Lecture 6: Polymers Characteristics, Applications, and Processing

Mechanical Properties
z i.e. stress-strain behavior of polymers
Fracture while deforming elastically

3 different stress-starin

brittle polymer

FS of polymer ca. 10% that of metals

Like metallic materials, initially elastic, followed by yielding and plastic deformation

plastic elastomer

Totally rubber like elasticitylarre recoverable stain at low stress rate

Stress at which fracture occursis the strength of plastic polymer

Is the max on curve, stress at max is yield strength

Example :T and Strain Rate of Thermoplastics

Decreasing T... -- increases E -- increases TS -- decreases %EL Increasing strain rate... -- same effects as decreasing T.

Viscoelastic Deformation
z Amorphous polymer z Behave like glass at low temperature z Rubbery at intermediate temp (above Tg) z Viscous liquid at high temperature z For intermediate temperature, ploymer is rubbery solid and exhibit combined mec characteristic viscoelasticity

Load versus time, load applied at t and released at tr

Elastic deformation-upon releasing the stress, deformation totally recoverable-specimen its in original dimension

Viscous behaviour-deformation is not instaneous with stress, deformation delayed depend on time and not reversible or recovered after stress released

Intermediate Viscouselastic behaviour- results in instaneous elastic strain, followed by viscous, time dependent strain, a form of 6 anelasticity

z Viscoelasticity behaviour dependent on time and temperature z Measured by stress relaxation test z Specimen initially strained rapidly in tension to determine the stain level.

 Stress relaxation test:

Stress necessary to maintain the strain is measured as a function of timeStress decrease with time- due to molecular relaxation process

To represent the influence of temp consider points taken at t1 Er vs temperature

tensile test

strain (t) time

Relaxation modulus:
(t ) E r (t ) = o
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glassy region materials rigid and brittle

Small relax

Molecular chain frozen at these temps Strain-time characteristic represent elastic behaviour

Transition region

Temp further increases, Er drops to about a factor 103 Define lathery or glass transition temperature, Tg amorphous solid polymer change to rigid rubbery state Strain-time not recoverable Rubbery plateau -> elastic and viscous manner
High temperature region rubbery flow and viscous flow then transition to viscous liquid (strain-time: viscous)

Large relax

Easily deformed as Er low

Polymer Fracture
Crack form at stress concentration point (scratches,sharp flaw) Stress amplified at tips of crack and leading to propagation and fracture Crazing associated with region of localized plastic deformation which lead to the formation of small and interconnected microvoids fibrillar bridges form between microvoids The bridges elongates and break causing the microvoids to grow and join together to form crack
alligned chains

Adapted from Fig. 15.9, Callister 7e.

fibrillar bridges

microvoids

crack

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Tensile Response: Brittle Failure

Near Failure

(MPa)
x brittle failure
onset of necking

plastic failure

x
Initial unload/reload

aligned, networked crosscase linked case

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Semicrystalline- Elastic and plastic deformation

(MPa)

onset of necking

plastic failure

x
unload/reload

fibrillar structure Orientation near of block failure segments and tie chain with the tensile axis

Interlamella amorphous region Lamella crystalline region Initial stageelongation of amorphous tie chain
crystalline regions slide

Separation of crystalline block segment

crystalline crystalline region regions align aligned due to

starching of crystalline regions

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Application -Predeformation by Drawing

Drawing(ex: monofilament fishline) -- stretches the polymer prior to use -- aligns chains in the stretching direction Results of drawing: -- increases the elastic modulus (E) in the stretching direction -- increases the tensile strength (TS) in the stretching direction -- decreases ductility (%EL) Annealing after drawing... -- decreases alignment -- reverses effects of drawing.

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Tensile Response: Elastomer Case

(MPa)
x brittle failure

plastic failure

elastomer

initial: amorphous chains are kinked, cross-linked. Deformation is reversible!

final: chains are straight, still cross-linked

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Melting and Glass Transition Temp.

Melting temperature z Transformation solid (ordered structure) to liquid (highly random) The Glass Transition Temp z Transition form rubbery to rigid state

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Factor affect the Tm and Tg

z z Both Tm and Tg increase with increasing chain stiffness Chain stiffness increased by { Bulky sidegroups (H compare CH3 on polyproplene-CH3 restrict molecular rotation) { Polar groups or sidegroups (Cl, OH increase in intermolecular bonding forces) { Double bonds or aromatic chain groups (lower chain flexibility)

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Factor affect the Tm and Tg

z Molecular weight (Refer to the diagram) z Degree of branching (more side branch-more defects-lower Tm. . High density PE (linear polymer), high Tm compare to low density PE which has more branching z In the case of Tg, small amount of branching lower Tg but high density of branches reduces chain mobility, and increase the Tg

T
mobile liquid viscous liquid Callister, rubber Fig. 16.9 tough plastic partially crystalline solid
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Tm Tg

crystalline solid

Molecular weight

Homework
z Read on the Polymer synthesis and Processing

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Processing Plastics - Molding

z Compression and transfer molding
{ thermoplastic or thermoset

Mixed polymer and additives placed in mold cavity Both mold are heated One mold is movable, so it is closed and heat and pressure applied-become viscous and flow to match to the mold shape
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Processing Plastics - Molding

z Injection molding
{thermoplastic & some thermosets
Pelletized materials fed into heating chamber by motion of ram

Once solidified, mold opened

Melts to form viscous liquid-then impelled by ram motion through nozzle to cavity
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Processing Plastics Extrusion

Solidification by water or blower

Is molding of a viscous thermoplastic under pressure through an open ended die

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Polymer Types
z Coatings thin film on surface i.e. paint, varnish
{ To protect item { Improve appearance { Electrical insulation

Adhesives produce bond between two adherent Usually bonded by:

1. Secondary bonds 2. Mechanical bonding

Films blown film extrusion Foams gas bubbles in plastic

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Fabrication of Fibre
Materials is heatedviscous liquid pumped through spinneret (small holes) fibre formed solidified by cooling Two technique 1. Dry spinning Polymer dissolved in volatile solvent pump through spinneret into heated zone fibre solidify as solvent evaporate 2. Wet spinning Fibre formed by passing a polymer solvent solution through spinneret direct into second solution that form fibres (precipitation)

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Fabrication of film
Film are extruded through die slit, followed by rolling or drawing to reduce thickness and improve strength

Or film can be blown-continuous tubing is extruded through die, then by applying gas pressure inside the tube and by drawing the film in axial direction the materials expands around trapped air bubble-the wall thickness reduces and form cylindrical film which can be sealed at end to make bags

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Advanced Polymers
z Ultrahigh molecular weight polyethylene (UHMWPE)
{ Molecular weight ca. 4 x 106 g/mol { Excellent properties for variety of applications
z bullet-proof vest, golf ball covers, hip joints, etc.

UHMWPE

Adapted from chapteropening photograph, Chapter 22, Callister 7e.

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