
Homology
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Basic steps in Homology Modeling
Database searching
Alignment (Pairwise/ Multiple)
Model building
Model refinement
Identify Homologues in PDB
Database Search
Alignment
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Specific Regions
Structurally Conserved Regions
Structurally Variable Regions Generate Core Coordinates
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Model Building
Replace SVR (Loops)
Add Side Chains Add Side Chains
Energy Minimization
Geometry Optimization
Replace SVR (Loops)
Add Side Chains
Energy Minimization
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Geometry Optimization
Model Validation
Structure Validation
Silk Fibroin (Bombyx Mori)
Two Peptide Chains
Light Chain Light Chain
Heavy Chain
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Light Chain Sequence
ORIGIN
1 mkpiflvllv atsayaapsv tinqysdnei prdiddgkas svisrawdyv
ddtdksiail
61 nvqeilkdma sqgdyasqas avaqtagiia hlsagipgda caaanvinsy
tdgvrsgnfa
f l ff h l l l l l df 121 gfrqslgpff ghvgqnlnli nqlvinpgql rysvgpalgc agggriydfe
aawdailass
181 dssflneeyc ivkrlynsrn sqsnniaayi tahllppvaq vfhqsagsit
dllrgvgngn
241 datglvanaq ryiaqaasqv hv
//
Blast Report
Final 3-D Prediction
Ramachandran Plot
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Model Quality Assessment
Q- Mean Score Calculation
C_betainteractionenergy:1.00(Zscore:1.58)
Allatompairwiseenergy:7.36(Zscore:1.68)
Solvationenergy:618.74(Zscore:1.44)
Torsionangleenergy:3.01(Zscore:2.41)
Secondary structure agreement: 0 1% (Zscore: 2 98) Secondarystructureagreement:0.1%(Zscore:2.98)
Solventaccessibilityagreement:54.9%(Zscore:0.98)
TotalQMEANscore:0.306(Zscore:2.49)
(estimatedmodelreliabilitybetween01)
PDB Comparison
HyperChem Prediction
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Heavy Chain Sequence
ORIGIN
1 agtgssgfgp yvanggysgy eyawssesdf gtgsgagags gagagsgaga gygagvgagy
61 gagygagaga gygagagsgv asgagagags gagagsgaga gsgagagsga gagsgagags
121 gagagygaga gygagagyga gagvgygaga gvgygagagy gagagvgyga
gagsgaasga
181 gagsgagags gagagsgaga gsgagagsga gagsgagags gagagsgaga gygagagvgy
241 gagagsgaas gagagsgaga gsgagagsga gagsgagags gagagsgaga
gsgagagsga
301 gsgagagsga gagygagaga gvgygagaga gygagygyga gagvgygaga 301 gsgagagsga gagygagaga gvgygagaga gygagygyga gagvgygaga
gsgaasgaga
361 gsgagagsga gagsgagags gagagsgags gagagsgaga gygagygagv
gagygagagv
421 gygagygvga gagygagags gaasgagags gagagsgaga gsgagagsga
gagsgagsga
481 gagygagags gaasgagaga gagtgssgfg pyvanggysr regyeyawss
ksdfetgsga
541 asgagagags gagagsgaga gsgagagsga gaggsvsyga grgygqgags aassvssass
601 rsydysrrnv rkncgiprrq lvvkfralpc vnc
//
Blast Report
Final 3-D Prediction
Ramachandran Plot
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Model Quality Assessment Q- Mean Score Calculation
C_betainteractionenergy:1.00(Zscore:2.31)
Allatompairwiseenergy:13.61(Zscore:3.10)
Solvationenergy:156.14(Zscore:2.07)
Torsionangleenergy:2.31(Zscore:2.22)
Secondarystructureagreement:9.5%(Zscore:5.82)
S l ibili 36 8% (Z 3 48) Solventaccessibilityagreement:36.8%(Zscore:3.48)
TotalQMEANscore:0.123(Zscore:5.81)
(estimatedmodelreliabilitybetween01)
PDB Comparison
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Amorphous&crystallinephases,
Crystallization,
EffectofCrystallinityonproperties
ofpolymers
Why do polymers crystallize ?
Random coil : conformational entropy of a
random coiled chain is very large, due to
significant number of accessible conformations.
crystallization
melting
Lowest energy conformation
3D ordered lattice
Higher entropy state
Only polymers of a regular configuration can crystallize (
isotactic, syndiotactic)
1. Polymer crystals are formed by lateral alignment of extended
chains
2. Alignment is a 3D order
A Chains will maintain their lowest energy conformation in A. Chains will maintain their lowest energy conformation in
crystal lattice
B. Chains will pack as close as possible. Distance of closest
packing is given by van der waals radii
C. Equivalent atoms of different monomer units along the chain
axis tend to assume equivalent positions wrt the atoms of
neighboring chains
SpheruliteGrowth
Nucleation-1
Nucleation-2
Kinetics of Polymer Crystals formation
A. Nucleation and Spherulitic growth
BranchingSpherulite
B. Spherulite
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C. Spherulite structure having
radial growth & branching
D. Orientation of chains
in an enlarged portion
of lamellae having
chain folding
Linear PE
Nucleation at a reasonable rate of growth must
involve chain folding.
The fully extended chain crystal (most stable)
requires unreasonably long time to form. Chain
folding is a compromise between
thermodynamics and kinetics of crystallization.
So, polymer chains choose an alternative way
to crystallize, i.e. through chain folding.
E.Chainfoldingintheformationof
singlecrystallamella
100 A
o
Lamellae form because it is the fastest way for long molecules to crystallize
F.IdealStackingof
lamellarcrystal
G.InterwovenStructureofpolymers
throughfoldedchainlamellae
H. Interlamellar amorphous str of semicrystalline polymer
I. Fringed micelle concept of partly
crystalline polymer
Shick-Kabab form
a
b
c
J. Folded chain lamellar structure
Thinness of polymer lamellae is very imp to
crystallize polymers because of the many
surfaces it creates that directly affect the
imp properties such as melting pt, chemical
reactivity, mechanical prop.
Thickness is related to crystallization, rather
than depending on chemistry of polymer
chain. It is affected by H- bonding, it
increases with crystallization temp.
Drawn
Fibrils
Drawn spherulite
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200 nm
TEM: Silk fibrils
Microfibrils
Extended
Noncrystalline
molecules
Crystallites
The growth of these structures
impeded by the presence of
entanglements and strained
regions, which constitute the
amorphous phase
(A) Crystallization during polymerization
Fringed fibrillar model
Fringed micelle model
Folded chain lamellar model
(B) Crystallization induced by orientation
stretching of long chains to form fibrous crystals
decrease in the conformational entropy
(C) Crystallization under quiescent condition
(1) Crystallization from dilute solutions
(2) Crystallization from the melt
melting temp to pre-determined crystallization temp
small-angle x-ray scattering
Density fluctuations (nucleation and growth processes)
Development of network structure
Plain polarizing microscopy,
Rheological and light
scattering studies
Development of network structure
(very early stages of crystallinity development)
Onset of autocatalytic, observable crystallization
(1) fringed micelle, (2) lamellar type of morphology
pseudo-equilibrium level of crystallinity
TEM, Birefringence
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Degree of crystallinity is determined by:
Molecular conformation & chain flexibility
Structural regularity & Chain configuration: linear polymers
crystallize relatively easily, branches inhibit crystallization,
network polymers almost completely amorphous,
crosslinked polymers can be both crystalline and amorphous
Complexity: crystallization less likely in complex structures.
Simple polymers, such as PE, crystallize relatively easily
Rate of cooling during solidification: time is necessary for
chains to move and align into a crystal structure
Isomerism: isotactic, syndiotactic polymers crystallize relatively
easily - geometrical regularity allows chains to fit together, atactic
difficult to crystallize
Copolymerism: easier to crystallize if monomer arrangements
are more regular - alternating, block can crystallize more easily
as compared to random and graft
Presence of Intermolecular forces: polarity, H-bonding etc
Branching / bulkyness of side groups:
Short irregular branches tend to decrease crystallinity %
Regular short branch, small side groups able to produce g , g p p
coiling, favours crystallization
Molecular weight: low mol wt favours mobility, higher
crystallization
Impurities present
More crystallinity: higher density, more strength, higher resistance to dissolution and
softening by heating
PMMA
at RT
100
o
C
120
o
C
GLASS TRANSITION, Tg
Rubber band vs PET bottle
at RT
Glassy state
Starts to soften
Rubbery state
Tg = -70
o
C, can we use it for making window pane ?
Tg = 100
o
C, can we use it for making car tire ?
Hardness is related to polymer mobility
Below Tg, molecules are frozen in.
When polymer is heated above Tg, thermal
energy imparted on the molecules is sufficient
What happens on polymer molecules at Tg?
energy imparted on the molecules is sufficient
to overcome the energy barrier for translational
& rotational motions.
Onset of large scale motion
Entanglement restrictions
Degradation
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Definitions
Tg is the temp at which the polymer
molecules start to perform large scale
(translational & rotational motions) motion
when we heat the polymer from glass state
Tg is the temp at which the polymer
molecules are frozen into a state where
large scale motion is prohibited when we
cool the polymer from the rubbery state
Does every material have a Tg?
Only amorphous materials
Crystals do not exhibit Tg, but shows melting phenomenon
Only vibrational motion is allowed
H d T ? How do we measure Tg?
Glassy state
Rubbery state
Specific
vol
Temp
Tg
Glassy state
Rubbery state
Enthalpy
H
Temp
Tg
Change of heat capacity (Cp)
Differential Scanning Calorimeter
Glassy
state
Rubbery state
Cp
Temp
Tg
Modulus
Stress/strain
Tem
p
Tg
Viscosity
Dielectric relaxation
Refractive index
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1. Freevolumetheory doesnotinvolvemicroscopic
description
2.Thermodynamictheory
Tgisathermodynamic2
nd
ordertransition,whichoccursas
TheoriesaboutGlasstransition
theconformationalentropyofpolymerchainsreaches
zero.
3.Kineticstheory Tgisthepointwheretherelaxation
ofmoleculesisunabletocatchupwiththeexperimental
coolingrate,sothemoleculesarefrozenintoanon
equilibriumstate.
FreevolumeVf =V V0
Vf =Freevolume
V=totalvolume
V0 =occupiedvolume
Emptyspace=freevolume
Ifthesystemhasalargerfreevolume,themolecules
havemorespacetoundergomotion.Themolecules
havealargermobility.
Doolittleequation
FreevolumereachesaconstantvalueatandbelowTg.
AtTgthefractionalfreevolumeistoosmalltoallowlarge
scalemolecularmotiontooccur.
Whenthetempisfurtherdecreased,moleculescannot
moveanymore,thusthefractionalfreevolumeisfrozen
inatthevalueoffractionalfreevolume(fg).
Freevolumetheoryisusefulininterpretingeffectsof
externalfactors(pressure,molwt,etc)onTg.
Conceptunderlyingfreevolmaynotbestrictlytrue.
1. Effect of increasing pressure on Tg
V
P1 < P2
Tg1 Tg2
A Polymer has less free volume at higher pressure.
So, a polymer has a higher Tg at higher pressure.
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2. Effect of Mol weight on Tg
Tg
Mol wt
Chain ends are connected only at
one side, they have more freedom
to move, compared to internal
segments
M1 < M2
Polymer with lower MW has more free volume.
Lower mol wt polymer has a lower Tg
Free volume
Tg1 Tg2
Temp
Thermodynamictheory
Glassystateisthermodynamicallyequilibriumstate.
Butpropertieslikevolume,enthalpy,mechapropertiesof
glassypolymerchangewithtime.
Considerphasetransitionfromphase1tophase2.
AtphasetransitiontempT,GibbsfreeenergyG1=G2
Butiftheirvolumes&entropiesarenotequal,thenthe
phasetransitioniscalled1
st
ordertransition.
Melting
Crystallization
Vaporization
Condensation
S = - (dG/ dT) p
V = (dG/dP)T
1
st
order transition is the phase transition where properties
related to 1
st
partial derivatives of G exhibit discontinuities at
the transition temp.
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2
nd
order transition is the phase transition where
properties related to 2nd partial derivatives of G exhibit
discontinuities at
the transition temp.
Cp = Specific heat capacity
at constant pressure
Tg is 2
nd
order transition
Tg is the temp where the conformational entropy of a
polymer approaches zero
No conformational arrangement will be possible.
Polymer molecules are randomly placed.
Equal probability
Can have any conformation
Trans: Low energy
Gauche: high energy conformation
Repulsive interaction between segments will make
some bond conformation less accessible effect of
interaction energy.
At high temp a very great no of conformational states
are accessible to each chain at high T thermal
energy can easily overcome the hindrance to rotation
and hence high energy conformation are accessible to
the chain..No of ways of arranging the polymer
molecules and holes are large.
As T is lowered, no of accessible conformation is As T is lowered, no of accessible conformation is
drastically reduced (high energy conformations are no
longer accessible).
When temp is reduced to Tg only ONE conformation
is accessible to the chain. So during glass transition
from rubbery to glassy state occurs, Glassy state
should be an eqlb state whose properties will not
change with time.
Criticism: 1. Glass state is a nonequilibrium state,
rather than equilibrium state. Properties change with
time.
Vol
Cooling a polymer to Ta (below Tg)
Volume relaxation or physical ageing
2. Value of measured Tg is dependent on rate at
which the experiment is done.
Higher Tg with faster cooling rate.
Temp
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Kinetictheory
IfTgismeasuredininfinitelyslowrate,itwouldbe
true2
nd
ordertransition.Butsuchextremelyslow
experimentisimpossibletoconduct.
Changeofmolecularmobilitywithtemp
Asystemhasaneqlbmstateateverytemp.Ifwe
coolapolymerfrom100degreeCto99degreeC
polymermoleculeswillrearrangethemselvesto
reacheqlbmstateat99degreeC.
Relaxationtime:timereqdforpolymermolecules
tomovetoreachtheireqlbmstateatevery
temp.
Athighertemp,moleculeshavehighermobility,
sotimereqdtoreacheqlbmstateisshorter.
Temp 100 95 91 90 89 88 85 79
Relax
time
0.01
sec
1
sec
40
sec
2
min
5
min
18
min
5
hours
1
year
Structural parameters affecting Tg
1. Chain flexibility: stiffer chain has higher difficulty to perform
motion (less free volume), hence has higher Tg.
O O PEEK
-(CH2-CH2)n- PE Tg = 145
o
C
Tg = 100
o
C Tg = - 100
o
C
2. Side groups : Polymer containing bulky side groups will
have more difficulty to move chains (less free vol), hence
higher Tg
-(CH2-CH2)n-
-(CH2-CH)n-
Tg = - 100
o
C Tg = 100
o
C
3. Chain branching:
Branched chains polymers will have more chain ends,
hence free volume of the molecule will be more, so Tg
will be less.
Chain branching will make the branch points in the
molecule less mobile, as internal segments are
connected to each other. So free vol will be less, and
higher Tg.
4. Cross linking:
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36
1. One students was trying to measure % crystallinity by
using FTIR, DSC, XRD. He got different values using
different technique. Explain Why?
2. Mention other methods for estimating % crystallinity
3. Tg of fibres can vary with RH (0% to 100%). Out of the
following fibres, which fibre will show this behaviour?
Polypropylene, cotton, nylon, polyester
Methods of Fibre preparation
1. Dry spinning: Solution of cellulose nitrate in a
alcohol/ether solvent. Solidification by solvent
evaporation
wide range of properties depending on the processing conditions
2. Viscose: Wet spinning: solidification by chemical
coagulation
3. PET, PP, Nylon: Melt spinning: solidification by
cooling
Liquid crystal Conventional (PET) melt spg
Solution
Extrusion
Nematic structure
Low entropy
Random coil
High entropy
Structure formation during spinning
Extrusion
Solid
state
Extended chain structure
High chain continuity
High mechanical properties
Folded chain structure
Low chain continuity
Low mechanical properties
Dilute solution of (super) high molecular weight PE
extruded into water by wet spinning, so that gel like
fibers are formed.
Then hot drawing is applied (30 times in length)
Gel spinning
Classical PE drawn only up to 10 times in length.
Dyneema, Spectra, Tekmilon.
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37
Diameter
Cr stalli ation
Birefriengence
Natural draw ratio
Maximum draw ratio
Stress
Drawing : as-spun fibres have poor elasticity, they undergo plastic
deformation on application of low stress. Polymer chains are in partially
folded conformation, can extend easily.
Heat setting: Polymer chains are unfolded, improved, more elastic
network of polymer is formed. Polymer chains assume extended
conformation, do not recover back to their original state when stress is
released.
Crystallization
point
Distance from spinneret
Elongation %
Nylon-6
single phase rubber like amorphous network, having rubber like
deformation
Winding, conditioning:
1. Orientation of crystalline phase: highly oriented amorphous
segments,
molecular chains get oriented in axial direction
Improvement in birefringence Improvement in birefringence
2. substantial amount of crystallinity develops,
even at low winding speed
Developed crystals are of alpha-type
-form : monoclinic unit
cell
(a = 9.56 ,
b = 17.24 (fiber axis),
c = 8.01 and = 67.5)
with eight
monomeric units, and
consists of an extended-
chain chain
sheet structure with
hydrogen bonding between
antiparallel chains
-form : monoclinic unit cell
(a = 9.33 ,
b = 16.88 (fiber axis),
c = 4.78 and = 121).
Low speed spg: -crystals
High speed spg: -crystals
Drawing is easier as -are
deformable
-form is more stable
Polyethylene fibers
Dyneema or Spectra
Orientation > 95%
Crystallinity up to 85%
Normal PE
Orientation low
Crystallinity < 60%
The theoretical elastic modulus of the covalent C-C bond in the fully
extended PE molecule is 220 Gpa.
Experimental value in PE fibres - 170 Gpa.
Stretching
Entanglement network Fibrillar crystal
8/16/2012
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Extended chain polyethylene
minimum chain folding
UHMPE fibre structure: (a) macrofibril consists of array of microfibrils;
(b) microfibril; (c) orthorhombic unit cell; (d) view along chain axis
Intensity of deformation
or
Strain
= l / L
Elongation
Unstretched length
=
Mechanical behaviour of polymers
1. Stress-Strain curve
Load intensity or Stress = Force P / cross sec area A
Rigid plastic Glassy
Flexible plastic
leather like
Elastomers
Rubber like
Stress
Strain %

For small values of strain, stiffness or Youngs modulus (E) is

equal to the tangent of the stress strain curve
E = tan
Adv:
1.Stiffness, stress at which fracture occurs.
2. relation between force and deformation at every point.
Limitation:
1.Applicable to the particular mode of loading.
Diff in mechanical behaviour due to the mode of loading (tension
vs compression) are not so serious at small deformations but is
significant at large deformation.
1. Load: application of a load to a specimen in its
axial direction causes a tension to be developed in the
specimen. The load may be expressed in Newtons (N)
or in gm force.
2. Breaking load: This is the load at which the
specimen breaks, usually expressed in gms, lbs or
Newton.
3. Stress: Load
Area of cross section dyn
/ cm
2
, N/m
2
or Pascal
4. Specific stress: Cross section of many fibres are
irregular in shape, and difficult to measure the area.
Specific stress = Load / linear density
Gm per tex or gm per denier
8/16/2012
39
5. Breaking length: length of the fibre which will just
break under its own weight when hung vertically.
6. Strain: when a load is applied to a specimen a
certain amount of stretching or elongation takes place.
Strain = Elongation / Initial length
7. Initial modulus: slope of the stress-strain curve at
the origin
2. Modulus temperature curves
Polymeric fibres are Viscoelastic, i.e. their mechanical
properties depend on rate of loading or on time under load. So
it is necessary to specify the time interval under load at which
the E-T data were obtained. 10 sec
1
Tg
Semicrystalline
2 2
3
4
4
Semicrystalline
Tm
Crosslinked
Uncrosslinked
Amorphous
T
o
C
E
N/m2
Region 1: Glassy
2. Transition or leather
like
3. Elastomeric or
rubber like
4. Liquid flow
E-T curves of amorphous (atactic),
semicrystalline (isotactic) polystyrene
3. Regions of mechanical equivalence
Polymer at a given temp can be said to be in one of four
regions of mechanical equivalence.
(i)Glassy region: Modulus E takes values in the range 10
9

10
10
N/m
2
in this region which is found below Tg. A polymer
below Tg is stiff, hard, brittle.
For many applications involving small deformations, polymers
in region 1 can be designed by use of the theory of Linear
elasticity.
This theory assumes that the stress-strain relation is linear and
that recovery of original shape, following unloading, is
instantaneous and complete, occuring along the identical
stress-strain path which was traversed during loading.
(ii) Transition region: The modulus of amorphous polymer
drops from about 10
9
10
6
N/m
2
as the material is heated
above Tg in the transition region between glassy (region 1)
and rubber-like (region 3) behaviour.
The modulus of semicrystalline polymer drops only from
about 10
9
10
7.5
N/m
2
as the material
.
is heated from Tg to
Tm. Mechanical properties of semicrystalline polymer in
this region resemble those of rather stiff leather this region resemble those of rather stiff leather.
Polymers in region 2 are typically ductile. Their mech
behaviour is strongly time-dependent. So the branch of
mechanics which may be used to describe small-
deformation behaviour in region 2 is the theory of linear
viscoelasticity, a modification of theory of linear
elasticity which accounts for time effects.
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40
(iii) Elastomeric (rubber like) region: Rubber like behavior is
monopolized by amorphous polymers. Crystallites stiffen the
structure and tie down macromolecules, thereby preventing
their large-scale unfolding.
Characteristics of region 3: Extension 500-1000 %, moduli 10
5
10
6
N/m
2
Crosslinked rubbers are capable of recovering their original p g g
shape fully after being released from very large extensions of
indefinite duration. Uncrosslinked rubbers may recover fully
only if stretched to a small extent over a short period of time.
Modulus of uncrosslinked suffers a dramatic drop with temp, &
the polymer flows like a viscous liquid (Region 4). But
crosslinking preserves the modulus almost intact until the temp
level above which 3D network undergoes chemical
decomposition.
(iv) Liquid flow region: Crosslinked polymer decomposes if
heated to a high temp but it does not undergo flow.
But uncrosslinked amorphous polymer gradually loses its
ability to recover from deformation while undergoing
permanent deformation (flow) as the temp is increased. At high
temp, amorphous polymer in region 4 behaves as a liquid with
very high viscosity, very limited elasticity.
When heated above Tm, semicrystalline polymers melt and
behave similarly to amorphous polymer in region 4.
In general, polymer fluids are non-Newtonian i.e., their flow
properties can be characterized by a nonlinear relation
between shear stress and flow rate.
Monomer
T
o
C
E
N/m2 Mn = 140,000
Mn = 217,000
T
o
C
E
N/m2
Crosslink
density