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Structure and properties of polymers

What are polymers?


Mostly long-chain hydrocarbon molecules with: Strong covalent bonds between the molecules along the chain, and EITHER weak secondary bonds between the carbon chains OR strong covalent bonds cross-linking adjacent carbon chains

Includes plastics (polypropylene, nylon, PVC, polystyrene.), natural polymers (shellac, amber, cellulose) and biopolymers (proteins etc). Mechanical properties vary from one polymer to another, and depend on temperature and processing.

If chains can be aligned, the structure can become partially crystalline. But frequently the chains are entangled (amorphous)

Tensile deformation of a semi-crystalline polymer


Elastic deformation:
Amorphous regions elongate i.e. untangling of the carbon chains

Plastic deformation:
Crystalline regions align i.e. orientate in direction of stress Cold drawing Crystalline regions slide past each other and Chains in the amorphous regions are drawn out

BUT, to move molecules around (plastic deformation) needs time and temperature (see later)

Mechanical properties of polymers tend to be very sensitive to (i) temperature and (ii) rate of deformation:

PMMA

Force vs. extension for polyethylene stretched at different strain-rates:

(i)

(ii)

Visco-elastic behaviour
Above the polymers glass transition temperature Tg, polymers show a visco-elastic behaviour as the polymer chains only slowly respond to the applied stress:

Load cycle

Elastic behaviour

Visco elastic

Viscous

Popular polymers
PE PVC PTFE polyethylene low density, low strength & impact resistant, Tmelt ~ 120oC polyvinyl chloride high strength, stiff unless plasticizer added, Tmelt~210oC Bottles, toys, filmwrap Flooring, pipes, wire insulation, old LPs Seals, pipes, bearings, high-T electronics Bottles, packaging film, luggage Wall tiles, toys, indoor lighting Lenses, outdoor signs

polytetrafluor high density, low stiffness, Tmelt oethylene ~327oC, chemically inert, good electrical insulator, low friction teflon polypropylene polystyrene low density, Tmelt~175oC, cheap low ductility, cheap medium strength, low ductility, transparent, weather resistant

PP PS

PMMA polymethyl methacrylate

http://video.google.co.uk/videoplay?docid=5994300959507748421&ei=SkL0SrTdPNCr-Aa7nt28BA&q=polymer+history+and+nylon&hl=en# http://www.youtube.com/watch?v=7nCfbZwGWK8&feature=player_embedded

Polyethylene

HIGH DENSITY POLYETHYLENE


Linear carbon chains Shorter, stronger secondary bond Higher strength and density

LOW DENSITY POLYETHYLENE


Branched carbon chains Longer, weaker secondary bond Lower strength and density

High levels of crystallinity poss.

Low levels of crystallinity

PVC and polypropylene


PVC # Very strong dipole (secondary bond) # Strong, stiff, brittle

POLYPROPYLENE
# Regular side groups ~>low density # Weak secondary bond

# Strength due to entangling caused by side groups

Polystyrene & PMMA

POLYSTYRENE

POLYMETHYLMETHACRYLATE Strong dipole; large side group Brittle; amorphous

(Further reading: William D Callister Chapters 14 & 15)

Structure and properties of ceramics

Types of ceramics
Ceramic materials Clay products Advanced ceramics

Glasses

Refractories

Abrasives

Glasses

Glass ceramics Structural clay products

Fireclay

Basic

Cements

Whitewares

Silica

Special

Inorganic, non-metallic materials: mostly compounds between metallic and non-metallic elements e.g. oxides, nitrides, carbides etc

Glasses
Glasses
Non crystalline (amorphous) silicates contain other oxides (notably CaO, Na2O, K2O and Al2O3) which influence properties

Glass ceramics
Fine grained polycrystalline structure Formed by heat treatment of glasses Better strength and thermal shock resistance

Refractories and Abrasives


REFRACTORIES ABRASIVES

Can withstand high temperatures without melting or decomposing


Used for furnace linings Mostly based upon alumina (Al2O3) and silica (SiO2) Basic refractories based on MgO

Used to wear, cut or grind away material


Require high hardness plus some toughness and refractoriness Silicon carbide (SiC) Tungsten carbide (WC) Corundum (Al2O3) Silica Diamond

Clays
A plastic, earthy natural mineral of alumina and silica found in the ground.
Formed from rocks that were slowly dissolved in water. When the solutions get supersaturated, tiny clay crystals start to grow from the solution.

Structural clay: bricks, tiles, sewer pipes Whiteware: tableware, sanitary ware

Cement
Produced by mixing clay and lime in proportion and heating together (calcination) Principle constituent are calcium silicates. Hardening due to the hydration reactions of calcium silicates (chemical reactions with water) NOT from drying.
Microstructure:

Constituent of concrete: added to bind aggregate particles (sand, gravel) to form a composite material.

voids (black)

hydrated cement (grey)


unhydrated cement (white)

Deformation of Ceramics
At room temperature, most ceramics fracture before any plastic deformation --> catastrophic BRITTLE fracture

Strength determined by porosity levels.

PLASTIC deformation can occur (eg at high temps), but it is difficult as most ceramics are either: (i) ionic crystals e.g. MgO, NaCl, ZnS etc - dislocations cannot easily move, or (ii) covalent crystals e.g. silcates, aluminates (rock etc), WC etc with VERY strong bonds between atoms, or (iii) non-crystalline (amorphous) e.g. fused/vitreous silica glass, - dislocations dont exist. Plastic deformation is by viscous flow of atoms (like a very viscous liquid)

Tension/Compression Testing of Ceramics


For metals, the compressive strength is basically the same as the tensile yield strength. However, CERAMICS are much stronger in compression than in tension, as they are often full of micro-cracks (causing failure in tension). Hence tend not to use the tensile test (gripping ceramic test specimens without breaking them is also difficult)! Instead often use a standard 3-point bend test to measure elastic (Youngs) modulus, and rupture strength (stress at failure): Youngs modulus (GPa) SiC Al203 Glass (steel 345 360 70 200

Rupture stress (MPa) 100-1100 300-700 100 200-600)

Concrete: compressive strength of concrete typically 15-40 MPa (c.f. a tensile strength of only 1-4 MPa), but only achieved after ~4 weeks of curing.

World consumption of hydrocarbons (left column), metals, polymers, building materials and C-fibre composites:

Fig 20.1 in Ashby

Structure and properties of composite materials

Materials.

Tyres are also composites: rayon cloth, steel bands and nylon belts all set in a matrix (binder) of rubber from Ashby

+ plastic

Bundle of fiberglass

CFRP tail

+ plastic

of an RC helicopter

Fabric made of woven carbon filaments

http://science.discovery.com/videos/how-its-made-bicycle-frames.html

What is a composite material?


Two or more individual materials (metal, polymer or ceramic) combined. Frequently two phases (Matrix & Dispersed reinforcement) Examples: FRP (fibreglass glass fibre reinforced polymer) CFRP (carbon fibre) i.e. Ceramic fibres bonded together (reinforced) by a polymer resin Principle of combined action: composite can exhibit combined properties of constituents, and allows property trade offs. Example: Polymer (ductile, weak and flexible) + Ceramics (strong, stiff but brittle) Strong, stiff and tough composite.
(Ceramic fibres/particles strengthen & stiffen polymer matrix. The Matrix protects brittle fibres from damage.

Mechanical properties
For continuous-aligned long fibre-reinforced composites stressed in the longitudinal direction:

Elastic deformation..

Summary: for continuous aligned fibre reinforced composites in the longitudinal direction:
Stage I elastic deformation of fibres and matrix

Modulus of composite: Ec = EfVf + EmVm


where V is the volume fraction

Strength of composite: sc = sfVf + smVm

Stage II plastic deformation of matrix; elastic deformation of fibres

Example
What is the modulus of a FRP containing 40% glass fibres modulus 69GPa in a resin modulus 3.5GPa?

Ec = EfVf + EmVm Ec = 69 * 0.4 + 3.5 * 0.6

Ec = 27.6 + 2.1
Ec = 29.7 GPa

Ans: 5.6 GPa

Ec

Concrete
Aggregate particles (usually 60-80%) act as (cheap) filler to reduce the amount of cement (expensive) Fine particles of sand fill spaces between gravel

Weak and brittle in tension, so increase strength by (steel) reinforcement Good bond between steel and concrete, and similar thermal expansion
Prestressed concrete: Steel reinforcement stretched before concrete is poured. Release tension once concrete has set Concrete placed into compression. Concrete now able to withstand tensile forces

Sufficient cement required to coat aggregate particles and bond them together.
Water:

Too little ~> incomplete bonding Too much ~> excessive porosity. Both ~> reduced strength

WOOD
a heterogeneous, hygroscopic, cellular and anisotropic material. composed of fibres of cellulose (40% 50%) and hemicellulose (15% 25%) impregnated with lignin (15% 30%).

A diffuse-porous hardwood (Black walnut), showing vessels ("pores"), rays (white lines) and annual rings

Black locust end grain, showing the ring-porous structure.

Mechanical testing of wood


Standard static-bending, compression, tension and shear testing used. generally conducted at 12% moisture content and at 20C.

e.g. soft-woods for structural parts of aircraft:


Strength value Density [kg.m-3] Static bending stress at elastic limit Static bending rupture stress Static bending modulus of elasticity Compression parallel to grain: maximum crushing strength Sitka spruce 432.5 42 MPa 72 MPa 10 GPa 38 MPa 5.6 MPa 72 MPa 0.9 MPa Hoop pine 520.6 56 MPa 90 MPa 13 GPa 48.7 MPa 90 MPa -

Parallel to grain

Compression strength perpendicular to grain


Tension strength parallel to grain [= modulus of rupture ] Tension strength perpendicular to grain

Density

Strength

Stiffness

Fracture Toughness