Mse 356 Engineering Properties of Polymers

MSE 356 ENGINEERING PROPERTIES
OF POLYMERS
• R.J Crawford, Plastics Engineering, Pergamon
Press
• M.F Ashby and D.R.H. Jones, Engineering
Materials 2: An Introduction to
Microstructures, Processing and Design,
Pergamon Press
• W.D. Callister Jr., Materials Science and
Engineering: An Introduction, Wiley & Sons
1
COURSE STRUCTURE
• Chemical structure and polymer properties
• Polymer morphology
• Solid structure, crystallography morphology
• Mechanical properties in glassy, rubbery and fluid
states
• Thermal stability
• Flammability and flame resistance
• Chemical resistance
• Product design
• Rheology, rheometry and polymer processing
2
MSE 356 ENGINEERING PROPERTIES
OF POLYMERS
• Mechanical properties of polymers
• Modulus of elasticity (Young’s Modulus)
• Tensile strength
• Impact strength
• Fatigue strength
• Polymeric materials characterized using the
simple stress-strain test.
3
Mechanical properties of polymers
• Mechanical properties of polymers
4
5
6
• Plastic deformation corresponds to the
breaking of bonds
• Yield point – initial departure from linearity
• Tensile strength is the maximum stress
• Ductility – measure of the degree of plastic
deformation that has been sustained at
fracture
l f  lo
% El   100
lo
7
Polymer Response to Stress
• Curve A – brittle polymers
• Curve B – similar to the behavior of metals
• Curve C – rubber-like elasticity, elastomers
8
• Typical modulus of elasticity for plastics –
7MPa to 4GPa,
• Modulus of elasticity for metals 48GPa to
410GPa
• Yield point is taken as the maximum on the
curve
• Tensile strength, TS, corresponds to the stress
at which fracture occurs
9
Room temperature Mechanical characteristics of
some common polymers
Material S.G Tensile Modulus Tensile Strength Yield Strength Elongation at Break (%)
(GPa) (MPa) (MPa)
Polyethylene low 0.91 – 0.93 0.17 – 0.28 8.30 – 31.40 9.00 – 14.50 100.00 – 650.00
density
Polyethylene high 0.95 – 0.96 1.06 – 1.09 22.10 – 31.00 26.20 – 33.10 100.00 – 1200.00
density
Polyvinyl Chloride 1.30 – 1.58 2.40 – 4.10 40.70 – 51.70 40.70 – 44.80 40.00 – 80.00
Nylon 6,6 1.13 – 1.15 1.58 – 3.80 75.90 – 94.50 44.80 – 82.80 15.00 – 300.00
Polyester (PET) 1.29 – 1.40 2.80 – 4.10 48.30 – 72.4 59.30 30.00 – 300.00
Polymethyl 1.17 – 1.20 2.24 – 3.24 48.30 – 72.4 53.80 – 73.10 2.00 – 5.50
methacrylate
10
• The mechanical characteristics of polymers,
for the most part are highly sensitive to the
• Rate of deformation
• Temperature
• Chemical nature of the environment
(presence of water, oxygen, organic solvents,
etc)
11
• Decreasing the rate of deformation has the
same influence on the stress-strain
characteristics as increasing the temperature,
i.e. the material becomes softer and more
ductile
12
Influence of temperature on the stress-
strain characteristics
• polymethylmethacrylate at varying
temperatures
13
• Deductions - increasing the temperature
produces the following responses:
– A decrease in elastic modulus
– A reduction in the tensile strength
– An enhancement in ductility e.g. at 4°C, the
material is totally brittle whereas considerable
plastic deformation is realized at both 50 and
60°C.
14
• Polyethylene: rate of elongation akin to
temperature changes
15
Deformation of Semi-crystalline
Polymers
• Many semi crystalline polymers in bulk form
will have the spherulitic structure
• Spherulite consists of numerous chain-folded
ribbons or lamellae that radiate outward from
the center
16
Schematic representation of a
spherulite
• Crystalline – amorphous composite
17
Mechanism of Elastic Deformation
• Starts with elongation of the chain molecules
from their stable conformations, in the
direction of the applied stress
• Stretching of the strong chain covalent bonds
• Slight displacement of adjacent molecules
• Polymer as a Composite – crystalline and
amorphous regions
• Elastic modulus – combination
18
Cold Drawing
• The tensile stress-strain curve cold drawn at
temperatures between Tg and Tm
19
Cold Drawing
• Necking – chains become oriented (i.e. chain
axis become aligned parallel to the elongation
direction) which leads to localized
strengthening
• Propagation of this neck region
• Contrasting to that found for ductile metals
20
Factors Influencing the Mechanical
Properties of Polymers
• Recapping
– increasing the temperature or
– diminishing the strain rate
• leads to
– a decrease in the tensile modulus,
– a reduction in tensile strength, and
– an enhancement of ductility
21
• A restraint placed on a polymeric material
(extensive chain entanglements or a
significant degree of intermolecular bonding)
leads to increase in strength
• Modulus of polymeric materials rises as both
the secondary bond strength and chain
alignment increase
22
• (A) Molecular Weight
• many polymers experience an increase in the
tensile strength with increasing molecular weight
A
TS  TS  
Mn
• TSα = tensile strength at infinite molecular weight
• Mn = Molecular weight
• A = constant
23
• (B) Degree of Crystallinity
• crystalline phase affects the extent of the
intermolecular secondary bonding
• tensile modulus of semi crystalline polymers
increases significantly with increased degree
of crystallinity
• modulus increases 10-fold as the crystallinity
fraction is increased from 0.3 to 0.6.
24
• Molecular chemistry as well as chain
configurations influences the ability of a
polymer to crystallize
• chemically complex mer structures (e.g.
polyisoprene) reduce ability to crystallize
• Linear polymers crystallize more easily since
there is no restriction to prevent chain
alignment (e.g. polyethylene and
polytetrafluoroethylene)
25
• Network polymers are almost totally
amorphous, whereas cross linked polymers
exhibit various degrees of crystallinity
• Isotactic and syndiotactic polymers crystallize
much more easily because of the regularity of
the geometry
26
• Isotactic
• Syndiotactic
27
• bulkier or large side-bonded groups of atoms
on polymers result in less crystallinity
• irregular and random mer arrangements,
leads to greater tendency for development of
non crystallinity
• Atactic
28
• the effects of both the percent crystallinity
and molecular weight on the physical state of
polyethylene.
29
• (C) Drawing
• Drawing is equivalent to strain hardening in
metals
• Commercially used to improve the mechanical
strength and tensile modulus of polymers
(fibers and films)
• degree of strengthening and stiffening
depends on the extent of deformation (or
extension)
30
• properties of drawn polymers are highly
anisotropic
• Tensile modulus may be increased by a factor
of 3 in the direction of drawing, relative to the
undrawn material.
• Tensile strength parallel to the direction of
orientation may be improved by a factor of 2
to 5
31
• the tensile strength in the direction
perpendicular to the direction of drawing is
reduced by about 1/3 to ½
• For an amorphous polymer drawn at an
elevated temperature, the oriented molecular
structure is retained only when the material is
quickly cooled to the ambient
32
• (D) Heat Treating
• Heat treating or annealing of semi crystalline
polymers leads to modifications in
• crystallite size and perfections,
• the spherulite structure
33
• For undrawn materials, increasing the
annealing temperature leads to the following
– An increase in ensile modulus
– Increase in yield strength
– Reduction in ductility
• Note that these qualities are opposite to those
typically observed for metallic materials
34
• For some polymer fibers that have been
drawn influence of annealing on the tensile
modulus is contrary to that for undrawn
materials
• modulus decreases with increased annealing
temperature due to loss of chain orientation
and strain-induced crystallinity
35
Crystallization
• Crystallization: an ordered (i.e. crystalline) solid
phase is produced from a liquid melt having a
highly random molecular structure
• Crystallization of a molten polymer occurs by
nucleation and growth
• Upon cooling
– nuclei form wherein
– small regions of the tangled and random molecule
become ordered and aligned in the manner of chain-
folded layers
36
Crystallization
• nuclei grow by the continued ordering and
alignment of additional molecular chain
segments
• chain-folded layers increase in lateral

dimensions
37
Crystallization
• for spherulitic structures, there is an increase
in spherulite radius
• Mathematically, the fraction crystallized, given
by the Avrami equation thus

y  1  exp  kt n

• k, n are time-independent constants, which
values depend on crystallizing system
38
Crystallization
• Plot of the fraction crystallized versus time
yields a sigmoidal-shaped curve as shown in
the figure below
39
Crystallization
• Extent of crystallization is measured by
specimen volume changes since there will be
a difference in volume for liquid and
crystallized phases
• Rate of crystallization is equal to the reciprocal
of time required for crystallization to proceed
to 50% completion
40
Crystallization
• This rate of crystallization is dependent on
crystallization temperature (fig 9 above) and
also on the molecular weight of the polymer
• Crystallization rate decreases with increasing
molecular weight
41
Melting
• Transformation of a solid material with an
ordered structure of aligned molecular chains
to a viscous liquid of highly random structure
• Melting of polymers takes place over a range
of temperatures.
• The melting behavior depends on the history
of the specimen, particularly the temperature
at which it crystallizes
42
Melting
• The thickness of chain-folded lamellae
depends on crystallization temperature
• The thicker the lamellae, the higher the
melting temperature
• The apparent melting behavior is a function of
the rate of heating
• Increasing the rate of heating results in an
elevation of the melting temperature
43
Melting
• An increase in lamellar thickness may be
induced by annealing just below the melting
temperature.
• Annealing also raises the melting
temperature of the polymer
44
Glass Transition
• Glass transition phenomenon occurs with
amorphous polymers
• Upon cooling, the glass transition corresponds
to the gradual transformation from a liquid to
a rubbery material
• glass transition temperature, Tg.
• Abrupt changes also occur in other physical
properties, e.g stiffness, heat capacity
45
Glass Transition
• Relaxation Modulus
46
Melting and Glass Transition
Temperature
• Melting and or the glass transition determined
from a plot of specific volume (reciprocal of
density) versus temperature (Next slide)
47
Temperature
• 3 different kinds of polymer
48
Temperature
• Meting and Glass Transition temperatures
Material Tg (°C) Tm (°C)
Polyethylene (LD) -110 115
Polyethylene (HD) -90 137
Polypropylene -18 175
Polyvinyl chloride 87 212
Polycarbonate 150 265

49
Factors Affecting Tm and Tg
• MeltingTemperature
• Molecular chemistry and structure affect
rearrangements of molecules
• Chain stiffness – rotation of the molecule
about chemical bonds along the backbone of
the chain
• Double chain and aromatic groups lower chain
flexibility hence Tm increases
50
• Size and type of side group restrict rotation
and Tm increases e.g. by large side groups
• CH3 – methyl of polypropylene melting
point 175°C
• H – Hydrogen of polyethylene Tm - 115°C
• Cl, OH, CN – Polar side groups have significant
intermolecular bonding forces therefore Tm
increases
51
• molecular weight
• Tm is over a range because polymer made up
of molecules of varying molecular weight.
• Branching introduces defects into crystalline
material and therefore Tm decreases
• E.g High density PE with linear polymer, Tm =
137 °C versus LDPE with some branching, Tm =
115 °C.
52
• Glass Transition Temperature, Tg
• Amorphous polymer has glass transition
temperature, Tg.
• Molecules experience rotational and
translational motion above Tg, from virtually
frozen position.
• molecular character of the polymer affects
chain stiffness.
53
• Chain flexibility is diminished and Tg increased
by the following:
• bulky side groups, e.g polypropylene Tg = -18
°C , Polystyrene Tg = 100 °C
• Polar side atoms, e.g PVC Tg = 87 °C,
Polypropylene Tg = -18 °C
• Double – chain bonds and aromatic chain
group tend to stiffen molecular backbone.
54
• As molecular weight increases Tg also
increases
• Branching: Small amount of branching
brings about a decrease in Tg but high density
of branches reduces chain mobility and Tg
increases
• Cross-links restrict molecular motion.
• Tg ≈ 0.5 – 0.8 Tm K.
55
Polymers and Plastics
• The polymer is the term used for the pure
material which results from the process of
polymerization
• when additives are present then the term
plastic is applied
56
• Main additives used in plastics
• Antistatic Agents: attract moisture from the air
to the plastic surface to reduce static build-up.
e.g aliphatic amine and amides.
• Coupling Agents: to improve the bonding of
the plastic to inorganic filler materials, such as
glass fibers; Examples of coupling agents
silanes and titanates
57
• Fillers:
– some improve the mechanical properties of a
plastic.
– Others, called extenders, permit a large volume of
a plastic to be produced with relatively little actual
resin
– Calcium carbonate, silica and clay are frequently
used extenders.
58
• Flame Retardants: Additives that contain
chlorine, bromine, phosphorous or metallic
salts reduce the likelihood that combustion
will occur or spread
• Lubricants: Lubricants such as wax or calcium

stearate reduce the viscosity of the molten
plastic and improve forming characteristics
59
• Pigments: Pigments are used to produce
colors in plastics.
• Plasticizers: alter the properties and forming
characteristics of the plastic. e.g phthalates
used in PVC.
• Reinforcement: The strength and stiffness of
polymers are improved by adding fibers of
glass, carbon etc.
60
• Stabilizers: prevent deterioration of the
polymer due to environmental factors
• Stabilizers also prevent deterioration due to
ultra-violet radiation.
61
Semi-Crystalline Plastics
• Plastics that form crystalline phases are
thermoplastics
• No completely crystalline structure due to the
complex physical nature of the molecular
chains
• polyethylene and nylon can achieve a degree
of crystallinity
• acrylic and polystyrene are always amorphous
62
• Degree of crystallinity is dependent on their
thermal history and hence on the processing
conditions used to produce the molded article
• higher density results when polymer
crystallizes due to closer packing of the
molecules
63
• Typical characteristics of crystalline plastics
• (1) High rigidity especially at elevated
temperatures.
• (2) Low friction and hard wearing
• (3) High hardness
• (4) Resistance to environmental stress
cracking
64
• (5) Can be effectively reinforced
• (6) Ability to be stretched
• (7) Greater creep resistance
• Demerits: (1) always opaque (2) exhibit a

relatively large shrinkage during molding
65
Engineering Plastics
• The term must have originated as a
classification distinguishing those that could
be substituted satisfactorily for metals e.g
aluminum
• A useful definition of an engineering material

is that it is able to support loads more or less
indefinitely
66
• By definition/criterion thermoplastics are at a
disadvantage compared with metals because
of
• (1) Low time-dependent moduli
• (2) Inferior strengths except in rather special
circumstances.
67
• Advantages for the use of polymers include
• (1) Low density
• (2) Resistance to many of the liquids that
corrode metals
• (3) Easy processability
68
• Currently the materials generally regarded as
making up the engineering plastics group are
• (i) Nylon
• (ii) Acetal
• (iii) Polycarbonates
• (iv) Modified polyphenylene oxide (PPO)
• (v) Thermoplastic polyesters
69
• (vi) Polysulphone
• (vii) Polyphenylene sulphide
• Latest developments of high performance,

high temperature plastics are such as
• (i) Polyethersulphone (PES)
• (ii) Polyetheretherketone (PEEK)
• (iii) Polyamide-imide
70
Composites
• Plastics attractive for engineering applications
because of possibility of property
enhancement through fiber reinforcement
• High demand in aerospace and automobile
industries
• Thermosets use long and indeed often
continuous fiber reinforcement
• Thermoplastics use short fiber and high
productivity molding methods
71
Composites
• Glass fibers are the principal form of
reinforcement used for plastics
• other fibers such as aramid (Kevlar) or carbon
fibers are used but these are expensive
• Hybrid systems offer a good balance of
properties at an acceptable price
• (i) the impact properties of carbon-fiber
composites can be improved by the addition
of glass fibers
72
Composites
• the stiffness of glass fiber reinforced plastics
(gfrp) can be increased by the addition of
carbon fibers
• reinforced plastics in a form of dough
• DMC has a dough-like consistency and consists
of short glass fibers (15 – 20%) and fillers (up
to 40%) in a polyester resin. The specific
gravity is in the range 1.7 – 2.1.
73
Composites
• SMC consists of a polyester resin impregnated
with glass fibers (20 – 30%).
• It is supplied as a sheet wound into a roll with
a protective polyethylene film on each side of
the sheet
74
Thermosets
• The use of thermosets have been on the
decline for the following reasons
• (a) Poor image as a material used for old-
fashioned items
• (b) Slow production methods
• (c) Introduction of high temperature
thermoplastics (engineering plastics)
• (d) Miniarization in the electronics industry
75
Polymer Alloys
• concept is similar to metal alloying
• Most common polymer alloy is ABS –
acrylonitrile butadiene and styrene.
• ABS is the largest volume of engineering
thermoplastic with the composition 50%
styrene, 25% butadiene and 25% acrylonitrile.
76
Typical Characteristics of Some
Important Plastics
• (A) Semi-crystalline Plastics
• (i)Low density polyethylene (LDPE): most
widely used plastics.
– Density is in the range 918-935 kg/m3
– Very tough and flexible
– Major Applications: packaging film, domestic
ware, tubing
– electrical insulator – outstanding dielectric
properties
77
Important Plastics
• (ii) Linear Low Density Polyethylene (LLDPE)
introduced by Union Carbide in 1977
• produced by a low pressure process
• has regular structure with short chain
branches.
• For any given density LLDPE is stiffer than
LDPE and
78
Important Plastics
• LLDPE exhibits a higher yield strength and
greater ductility.
• It is replacing LDPE.
• (iii) High density polyethylene (HDPE): has

density in the range 935 – 965 kg/m3
• more crystalline than LDPE.
79
Important Plastics
• Slightly more expensive, much stronger and
stiffer.
• Applications: dustbins, bottle crates, pipes
• (iv) Polypropylene (PP): an extremely versatile

plastic
• Available in many grades and also as a
copolymer (ethylene/propylene).
80
Important Plastics
• It has the lowest density of all thermoplastics
(900 kg/m3)
• Applications: Crates, small machine parts,
tool handles,
• integral hinges – accelerator pedals,
forceps/tweezers because of good fatigue
resistance,
• Fibers e.g ropes, carpet backing, film for
packaging
81
Important Plastics
• (v) Polyamides (nylon): There are several
different types of nylon e.g nylon 6, nylon 66,
nylon 11
• They are noted for strength, stiffness and
toughness
• Applications: Small gears, Bearings, Housing
for power tools.
82
Important Plastics
• Nylon is hygroscopic i.e absorbs moisture
which can affect its structural properties.
• Glass reinforcement reduces this problem to
give extremely strong, impact resistant
materials
• Density of nylon is about 1100 kg/m3.
83
Important Plastics
• (vi) Acetals have superior properties in
strength, stiffness and toughness to nylon
• denser than nylon but in many ways their
properties are similar
• is used for same applications as nylons.
• Acetals have lower water absorption
properties
84
Important Plastics
• available as homopolymer and copolymers
• Homopolymer is slightly stronger and stiffer
than the copolymer
• The copolymer has improved high
temperature performance.
• Copolymer applications are – hot water
plumbing, body for electric kettles.
85
Important Plastics
• (vii) Polytetrafluoroethylene (PTFE): has
excellent chemical resistance and extremely
low coefficient of friction.
• Applications: Bearings in aggressive
environments, insulating tape, gaskets,
pumps, diaphragms, non-stick coatings on
cooking utensils
86
Important Plastics
• (viii) Thermoplastic polyesters: linear
polyesters which are highly crystalline
• Exhibit
– toughness,
– strength and
– abrasion resistance,
– low friction,
– chemical resistance,
– low moisture absorption
87
Important Plastics
• e.g polyethylene terephthalate (PET) whose
processing difficulties have been imposed by
adding polybutylene terephthalate (PBT)
• Applications: Gears, Bearings, Housings,
Impellers, Pulleys, Bumper extensions,
• Replacement for glass in beverage bottles.
88
Important Plastics
• (ix) Polyetheretherketone (PEEK) affords the
possibility of high service temperature.
• Crystalline nature accounts in part for high
resistance to attacks from acids, alkalis and
organic solvents
• commonly used at 200ºC
• Exhibits
– good abrasion resistance
89
Important Plastics
• Exhibits
– low flammability,
– High toughness,
– Good strength, and
– good fatigue resistance
• Applications:
– Wire coatings,
— Electrical connections, Fans, Impellers.
90
Important Plastics
• (B) Amorphous Plastics
• (i) Polyvinyl Chloride (PVC): the most widely
used of the amorphous plastics
• Two forms (a) Plasticized and (b) Unplasticized
• Characteristics include:
– Good weathering,
– Excellent electrical insulation,
– Good surface properties,
– Self-extinguishing
91
Important Plastics
• (a) Plasticized PVC is flexible and used in wire
covering, floor tiles, gloves, rainwear
• (b) Unplasticized PVC (uPVC) is hard, tough
and strong mostly used as building material
e.g Pipes, Window frames, Credit cards.
92
Important Plastics
• (ii) Polymethyl Metharcrylate (PMMA): has
exceptional optical clarity and resistance to
outdoor exposure.
• It is resistant to Alkalis, Detergents, Oils, Dilute
acids but attacked by most solvents.
• Typical Applications:
– Control panels,
– Baths,
– Face guards, Lenses.
93
Important Plastics
• (iii) Polystyrene (PS): available with varying
impact strength from brittle to very tough.
• For its clarity and low cost used for
– vending cups,
– light fittings,
– disposable syringes,
– casings for ball point pens.
94
Important Plastics
• In expanded form it can be used as packaging
material, thermal insulator
95
Important Plastics
• (iv) Acrylonitrile-butadiene-styrene (ABS) have
– superior strength,
– stiffness and
– toughness properties.
• Considered an engineering plastic.
• Comparable to nylon and acetal and generally
less expensive.
96
Important Plastics
• Typical Applications:
– Telephones,
– Fascia panels,
– Hair brush handles,
– Luggage,
– Helmets,
– Lining for refrigerators
97
Important Plastics
• (v) Polycarbonates: It is considered an
engineering plastic because of extreme
toughness.
• They are
– transparent and have
– good temperature resistance
• But are attacked by
– alkaline solutions and
– hydrocarbon solvents.
98
Important Plastics
• Applications:
– Street lamp covers,
– Baby feeding bottles,
– Camera parts,
– Safety equipment,
– Compact discs
99
Important Plastics
• (C) Thermoplastic Rubbers
• 5 types are available based on the source
• (i) Olefinics e.g Santoprene, Alcryn
• (ii) Polyurethanes e.g Caprolan, Pellethane
• (iii) Polyesters e.g Hytrel, Arnitel
• (iv) Styrenics e.g Solprene, Cariflex
• (v) Polyamides e.g Pebax, Dinyl
100
Important Plastics
• (D) Thermosetting Plastics
• very varied in nature. Following are
classifications of these plastics.
• (i) Amines: 2 basic types that exist namely
– (1) Urea formaldehyde and
– (2) Melamine formaldehyde
101
Important Plastics
• hard rigid materials with good abrasion
resistance and mechanical characteristics
which are maintained at continuous use at
100ºC
• Urea formaldehyde is less expensive but
absorbs moisture which can lead to poor
dimensional stability.
• Uses: Bottle caps, Electrical switches, Plugs,
Utensil handle, Trays
102
Important Plastics
• Melamine Formaldehyde: It has lower water
absorption and improved temperature and
chemical resistance.
• Uses:
– Table ware,
– Laminated worktops,
– Electrical fittings
•
103
Important Plastics
• (ii) Phenolics: Phenol formaldehyde (Bakelite)
is the oldest synthetic material available.
• It is
– strong,
– hard and brittle material
– with good creep resistance and
– excellent electrical resistance properties.
– only available in dark colors
104
Important Plastics
• susceptible to attacks by alkalis and oxidizing
agents.
• Uses:
– Domestic electrical fittings,
– Saucepan handles,
– Fan blades,
– Pump parts
105
Important Plastics
• (iii) Polyurethanes: They are available in three
forms namely
– (1) rigid foams
– (2) flexible foam
– (3) elastomer.
• They are characterized by high strength and
good chemical and abrasion resistance.
106
Important Plastics
• Uses:
• (1) Rigid foams are for insulation material
• (2) Flexible foam is for cushion material for
furniture.
• (3) Elastomeric materials are used in solid
tyres and shock absorbers.
107
Important Plastics
• (iv) Polyesters: Main application is as a matrix
for glass fiber reinforcement e.g small boats,
tanks, repair kits for cars.
108
Important Plastics
• (v) Epoxides: Epoxy resins are more expensive
than equivalent thermosets e.g polyesters but
can outperform these materials due to
– better toughness,
– less shrinkage during curing,
– better weatherability,
– lower moisture absorption.
109
Important Plastics
• Uses: Aircraft industry especially when
reinforced with fibers.
• Operating temperature range -25 to 150ºC.
110
Selection of Plastics
• Material selection requires an awareness of
the general behavior of plastics as a group, as
well as familiarity with special characteristics
of individual plastics.
• First and most important steps in the design
process are
– (i) Define clearly the purpose and function of
proposed product
111
• Continuing
– (ii) Identify the service environment
– (iii) Assess the suitability of a range of candidate
materials.
• Important characteristics requiring
consideration for most engineering
components are
• (A) Mechanical properties
112
• (A) Mechanical properties
– Strength
– Stiffness
– Specific strength and stiffness
– Fatigue and toughness
– Influence of high or low temperature on these
properties
– (B) Corrosion susceptibility and degradation
113
• (C) Wear resistance and frictional properties
• (D) Special properties:
– Thermal, electrical,
– optical and
– magnetic properties,
– damping capacity.
• (E) Moulding and/or other methods of
fabrication
114
• (F) Total cost attributable to the selected
material and manufacturing routes
115
Stiffness
• Expressed in terms of a modulus of elasticity
• Young’s Modulus is sometimes difficult to
determine precisely
• Method used is tangent modulus and
determined from the origin
• secant modulus is often quoted to remove
ambiguity
116
Stiffness
• A selected strain value of say 2% (point C')
enables a precise point C on the stress -strain
curve. Young’s Modulus is only useful for
quality control purposes.
117
Stiffness
118
Material Selection for Strength
• to compare the structural efficiency to
calculate their strength desirability factor
• Accepting Load/Weight as a desirability factor,
Df, for a beam y 1/ 2
Df 

• σy = strength of a material
• ρ = density of a material
119
Material Selection for Strength
• Similar desirability factors may be derived for
other geometries
120
Material Selection for Stiffness
• If the service of a compound is in deflection or
stiffness which is the limiting factor rather
than strength, then we need a different
desirability factor
1/ 3
E
Df 

• E = Elastic modulus
• ρ = density of a material
121
Material Selection for Stiffness
• Since for plastics the Modulus, E, is not a
constant it is often necessary to use a long-
term (creep) modulus rather than a short-
term for quality control
122
Ductility
• Inherent nature of plastics is such that high
modulus is associated with low ductility and
steps that are taken to improve the one
causes the other to deteriorate.
123
Ductility
• Relationship between ductility and stiffness
124
Creep and Recovery Behavior
• Plastics exhibit a time-dependent strain
response to a constant applied stress, called
creep.
125
Creep and Recovery Behavior
126
Viscoelasticity
• For an amorphous material:
• At low temperature, amorphous polymer
behaves like a glass.
• At intermediate temperature (above Tg) a
rubbery solid is obtained.
• At high temperature a viscous liquid is
obtained.
127
Viscoelasticity
• For thermoplastic material:
• At low temperature a polymer behaves
elastically obeying Hooke’s law.
• σ = Eε
• At intermediate temperature the polymer in
the rubbery state exhibits combined character
of elastic and fluid flow. This is termed
Viscoelasticity.
128
Viscoelasticity
129
Viscoelasticity
• Elastic deformation is instantaneous as shown
in (12a), (12b). Upon removal of load the
specimen assume its original dimensions.
• For viscous polymer (Fig. 12d)
• Deformation is not instantaneous,
deformation is delayed.
• Deformation is not reversible or completely
recovered after release of stress.
130
Viscoelasticity
• For viscoelastic behavior, (Fig. 12c)
• Deformation is instantaneous followed by a
viscous, time-dependent strain. E.g. silicone
polymer, “silly putty”.
• When rolled into a ball and dropped unto a
solid horizontal surface, it bounces elastically
• When pulled in tension it flows like a highly
viscous liquid
131
Viscoelastic Relaxation Modulus
• Viscoelastic behavior of polymeric materials is
dependent on both time and temperature.
 t 
E r t  
o
• σ(t) – measured time-dependent stress
• εo – constant strain level.
132
• Relaxation modulus
• vs time at different
• temperatures
133
• Stress decreases as time increases due to
molecular relaxation process.
• Temperature increase lowers Er(t)
• For amorphous material
134
135
• Five regions are identifiable
• (1) Glassy Region
• Considering 10sec after stress, material is rigid
and brittle,
• Er(10) is that of elastic modular Strain – time
characteristic as shown in fig 12(b) earlier.
• Long molecular chains are essentially frozen in
position.
136
• (2) Leathery/Glass Transition Region
• As temperature increases, Er decreases
abruptly by factor of 103 in 10°C interval
• Leathery nature, deformation is time
dependent and not totally recoverable on
release of applied load
137
• (3) Rubbery Plateau
• Both elastic and viscous components are
present.
• Deformation is easy to produce because
relaxation modulus is relatively low.
138
• (4,5) Rubbery Flow, Viscous Flow
• The material experiences gradual transition to
soft rubbery state and finally viscous liquid.
• In the viscous region, E decreases dramatically
with temperature increase
• Molecular standpoint, chain motion intensifies
greatly for viscous flow
139
140
• Graph of Er(10) vrs temp for crystalline isotactic
polystyrene, cross-linked atactic and amorphous
polystyrene
• (A) – Crystalline isotactic polystyrene
• (B) – Lightly cross-linked atactic
• (C) – Amorphous polystyrene
• With B Plateau extends to temperature at which
polymer decomposes. Does not experience
melting e.g. Rubber or elastomeric materials
141
• For A – The decrease in Er(10) at Tg is much
less pronounced than the other polystyrene
materials since only a small volume fraction of
this material is amorphous and experiences
the glass transition.
142
Viscoelastic Creep
• Many polymeric materials are susceptible to
time-dependent deformation when the stress
level is maintained constant even at room
temperature
• That is viscoelastic creep
• For example, automobile tyres may develop
flat spots on their contact surfaces after
prolonged time.
143

• Creep tests are performed under isothermal

conditions.
• Creep modulus, Ec(t) defined by

E c t  
 t 
• Where 𝜎𝑜 = constant applied stress
• 𝜀(𝑡) = time-dependent strain
144
Viscoelastic Creep
• Creep modulus is temperature sensitive and diminished with
increasing temperature
• As a general rule, the susceptibility to creep decreases [i.e. Ec(t)
increases] as degree of crystallinity increases.
1
Mathematical Models of Viscoelastic
Behaviour (Maxwell Model)
• spring and dashpot in series
2
• Stress – Strain Relations
• For spring
•  1    1 -------(1)
•  is a material constant
• For the dashpot stress is proportional to strain rate
• 𝜎2 = 𝜂𝜀2 , 𝜂 is a material constant ----(2)
3
• Equilibrium Equation
• For equilibrium of forces, assuming constant area, Applied stress
•    1   2 --------(3)
• Geometry of Deformation Equation
• Total strain equals sum of the two strains
•   1   2 ---------(4)
4
Where

• From equations (1), (2) and (4)
1 1
•𝜀= 𝜎 + 𝜎2
𝜆 1 𝜂
d
 
dt
1 1
•𝜀= 𝜎 + 𝜎 −−−−− −(5)
𝜆 𝜂
• Governing equation of the Maxwell Model
5
• Study its response to predictions of three common time dependent
modes of deformation
• Creep
• Relaxation
• Recovery
6
• Creep
• If a constant stress is applied then equation (5) becomes,
1
   

• Strain rate increases with time
• At t=0, 𝜎 = 𝜎0
7
 


• Strain
8
• For the Maxwell Model (Fig on previous slide), the strain at any time,
t, after application of a constant stress 𝜎𝑜 given by
𝜎𝑜 𝜎𝑜 𝑡
•𝜀 𝑡 = +
𝜆 𝜂
• Hence creep modulus given as
𝜎𝑜 𝜆𝜂
• 𝐸 𝑡 = = −−−−− −(7)
𝜀(𝑡) 𝜂+𝜆𝑡
9
• Relaxation
• If strain is held constant then equation (5) (governing equation)
becomes
1 1
•0= 𝜎 + 𝜎
𝜆 𝜂
• Integrating with    at t = to

 (t )    exp t
  
10
• stress decays exponentially with a time constant η / λ.
• Recovery
• When the stress is removed there is an instantaneous recovery of the
elastic strain, έ,
• From equation 5 (next), the strain rate is zero so that there is no
further recovery (See Fig)
11
1 1
•𝜀= 𝜎 + 𝜎 −−−−− −(5)
𝜆 𝜂
12
• Strain
13
Behaviour (Kelvin or Voigt Model)
• spring and dashpot elements are connected in parallel
14
•  1     1------------(1)
• 𝜎2 = 𝜂𝜀2 −−−− −(2)
• For equilibrium of forces, Eqn 9
  1   2
15
• total strain is equal to the strain in each of the elements, Eqn 10
•    1   2 -----(10)
• From equations (1), (2) and (9) we have
     1  2
• Using equation (10) above, => Kelvin Model
•      ------(11)
16
• Considering Kelvin Model prediction of
• Creep
• Relaxation
• Recovery
• If a constant stress, σo is applied then equation (11) becomes,
     
17
• Solving the differential equation for the total strain, ε,
•        ---------- (12)
 1  exp t 
    
• indicates an exponential increase in strain from zero up to a value


18
• Stress-Time graph of the Kelvin (Voigt) Model
19
• Relaxation
• If the strain is held constant then equation (11) becomes
  
• Stress is constant since in Relaxation strain is constant
20
• Recovery
• If the stress is removed, then equation (11) becomes
0    
• Solving this differential equation with initial condition
  

    exp  t
  
21
• This represents can exponential recovery of strain which is a reversal
of the predicted creep.
22
Behaviour (More Complex Models)
• Kelvin model gives an acceptable first approximation to
• (i) creep and (ii) recovery behavior
• but does not account for (iii) relaxation
• Maxwell model can account for
• relaxation but
• poor in relation to creep and recovery.
• Compromise by combining the two models
23
• Maxwell and Kelvin models in series
24
• Total strain, Eqn (14)
  1   2   k
• where εk is the strain response of the Kelvin model
• From equations (1), (2) and (12), we get Eqn 15 below
   t      2  
   1  exp  t 
1 1 2   2  
25
• From Eqn (15) we derive the Strain rate to be Eqn 16
.     2 
  exp  t
1  2  2 
• The response of this model to creep, relaxation and recovery
26
• Response of combined Maxwell and Kelvin models
27
Behaviour (Standard – Linear Solid)
• The Standard Linear Solid – Zener Model
28
•  1  1 (17)
•  2  2 2 (18)
•  3   3  3 (19)
29
1   3
• Therefore
   1   2
30
• Total deformation
•   
2 1 3 (21)
• From equation (21)

 
1  
3
31
• From equation (20)
 1     2
3   2
1  3

3 
1  3
   2     2 

3 
1 3
32
• Rearranging gives Eqn (22) as the Governing Eqn
 3  1   3 1  2  2 1 

• Rewritten in the form
a1  a o  b1 
  b
• Where a1 , a  , b1are material constants
33
Superposition Principle
• simplest theoretical model to predict the strain response to a
complex stress history
• for a linear viscoelastic material, loading history is simply the
algebraic sum of the strains due to each step in load
• (a) Step change of stress (b) Continuous change of stress
34
• Step Change of Stress
• For material is subjected to a constant stress  

• creep strain t at any time t is
 t  
1
 
E t 
• E(t) is the expression for the time dependent modulus
35
• If another stress  1 is applied at time , u1,
• stress will have been applied for a time (t – u1)
• strain will be given by
 t  
1
1
E t  u1 
• Strain for  and  1 given by
 t  
1 1
  1
E t  E t  u1 
36
• for any series of N step changes of stress we have strain as
 
 t     i 
1

 E t  u i  
•  i step change of stress which occurs at time, u . i
37
COURSE STRUCTURE
• Chemical structure and polymer properties
• Polymer morphology
• Solid structure, crystallography morphology
• Mechanical properties in glassy, rubbery and fluid
states
• Thermal stability
• Flammability and flame resistance
• Chemical resistance
• Product design
• Rheology, rheometry and polymer processing
2
Analysis of Continuous Fiber
Composites
• Greatest improvement in the strength and
stiffness of a plastic achieved with
unidirectional continuous fibers
• Consider a composite with continuous aligned
fibers as shown below.
• Unidirectional fiber composite subjected to

axial force.
3
Composites
4
Composites
• (i) Equilibrium Equation
• The applied force shared by the fibers and the
matrix. Hence
• FcL = Ff + Fm ------------ (1)
• where L = longitudinal fiber direction
• (ii) Geometry of Deformation Equation

• The strain, ε, is the same in the fibers and matrix
and is equal to the strain in the composite.
• εcL = εf = εm -------------- (2)
5
Composites
• Stress – Strain Relationship
• cL = EcLεcL
• σf = Efεf ---------------- (3)
• σm = Emεm
• Combining (2), (3) and (1)
6
Composites
𝐴𝑓 𝐴𝑚
• 𝐸𝑐𝐿 = 𝐸𝑓 + 𝐸𝑚
𝐴𝑐 𝐴𝑐
• Fiber with uniform cross-sectional area
fraction equals the volume fraction so,
• 𝐸𝑐𝐿 = 𝐸𝑓 𝑉𝑓 + 𝐸𝑚 𝑉𝑚 −−−− −(4)

• Rule of Mixtures.
7
Composites
• Used to determine other properties such as
density,
• strength,
• thermal conductivity and
• electrical conductivity in the fiber direction.
8
Composites
• Example 1
• The density of a composite made from
unidirectional glass fibers in an epoxy matrix is
1950kg/m3. If the densities of the glass and
epoxy are known to be 2450kg/m3 and
1300kg/m3, calculate the weight fraction of
fibers in the composite.
9
Composites
• Solution
• From the rule of mixtures
• 𝜌𝑐 = 𝜌𝑓 𝑉𝑓 + 𝜌𝑚 𝑉𝑚
• 𝜌𝑐 = 𝜌𝑓 𝑉𝑓 + 𝜌𝑚 (1 − 𝑉𝑓 )
• Giving Vf = 0.5652
10
Composites
• Using equation (A):
𝑤𝑓 𝜌𝑓 𝑣𝑓 𝜌𝑓
• 𝑊𝑓 = = = 𝑉𝑓 −−− −(𝐴)
𝑤𝑐 𝜌𝑐 𝑣𝑐 𝜌𝑐
•
𝜌𝑓 2540
• 𝑊𝑓 = 𝑉𝑓 = 0.5652 = 0.710
𝜌𝑐 1950
11
Composites
• PEEK is to be reinforced with 30% by volume
of unidirectional carbon fibers and the
properties of the individual materials are
given below. Calculate the density, modulus
and strength of the composite in the fiber
direction.
12
Composites
Material Density Tensile Modulus
(kg/m3) strength (GN/m2)
(GN/m2)
PEEK 1300 0.058 3.8
Carbon 1800 2.1 400

fiber
13
Composites
• Solution
• From the rule of mixtures
• Density of composite in longitudinal direction
• 𝜌𝑐 = 𝜌𝑓 𝑉𝑓 + 𝜌𝑚 𝑉𝑚
• 𝜌𝑐 = 0.3 1800 + 0.7 1300 =
1450 𝑘𝑔/𝑚3
14
Composites
• Strength of composite
• 𝜎𝑐 = 𝜎𝑓 𝑉𝑓 + 𝜎𝑚 𝑉𝑚
• 𝜎𝑐 = 0.3 2.1 + 0.7 0.058 = 0.67 𝐺𝑁/
𝑚2
• Modulus of composite
• 𝐸𝑐𝐿 = 𝐸𝑓 𝑉𝑓 + 𝐸𝑚 𝑉𝑚
• 𝐸𝑐𝐿 = 0.3 400 + 0.7 3.8 = 122.7 𝐺𝑁/
𝑚2
15
Composites
• Example 3
• Calculate the fraction of the applied force
which will be taken by the fibers in the
composite referred to in Example 2.
• Solution
• From Equations (1), (2) and (3)
16
Composites
• 𝐹𝑓 = 𝜎𝑓 𝐴𝑓 = 𝐸𝑓 𝜀𝑓 𝑉𝑓 𝑣𝑐
• Since for uniform cross section,
• 𝐴𝑓 = 𝑉𝑓
• And
𝑣𝑓 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑓𝑖𝑏𝑒𝑟
• 𝑉𝑓 = =
𝑣𝑐 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑒
•
17
Composites
• Similarly, the force in the composite is given
by
• 𝐹𝑐𝐿 = 𝐸𝑓 𝜀𝑓 𝑉𝑓 𝑣𝑐 + 𝐸𝑚 𝜀𝑚 𝑉𝑚 𝑣𝑐
• Hence
𝐹𝑓 𝐸𝑓 𝑉𝑓
• = = 0.978
𝐹𝑐𝐿 𝐸𝑓 𝑉𝑓 +𝐸𝑚 𝑉𝑚
• A very large percentage of the applied force is
carried by the fibers.
18
Composites
• From the rule of mixtures,
• 𝜎𝑐 = 𝜎𝑓 𝑉𝑓 + 𝜎𝑚 𝑉𝑚
𝜎𝑐𝐿 𝜎𝑚
• = 𝑉𝑓 + 1 − 𝑉𝑓
𝜎𝑓 𝜎𝑓
• As the strains are the same in matrix and
fibers,
𝜎𝑚 𝐸𝑚
• =
𝜎𝑓 𝐸𝑓
19
Composites
𝜎𝑐𝐿 𝐸𝑚
• = 𝑉𝑓 + 1 − 𝑉𝑓
𝜎𝑓 𝐸𝑓
𝜎𝑐𝐿 3.8
• = 0.3 + 0.7 = 0.307
𝜎𝑓 400
𝜎𝑓
• Thus, = 3.26
𝜎𝑐𝐿
20
C’est Finis
21

Mse 356 Engineering Properties of Polymers

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Mse 356 Engineering Properties of Polymers

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MSE 356 ENGINEERING PROPERTIES

• chain-folded layers increase in lateral

Material Tg (°C) Tm (°C)

Polyethylene (LD) -110 115

Polyethylene (HD) -90 137

Polypropylene -18 175

Polyvinyl chloride 87 212

Polycarbonate 150 265

• Lubricants: Lubricants such as wax or calcium

• Demerits: (1) always opaque (2) exhibit a

• A useful definition of an engineering material

• Latest developments of high performance,

• (iii) High density polyethylene (HDPE): has

• (iv) Polypropylene (PP): an extremely versatile

• For amorphous material

• Creep tests are performed under isothermal

Mathematical Models of Viscoelastic

• From equation (21)

 3  1   3 1  2  2 1 

• Strain for  and  1 given by

• Unidirectional fiber composite subjected to

• (ii) Geometry of Deformation Equation

• Combining (2), (3) and (1)

• 𝐸𝑐𝐿 = 𝐸𝑓 𝑉𝑓 + 𝐸𝑚 𝑉𝑚 −−−− −(4)

Carbon 1800 2.1 400

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