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MATERIAL PROPERTIES
Increasing Degree of Polymerization, DP
H ig h D e n s it y P E
P r o p e r tie s
B rittle W a x
Tough
W ax
m e lt in g
p o in t
L o w D e n s it y P E
O lig o m e r s
d e n s ity
c r y s t a llin it y
T e n s ile
S tre n g th
E lo n g a t io n
100
1 0 ,0 0 0
1 ,0 0 0
1 0 0 ,0 0 0
X
H
CH3
Cl
Phenyl
CN
COOCH3
O-COCH3
Polymer
Abbreviation
Polyethylene
PE
Polypropylene
PP
Poly(vinyl chloride) PVC
Polystyrene
PSt
Polyacrylonitrile
PAN
Poly(methyl acrylate) PMA
Poly(vinyl acetate) PVAc
M o le c u la r W e ig h t
Y Polymer
Abbreviation
CH3 CH3
Polyisobutylene
PIB
Cl Cl Poly(vinylidene chloride)
PVDC
F
F Poly(vinylidene fluoride)
PVDF
Phenyl CH3 Poly(-methyl styrene)
CH3 COOCH3
Poly(methyl
methacrylate)
PMMA
Poly(alkyl -cyanoacrylate
CN COOR
Tacticity
H
Syndiotactic
Tacticity of Enchainments
Branching
Copolymers
Isotactic
Homopolymers
X X
X X
Statistical
X X
Alternating
Gradient
Blocks
Grafts
Molecular Weight
Molecular Weight Distribution, MWD
Polydispersity Index, PDI
Hydrolysis
Dehydrohalogenation
Crosslinking Density
Photodegradation
Length of Crosslinks
Oxidation
Thermal Degradation
Processing
Aging
Crystallization
Changes in Polymorphism
Weathering-- Combination of Above
Plasticizer Loss -- Imbrittlement
Polymer
Dispersion or
Van der Waals
Weak
Methane
Hexane
Polyethylene
Polypropylene
Dipole-Dipole
Medium
CH3Cl
CH3CO2CH3
PVC
PMMA
Very Strong
H2O
Cellulose
CH3CONH2
Proteins
CH3CO2-Na+
Ionomers
Microscopic Properties
(Intermolecular Interactions)
Chain entanglement amorphous
Chain ordering--liquid crystalline
Crystallinity
Phase separations (microdomains)
Morphology
Macroscopic Properties
(Physical Behavior)
Tensile and/or Compressive Strength
Elasticity
Toughness
Thermal Stability
Degradability
Solvent Resistance
Permeability
GLASS TRANSITION, Tg
Definition: The onset of seqmental motion of
seqments with 40-50 carbons atoms
Physical Change Expansion of volume
Free volume required to allow segmental motion
Tg is an approximation
Polystyrene MW = 4000
Tg = 40C
= 300,000
= 100
GLASS TRANSITION, Tg
Properties Affected
Specific Heat, Cp
Refractive Index
Modulus
Dielectric Constant
Permeability
FACTORS INFLUENCING Tg
FACTORS INFLUENCING Tg
Tg is proportional to Rotational Freedom
For symmetrical polymers Tg, / Tm in K
1/2
unsymmetical polymers
2/3
1. Chain flexibility
Silicone > Ether > Hydrocarbon > Cyclic
HC > Aromatics
Tg = -120C
5C
-24C
-50C
Tg =
-55C
88C
FACTORS INFLUENCING Tg
3. Molecular Symmetry
Asymmetry increases chain stiffness.
4. Polar Interactions increase Tg
Hydrogen bonding
5. Molecular Weight up to Critical Limit
6. Crosslinking
Reduces Segment Mobility
FACTORS INFLUENCING Tm
1. Chain flexibility
Silicone > Ether > Hydrocarbon > Cyclic
HC > Aromatics
2. Substituents Producing Lateral
Dipoles
Hydrogen bonding
3. Molecular Symmetry
FACTORS INFLUENCING Tm
4. No Bulky Substituents to Disrupt Lattice if
placement is Random
5. Structural Regularity
monomer placement
head to tail
1,2- vs 1,4
1,2- vs 1,3- vs 1,4- aromatic substitution
tacticity
FACTORS REQUIRED TO
PROMOTE CRYSTALLIZATION
Thermodynamic
1. Symmetrical chains which allow regular
close packing in crystallite
2. Functional groups which encourage
strong intermolecular attraction to stabilize
ordered alignment.
Multidimensional Order
FACTORS REQUIRED TO
PROMOTE CRYSTALLIZATION
Kinetic
1. Sufficient mobility to allow chain
disentanglement and ultimate alignment
Optimum range for mobility
Tm -10 Tg + 30
at Tm segmental motion too high
at Tg viscosity too high
2. Concentration of nuclei
Microscopic
Molecular
Microscopic
*Crystallinity
*Phases
*Orientation
Molecular
Synthesis and
Processing
*Chemical Composition
Macroscopic
*MW/MWD
*Branching and/or
Cross-linking
*Strength
Macroscopic
*Modulus
*Impact Resistance
Permeability
Clarity