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Essentials of Polymer Engineering (Introduction to Polymers

ChE 197 Mechanical Properties of Polymers

What we have discussed so far
• • • • • • • • • • Introduction – basic concepts and definitions; classification of polymers Polymerization mechanisms – chain-reaction; ionic and coordination polymerization; step-growth and ring-opening polymerization Chemical bonding and polymer structure – primary, secondary, and tertiary structures Thermal transition in polymers – Tg and Tm Polymer modification – copolymerization; postpolymerization reactions; functional polymers Condensation (Step-Reaction) polymerization – mechanism; kinetics; stoichiometry; molecular weight control and distribution Chain-Reaction (Addition) Polymerization Copolymerization Solution properties of polymers – solubility parameter, conformations of polymer chains in solutions, thermodynamics of polymer solutions, solution viscosity Mechanical properties of polymers – mechanical tests, stress-strain behavior, deformation, compression vs tensile tests, effects of structural and environmental factors

General Outline
• Mechanical tests – stress-strain experiments; creep experiments; stress relaxation experiments; dynamic mechanical experiments; impact experiments • Stress-strain behavior – elastic stress-strain relations; deformation of solid polymers; compression vs. tensile tests • Effect of structural and environmental factors on mechanical properties – MW, cross-linking, crystallinity, copolymerization, plasticizers, polarity, streric factors, temperature, strain rate, pressure

Overview on mechanical properties of polymers
• Mechanical stability and durability coupled w/ their light weight – preferable alternative to ceramics and metals • Mechanical behavior – function of microstructure or morphology • Strong dependence to temperature and time (viscoelastic behavior) • Linear elastic behavior yield phenomena plastic deformation/cold drawing

no visible signs of yielding since they occur at strengths well below the tensile strength of the material A variety of test methods exist for predicting mechanical performance limits under a variety of loading conditions. . controlling property is the yield strength and corresponding strain Fracture– cracks are regions of material discontinuity. fracture can be brittle or through fatigue Brittle fracture – occurs where the absence of local yielding results in a build-up of localized stresses Fatigue failure . controlling property is the elastic modulus Yielding or excessive plastic deformation – in carrying design loads and occasional accidental overloads. load-bearing applications. inadequate rigidity or are subjected to alternating or repeated loads.Mechanical tests Failure of a polymer to perform its function can be due to: Excessive elastic deformation – in structural. precipitates failure through fracture. inadequate strength properties.

Stress-Strain Experiments Specimen is deformed (pulled) at a constant rate. and the stress required for this deformation is measured simultaneously This test can be enhanced if they can be carried out over a wide range of temperatures and strain rates .

and the strain is measured as a function of time The elongation may be measured at time intervals using a travelling microscope. Can be done in tension. flexure.Creep Experiments Specimen is subjected to a constant load. Measurements may be conducted in an environmental chamber. torsion. shear. or compression Usually measures compliance .

instantaneously) extended a given amount. and the stress required to maintain this constant strain is measured as a function of time Stress that is required to maintain the strain constant decays with time Usually measures the relaxation modulus Er(t.T) = time-varying stress over constant strain .Stress Relaxation Experiments Specimen is rapidly (ideally.

a polymer sample is clamped at one end.Dynamic Mechanical Experiments Response of a material to periodic stress is measured Torsion pendulum . and the other end is attached to a disk that is free to oscillate Provide useful information about the viscoelastic nature of a polymer .

Sinusoidal stress and strain are out of phase by an angle δ .Dynamic Mechanical Experiments Assume we impose a sinusoidal strain to two types of materials (extreme): 1) elastic and 2) viscous ε0 – amplitude ω – frequency (rad/s. response falls between the two extremes. by Newton’s law of viscosity: Stress and strain are 900 out of phase! G – shear modulus In case of polymers (viscoelastic materials). = 2πf) Stress response if material is purely elastic. by Hooke’s law: Stress and strain are in phase! Stress response if material is purely viscous.

and viscoelastic materials. . elastic.Dynamic Mechanical Experiments Phase relation is shown between dynamic strain and stress for viscous.

Dynamic Mechanical Experiments Lag angle between stress and strain is defined by the dissipation factor or tan δ Denotes material damping characteristics Ratio of energy viscously dissipated as heat G” over the maximum energy stored in the material G’ during one cycle of oscillation Complex modulus G = G’ + iG” We can measure damping from experiments: A1 and A2 are the amplitudes of two consecutive peaks This may be expressed in terms of log decrement (Δ) for free vibration instruments like the torsional pendulum .

notched cantilever specimen that is clamped rigidly at one end and then struck at the other end by a pendulum weight Brittle polymers (e.Impact Experiments Prediction of failure due to rapid stress loading (impact load) Measurement of the area under the stress strain curve in the high-speed (rapid) tensile test Falling ball or dart test .g. PA.measurement of the energy required to break a H × H in.measurement of the energy required to break a specimen by a ball of known weight released from a predetermined height Izod test .g. PS) – low impact resistance Engineering thermoplastics (e. PC) – high impact resistance/impact strength Charpy test .hammerlike weight strikes a notched specimen that is rigidly held at both ends .

Stress-Strain Behaviors of Polymers Typical polymer specimen for the tensile test L0 – initial gauge length Dog bone shape – encourages failure at the thinner middle portion It is clamped at both ends and pulled at one of the clamped ends (usually downward) at constant elongation Engineering (nominal) stress Engineering (nominal) strain .

Stress-Strain Behaviors of Polymers Engineering stress–strain curves generally depend on the shape of the specimen Plot of true stress vs true strain . dL. divided by the instantaneous length L True strain and engineering strain σt = σ ⋅ L = σ ⋅ (1 + ε ) L0 True stress and engineering stress Note: AL = A0L0 since plastic deformation is a constant volume process up to the onset of necking For small deformations true stress ≈ engineering stress .more accurate measure of intrinsic material performance Ratio of the measured force (F) to the instantaneous cross-sectional area (A) at a given elongation Sum of all the instantaneous length changes.

it responds elastically Since stress may act on a plane in different ways. this constant is defined in different ways depending on the applied force and the resultant strain τ = Gγ τ – shear stress G – shear modulus Elastic shear strain = tangent of angle of deformation .Elastic Stress-Strain Relations When a material is subjected to small stresses.

Elastic Stress-Strain Relations D= ∆V Dilatation strain V K – bulk modulus E – Young’s modulus (or modulus of elasticity) σ = KD Majority of cases – mixture of shear and dilatation (tensile and compressive tests) For most polymers.5 (incompressible materials. constant volume deformation) Axial elongation accompanied by transverse contractions For isotropic materials w/ elastic deformations: . there is a change in volume Poisson’s ratio v = 0.

Calculate: a) True stress. b) True strain.Example 1 In a tension test. a brittle polymer experienced an elastic engineering strain of 2% at a stress level of 35 MN/m2. and c) fractional change in crosssectional area .

. For a strain of 0. calculate the shear stress and the percentage change in volume.Example 2 Polypropylene has an elastic modulus of 2 × 105 psi and Poisson’s ratio of 0.32.05.

ability of deformed bodies to recover their original dimensions Plastic deformation . a material will experience a permanent set or deformation even when the load is removed .beyond the limit of elastic behavior (elastic limit). a solid will recover its original dimensions on the removal of the applied loads.up to a certain limiting load. Elastic deformation . all materials under the influence of external load undergo some deformation.Deformation of Solid Polymers To relieve stress.

or Young’s.Deformation of Solid Polymers Gradient of the initial linear portion of the curve. modulus Maximum on the curve denotes the yield strength marks the limit of usable elastic behavior or the onset of plastic deformation Stress at which fracture occurs (material breaks apart) = ultimate tensile strength or. simply. tensile strength σB . within which Hooke’s law is obeyed. gives the elastic.

tensile strength or stress at which the specimen ruptures σB. area under the elastic portion of the stress-strain curve gives the resilient energy • Strength — ability to sustain dead load. magnitude of the modulus of elasticity is a measure of this ability or property • Elasticity — ability to undergo reversible deformation or carry stress without suffering a permanent deformation. • Toughness — ability to absorb energy and undergo extensive plastic deformation without rupturing. area under the stress-strain curve .Deformation of Solid Polymers – Physical Significance of Measured Parameters • Stiffness — ability to carry stress without changing dimension. elastic limit or yield point • Resilience — ability to absorb energy without suffering permanent deformation.

reaching a critical level at which abrupt failure occurs Ductile polymers .ability to undergo plastic with little or no plastic deformation. no ability for local yielding. this property assists in the redistribution of localized stresses . local stresses build up around inherent flaws.Deformation of Solid Polymers Brittle polymers .

Deformation of Solid Polymers At small strains. reduction of the instantaneous modulus. from bond angle deformation and bond stretching Further increase in strain straininduced softening . become oriented in the direction of the applied tensile stress . uncoiling and straightening of chains Onset of necking increase in the local stress at the necked region due to the reduction in the load-bearing cross-sectional area (cold drawing) Schematic representation of macroscopic changes in Polymer chains in the amorphous tensile specimen shape during cold drawing regions undergo conformational changes. polymers (both amorphous and crystalline) linear elastic behavior.

Example 3 The mechanical properties of nylon 6.5% has an elastic modulus of 1.8 GN/m2. In the elastic region: . A nylon specimen with a moisture content (MC) of 2.2% is 2. Calculate the elastic energy or work per unit volume in each sample subjected to a tensile strain of 10%.2 GN/m2. while that for a sample of moisture content of 0.6 vary with its moisture content.

5% and 0.Example 4 Two nylon samples of moisture contents 2.2% have εB of 300% and 60%. respectively. Calculate the toughness of each sample if the stress-strain curve of nylon for plastic deformation is given by: .

Compression versus Tensile Tests Normal stresses can be either tensile or compressive Compressive stress–strain data for two amorphous polymers: polyvinyl chloride (PVC) and cellulose acetate (CA) Compressive stress–strain data for two crystalline polymers: polytetrafluoroethylene (PTFE) and polychlorotrifluoroethylene (PCTFE) Stress–strain curves for the amorphous polymers are characteristic of the yield behavior of polymers. no clearly defined yield points for the crystalline polymers .

polystyrene. under tension and compression. Compressive stresses close open cracks. brittle fracture occurs by propagation of these cracks Stress–strain behavior of a normally brittle polymer.Compression versus Tensile Tests In tension polystyrene exhibited brittle failure In compression behaved as a ductile polymer Strength and yield stress are generally higher in compression than in tension Tensile properties of brittle materials depend to a considerable extent on the cracks and other flaws inherent in the material. enhances strength .

the tensile strength must be at least twice the shear strength (theoretical only) .Criterion for plastic deformation to occur during application of tensile stress Shear stress on A’ Max shear stress at φ = π/4 Plastic deformation occurs when τmax is at least equal to the yield strength of the material Generation of shear stress due to uniaxial loading for plastic deformation to occur. the imposed tensile stress must be at least twice the magnitude of the shear stresses generated.

and high-molecular-weight materials. also in location of Tg and modulus drop High MW high number of entanglements high T at which viscous flow becomes predominant over rubbery behavior. polymer is rubbery or viscous at room temp MW has practically no effect on the modulus in the glassy region.Effects of Structural and Environmental Factors on Mechanical Properties – Molecular Weight T < Tg – glassy region T = Tg – transition from glassy to rubbery T > Tg – rubbery region T = Tfl – transition from rubbery to melt flow If Tg > room temp.represent low-. medium-. Tfl′. polymer is rigid at room temp If Tg < room temp. longer rubber plateau Schematic representation of the effect of molecular weight on shear modulus temperature curve. respectively . Tfl″. Tfl”’ . Tg is the glass transition temperature while Tfl is the flow temperature.

mean number of chain atoms between successive cross-links is indicated (Mc). low Mc.Effects of Structural and Environmental Factors on Mechanical Properties – Cross-Linking Glassy region increase in modulus due to cross-linking is relatively small Increase in modulus in the rubbery region and the disappearance of the flow regions Cross-linking raises the glass transition temperature at high values of cross-link density Cross-linking increases polymer ability to resist deformation under load increases its modulus Effect of cross-linking on shear modulus of natural rubber. high cross-link density .

Estimate the average molecular weight between cross-links for both materials if their respective moduli at room temperature are 106 and 108 dynes/cm2. T = absolute temperature. and G = shear modulus Hard rubber Soft rubber .90 g/cm3. average molecular weight between cross-links ρ = density.19 and 0. respectively. R = gas constant.Example 5 The densities of hard and soft rubbers are 1.

Effects of Structural and Environmental Factors on Mechanical Properties – Crystallinity Crystallinity has only a small effect on modulus below the Tg but has a pronounced effect above the Tg Intensity of modulus drop at the Tg decreases with increasing degree of crystallinity Sharper drop at the melting point Effect of crystallinity on the modulus temperature curve. The numbers of the curves are rough approximations of the percentage of crystallinity Melting temperature generally increases with increasing degree of crystallinity .

(A) either a second homopolymer or plasticized B. (B) Unplasticized homopolymer. . shifts the the modulus–temperature curve Effect of plasticization or copolymerization on the modulus–temperature curve. The curves correspond to different copolymer compositions. block and graft copolymers with sufficiently long sequences exhibit phase separation Random and alternating copolymers single transition that is intermediate between those of the two homopolymers of A and B.Effects of Structural and Environmental Factors on Mechanical Properties – Copolymerization Random and alternating copolymers are homogeneous.

Tg of postyrene = 100oC) Behaves like a polybutadiene (rubber) matrix reinforced with polystyrene (hard) phase Shear modulus as a function of temperature for styrene–butadiene–styrene block copolymers.Effects of Structural and Environmental Factors on Mechanical Properties – Copolymerization Block and graft copolymers.% styrene is indicated on each curve . one for each of the homopolymers modulus–temperature curve shows two steep drops (Tg of poly butadiene = -800C. which exist as a two-phase system. Wt. have two distinct glass transitions.

Effects of Structural and Environmental Factors on Mechanical Properties . (B) Unplasticized homopolymer.Plasticizers Effect of plasticization or copolymerization on the modulus–temperature curve. The curves correspond to different copolymer compositions. (A) either a second homopolymer or plasticized B. .

Effects of Structural and Environmental Factors on Mechanical Properties . Effect of the substitution of the chlorine atom for the methyl group depends on the molecular environment of the chlorine atom. Shear modulus (a) and damping (b) as a function of temperature: solid line is PVC. dashed line is PP .Polarity Tg of polar poly(vinyl chloride) is about 90°C higher than that of the nonpolar polypropylene.

Effects of Structural and Environmental Factors on Mechanical Properties . (––––) poly(n-propyl methacrylate .Polarity Tg of poly(2-chloroethyl methacrylate) is only 20°C higher than that of poly(npropyl methacrylate) Shear modulus (a) and damping (b) at 1 Hz as a function of temperature: (———) poly(2-chloroethyl methacrylate).

while stiff side chains increase Tg Long.Effects of Structural and Environmental Factors on Mechanical Properties – Steric Factors Long. flexible side chains increase the free volume and ease the steric hindrance from neighboring chains and as such facilitate the movement of the main chain Increase in modulus in the glassy region with increase in length of the alkyl group for poly(n-alkyl methacrylate). flexible side chains reduce Tg. Shear modulus (a) and damping (b) at 1 Hz as a function of temperature for poly(n-alkyl methacrylate): (––––) Polymethyl methacrylate. (· · · ·) poly(n-butyl methacrylate) . (— — —) poly(n-propyl methacrylate). (– – –) polyethyl methacrylate.

Effects of Structural and Environmental Factors on Mechanical Properties – Steric Factors Brittleness temperatures for polyacrylates as a function of the total length of the side chain Softening temperature of polyolefins with branched side chains .

Effects of Structural and Environmental Factors on Mechanical Properties – Steric Factors Effects of the Introduction of Rings into the Main Chain of Some Polyamides .

Effects of Structural and Environmental Factors on Mechanical Properties – Steric Factors Polymer Stiffening Due to the Introduction of Rings into the Main Chain .

brittle polymer As the temperature is increased. the modulus and yield strength decrease and the polymer becomes more ductile Stress–strain behavior of cellulose acetate at different temperatures .Effects of Structural and Environmental Factors on Mechanical Properties – Temperature Modulus of a polymer decreases with increasing temperature Below the Tg. the modulus is high. no yield point.

Effects of Structural and Environmental Factors on Mechanical Properties – Strain Rate Polymers are very sensitive to the rate of testing As the strain rate increases. polymers in general show a decrease in ductility while the modulus and the yield or tensile strength increase Effect of decreasing temperature is equivalent to that of increasing the strain rate Schematic illustration of the effect of strain rate on polymers .

Effects of Structural and Environmental Factors on Mechanical Properties – Pressure Modulus and yield stress increase with increasing pressure Tensile strength tends to increase for ductile polymers. but decreases for most brittle polymers The stress–strain behavior of polypropylene at different pressures Increase in pressure decrease in free volume increase in packing density . but decrease for some brittle polymers Elongation at break increases for some ductile polymers.