MENG 3319 MATERIAL SCIENCE AND MANUFACTURING

Polymers
Dr. Tafesse Borena

Lecture outline

Polymeric Materials Classification of polymers Molecular Structure Chemistry of polymers Plastics and additives Crystallinity of polymers Additives to polymers Mechanical and physical properties of plastics Thermoplastics,Thermoset plastics and Elastomers Plastic Identification Plastic recycling Biodegradable polymers

Plastic facts
We live in a plastic society. Everything around us is plastic. Could you go for a day without plastic? Toothbrush, clothing, food containers, cooking spatulas, pans, bottled water, automobile parts, bicycle parts, eye glasses, iPod, calculator, mouse, computer parts, printer, stapler, head phones, TV, clock, flash memory housing, usb connector, keyboard, shoes, backpack parts, cell phone, credit cards..

Polymer Structures

Polymer

Greek root poly (many), mer (unit) Substance made up of many of repeating units (mers) Synonym for plastic Greek, plastikos, means to mold and shape

Plastic

Materials
Most polymers are based on carbon and are therefore considered organic chemicals
Solid material Metals Ceramics Plastics Composites

Thermoplastics

Thermosetts

Elastomers

Examples of Polymers

Thermoplastics:

Polyethylene, polyvinylchloride, polypropylene, polystyrene, and nylon Phenolics, epoxies, and certain polyesters Natural rubber (vulcanized) Synthetic rubbers, which exceed the tonnage of natural rubber

Thermosets:

Elastomers:

Polymer Structures

Metal: single atoms, metallic bond Ceramic: metallic oxides, ionic bond or dipole interactions, van der Waals bonds Polymer: long molecule chain
(most are made from oil)
-[C2H4]n- , poly[ethylene]

Spaghetti

Polymer Structures

Polymer
-[C2H4]n- , poly[ethylene]

Covalent Bonding: link monomers to form a chain Occurs when two nonmetal atoms are in close proximity Both atoms share outer electron shells Strong Bond

Polymer Structures

Secondary Bonding: hold polymer chains Van der Waals Due to the attraction of all molecules have for each other, e.g. gravitational. Forces are weak since masses are small

Secondary Bonding

Hydrogen bonds Ionic bonds Weaker than metallic, covalent

Molecular shape

The angle between the singly bonded carbon atoms is ~109o carbon atoms form a zigzag pattern in a polymer molecule. While maintaining the 109o angle between bonds polymer chains can rotate around single C-C bonds (double and triple bonds are very rigid). Random kinks and coils lead to entanglement, like in the spaghetti structure:

Hydrocarbon molecules
Most polymers are organic, and formed from hydrocarbon molecules Each C atom has four e- that participate in bonds, each H atom has one bonding eExamples of saturated (all bonds are single ones) hydrocarbon molecules:

Methane, CH4

Ethane, C2H6

Propane, C3H8

Hydrocarbon molecules
Double and triple bonds can exist between C atoms (sharing of two or three electron pairs). These bonds are called unsaturated bonds. Unsaturated molecules are more reactive

H-CC-H
Ethylene, C2H4 Acetylene, C2H2

Isomers are molecules that contain the same atoms but in a different arrangement. An example is butane and isobutane:

Butane C4H10 Isobutane

Hydrocarbon molecules

Other organic groups can be in a polymer. R represent radical: organic groups that remain a unit during reactions (e.g. CH3, C2H5, C6H5)

Chemistry of polymer molecules

Ethylene (C2H4) a gas at room T and P Ethylene-->polyethylene (solid) though active mer formed by reaction with initiator / catalytic radical (R.) (.) denotes unpaired electron (active site) Polymerization: 1.Initiation reaction: 2. Rapid propagation ~1000 mer units in 1-10 ms:

3. Termination: two active chain ends meet or active chain end meet with radical (R.)

Chemistry of polymer molecules

Replace hydrogen in polyethylene polytetraflouroethylene (PTFE) Teflon Replace every fourth hydrogen in polyethylene with Cl polyvinyl chloride(PVC) Replace every fourth hydrogen in polyethylene with CH3 methyl group polyproplylene

Addition and Step Polymerization

Model of addition polymerization(chain) polymerization: (1) initiation, (2) rapid addition of monomers, and (3) resulting long chain polymer molecule with n mers at termination of reaction (e.g. ,Polyethylene, paolypropylene, polyvinylchloride, polyisoprene)

Model of step polymerization showing the two types of reactions occurring: (left) n-mer attaching a single monomer to form a (n+1)-mer; and (right) n1-mer combining with n2-mer to form a (n1+n2)-mer (e.g., Nylon, polycarbonate, phenol formaldehyde)

Polymer Structures

Linear Polymers

Sequential chains Thermoplastics: acrylics, nylons, Side branch chains Thermoplastics: polyethylene,
(Chain packing efficiency is reduced compared to linear polymers - lower density)

Branched Polymers

Linear

Branched

Polymer Structures

Cross-linked Polymers

Adjacent chains linked by covalent bonds(often achieved by adding atoms or molecules that form covalent links between chains). Many rubbers have this structure Thermosetts: epoxies, silicones, 3D networks of 3 or more active covalent bonds( trifunctional mers) Examples: epoxies, phenol-formaldehyde

Network Polymers

Cross-linked

Network

Copolymers (composed of different mers)

Copolymers: at least two different types of mers, can differ in the way the mers are arranged:
Random copolymer

Alternating copolymer

Block copolymer

Graft copolymer

Synthetic rubbers are copolymers

Polymer Structures

Thermoplastic (TP) vs. Thermoset (TS)

TP (Solid materials at room temperature but viscous liquids when heated to temperatures of only a few hundred degrees) easily and economically shaped into products They can be subjected to heating and cooling cycles repeatedly without significant degradation TS - (Cannot tolerate repeated heating cycles ) When initially heated, they soften and flow for molding Elevated temperatures also produce a chemical reaction that hardens the material into an infusible solid If reheated, thermosets degrade and char rather than soften

Crystallinity in Polymers

The crystalline state may exist in polymeric materials. However, since it involves molecules instead of just atoms or ions, as with metals or ceramics, the atomic arrangement will be more complex for polymers. There are ordered atomic arrangements involving molecular chains. Example shown is a polyethylene unit cell
(orthorhombic).

Polymer Crystallinity
Polymers are rarely 100% crystalline Difficult for all regions of all chains to become aligned
crystalline region

Degree of crystallinity expressed as % crystallinity. -- Some physical properties depend on % crystallinity. -- Heat treating causes crystalline regions to grow and % crystallinity to amorphous increase.
region

Crystal Structures

Fe3C iron carbide orthorhombic crystal structure

Crystallinity and Properties

As crystallinity is increased in a polymer

Density increases Stiffness, strength, and toughness increases Heat resistance increases If the polymer is transparent in the amorphous state, it becomes opaque when partially crystallized
Polyethylene type Degree of crystallinity Specific gravity Modulus of elasticity Melting temperature Low density 55% 0.92 140 MPa (20,000 lb/in2) 115C (239F) High density 92% 0.96 700 MPa (100,000 lb/in2) 135C (275F)

Factors for Crystallization

Slower cooling promotes crystal formation and growth Mechanical deformation, as in the stretching of a heated thermoplastic, tends to align the structure and increase crystallization Plasticizers (chemicals added to a polymer to soften it) reduce crystallinity

Crystal Structures

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

The effect of temperature on the structure and behavior of thermoplastics.

Thermal Behavior of Polymers

Specific volume (density)-1 as a function of temperature

Additives and their Function

Properties of a polymer can often be beneficially changed by combining it with additives

Additives either alter the molecular structure or Add a second phase, in effect transforming the polymer into a composite material

Fillers strengthen polymer or reduce cost Plasticizers soften polymer and improve flow Colorants pigments or dyes Lubricants reduce friction and improve flow Flame retardents reduce flammability of polymer Cross-linking agents for thermosets and elastomers Ultraviolet light absorbers reduce degradation from sunlight Antioxidants reduce oxidation damage

Mechanical Properties of Thermoplastics

Thermoplastic polymers

Heating and cooling can be repeated many times without degrading the polymer

Reason: TP polymers consist of linear and/or branched macromolecules that do not cross-link

Low modulus of elasticity (stiffness)

E is much lower than metals and ceramics TS is about 10% of metal

Low tensile strength

Much lower hardness than metals or ceramics Greater ductility on average

Tremendous range of values, from 1% elongation for polystyrene to 500% or more for polypropylene

Strength vs. Temperature

Deformation resistance (strength) of polymers as a function of temperature

Physical Properties of Thermoplastics

Lower densities than metals or ceramics

Typical specific gravity for polymers are 1.2 (compared to ceramics (~ 2.5) and metals (~ 7) Roughly five times the value for metals and 10 times the value for ceramics

Much higher coefficient of thermal expansion

Much lower melting temperatures Insulating electrical properties Higher specific heats than metals and ceramics

Commercial Thermoplastic Products and Raw Materials

Thermoplastic products include

Molded and extruded items Fibers and filaments Films and sheets Packaging materials Paints and varnishes

Starting plastic materials are normally supplied to the fabricator in the form of powders or pellets in bags, drums, or larger loads by truck or rail car

Thermosetting Polymers (TS)

Thermosets and elastomers change chemically when heated, which cross-links their molecules and permanently cures these polymers TS polymers are distinguished by their highly cross-linked three-dimensional, covalently-bonded structure Chemical reactions associated with cross-linking are called curing or setting In effect, formed part (e.g., pot handle, electrical switch cover, etc.) becomes a large macromolecule Always amorphous and exhibits no glass transition temperature

General Properties of Thermosets

Rigid - modulus of elasticity is two to three times greater than thermoplastics Brittle, virtually no ductility Less soluble in common solvents than thermoplastics Capable of higher service temperatures than thermoplastics Cannot be remelted - instead they degrade or burn

Cross-Linking in TS Polymers

Three categories:
1. 2. 3.

Temperature-activated systems Catalyst-activated systems Mixing-activated systems

Curing is accomplished at the fabrication plants that make the parts rather than the chemical plants that supply the starting materials to the fabricator

Temperature-Activated Systems

Catalyst-Activated Systems

Curing caused by heat supplied during part shaping operation (e.g., molding) Starting material is a linear polymer in granular form supplied by the chemical plant When heated, material softens for molding, but continued heating causes cross-linking Most common TS systems The term thermoset" applies best to these polymers

Cross-linking occurs when small amounts of a catalyst are added to the polymer, which is in liquid form Without the catalyst, the polymer remains stable and liquid Once combined with the catalyst it cures and changes into solid form

Catalyst-Activated Systems

Cross-linking occurs when small amounts of a catalyst are added to the polymer, which is in liquid form

Without the catalyst, the polymer remains stable and liquid Once combined with the catalyst it cures and changes into solid form

Mixing-Activated Systems Mixing of two chemicals results in a reaction that forms a cross-linked solid polymer
Elevated temperatures are sometimes used to accelerate the reactions Most epoxies are examples of these systems

Elastomers

Polymers capable of large elastic deformation when subjected to relatively low stresses Some can be extended 500% or more and still return to their original shape Two categories:
1. 2.

Natural rubber - derived from biological plants Synthetic polymers - produced by polymerization processes like those used for TP and TS polymers

Elastomers consist of long-chain molecules that are cross-linked (like thermosetting polymers) They owe their impressive elastic properties to two features: 1. Molecules are tightly kinked when unstretched 2. Degree of cross-linking is substantially less than thermosets

Elastomer Molecules

Model of long elastomer molecules, with low degree of cross-linking: (left) unstretched, and (right) under tensile stress

When stretched, the molecules are forced to uncoil and straighten Natural resistance to uncoiling provides the initial elastic modulus of the aggregate material Under further strain, the covalent bonds of the cross-linked molecules begin to play an increasing role in the modulus, and stiffness increases With greater cross-linking, the elastomer becomes stiffer and its modulus of elasticity is more linear

Vulcanization

The term for curing (cross-linking) in the context of natural rubber (and certain synthetic rubbers) Typical cross-linking in rubber is one to ten links per hundred carbon atoms in the linear polymer chain, depending on degree of stiffness desired

Considerable less than cross-linking in thermosets

Natural Rubber (NR)

NR = polyisoprene, a high molecular-weight polymer of isoprene (C5H8)

Derived from latex, a milky substance produced by various plants, most important of which is the rubber tree that grows in tropical climates Latex is a water emulsion of polyisoprene (about 1/3 by weight), plus various other ingredients Rubber is extracted from latex by various methods that remove the water

Vulcanized Natural Rubber

Properties: noted among elastomers for high tensile strength, tear strength, resilience (capacity to recover shape), and resistance to wear and fatigue Weaknesses: degrades when subjected to heat, sunlight, oxygen, ozone, and oil

Some of these limitations can be reduced by additives

Market share of NR 22% of total rubber volume (natural plus synthetic)

Natural Rubber Products

Largest single market for NR is automotive tires Other products: shoe soles, bushings, seals, and shock absorbing components In tires, carbon black is an important additive

It reinforces the rubber, serving to increase tensile strength and resistance to tear and abrasion

Other additives: clay, kaolin, silica, talc, and calcium carbonate, as well as chemicals that accelerate and promote vulcanization

Synthetic Rubbers

Development of synthetic rubbers was motivated largely by world wars when NR was difficult to obtain Tonnage of synthetic rubbers is now more than three times that of NR Most important synthetic rubber is styrene-butadiene rubber (SBR), a copolymer of butadiene (C4H6) and styrene (C8H8) As with most other polymers, the main raw material for synthetic rubbers is petroleum

Thermoplastic Elastomers (TPE)

Thermoplastic that behaves like an elastomer Elastomeric properties not from chemical cross-links, but from physical connections between soft and hard phases in the material Cannot match conventional elastomers in elevated temperature strength and creep resistance Products: footwear; rubber bands; extruded tubing, wire coating; molded automotive parts, but no tires

Plastics Identification Code (PIC)

In 1988 the Society of the Plastics Industry developed a numeric code to provide a uniform convention for different types of plastic containers. The symbol consists of a triangle formed by three bent arrows enclosing a number to identify the plastic: These numbers can be found on the underside of containers. PET; PETE (polyethylene terephthalate): plastic water and soda bottles. HDPE (high density polyethylene): laundry/dish detergent V (Vinyl) or PVC: Pipes, shower curtains LDPE (low density polyethylene): grocery bags, sandwich bags PP (polypropylene): Tupperware, syrup bottles, yogurt cups, PS (polystyrene): Coffee cups, disposable cutlery Miscellaneous: any combination of 1-6 plastics

1. 2. 3. 4. 5. 6. 7.

Plastics Identification Code (PIC)

All of the plastics covered by the PIC are thermoplastic polymers The PIC facilitates sortation of items made of different plastics for reprocessing

Sorting is a very labor intensive activity

Recycling of thermosets and elastomers is more difficult because of cross-linking (cannot be remelted)

Recycling involves retreading of tires, grinding the TS polymers to be used as fillers, etc.

Plastics Recycling

Approximately 200 million tons of plastic products are made annually throughout the world

U.S. production is about 25 million tons Only about 6% of the U.S. tonnage is recycled as plastic waste

The rest either remains in products or ends up in garbage landfills

Recycling means recovering the discarded plastic items and reprocessing them into new products

Problems in Plastics Recycling

1.

Economics of metal recycling are more favorable because the items are usually larger Economics of glass recycling are more favorable because glass products are all based on silicon dioxide By contrast, plastic products are generally small and made of a great variety of chemical compositions that do not mix well

2.

3.

Biodegradable Polymers

Defined as plastics that decompose due to the actions micro-organisms in nature

Conventional plastics are not biodegradable

1. 2.

Two forms of biodegradable plastics:

Partially biodegradable consist of a conventional polymer plus biodegradable filler Completely biodegradable (a.k.a. bioplastics) consist of polymer plus filler, both of which are biodegradable

Of greatest interest are the completely biodegradable plastics Both polymer and filler are derived from natural and renewable sources

Polymer various agricultural products can be used as the raw material for biodegradable plastics

Starch from corn, wheat, rice, potatoes

Filler cellulose from flax or hemp

Reference Materials
1. 2. 1. 3. 4.

Fundamentals of Modern Manufacturing 5/e M P Groover,, John Wiley & Sons, Inc. , 2012 Manufacturing Processes for Engineering Materials, 5 th edition, S. Kalpakjian and S.R. Schmid, Prentice Hall, 2006 Materials and Processes in Manufacturin g, 11th ed., E.P. DeGarmo, J.T. Black, R.A. Kohser, Wiley, 2013 Callister,W.D., Materials Science and Engineering, 8th Ed., 2003 The Science and Engineering of Materials, by Donald Askeland any edition