Course Code :

Course Title :

MSE-240 [3-1]
Engineering Polymers

Polymers: Chemistry and Physics of Modern Materials by J. M. G. Cowie and Valeria Arrighi, 3rd Edition, CRC Press, 2007. Assessment : Assignments 5% Quizzes 15% OHT Exam 30% Final Exam 50% Total 100%

Introduction
Macromolecules

Materials Classification

Polymers

Monomer Covalent bond

Basics
Polymers form a large class of engineering materials, which include plastics, rubbers and adhesives They are large organic molecules, which have molecular weights of 10,000 to 100,000 g/mole Polymerization is the process used to join the small organic molecules into these huge molecules

Introduction
Polymers many parts Polymers

Plastics

Elastomers

Thermoplastics Can be reheated and formed into new materials

Thermosetting Plastics Cannot be reformed by reheating. Set by chemical reaction.

Monomer vs. polymer

Propylene monomer

Polypropylene A polymer

A monomer is the simple molecule that is covalently bonded with other monomers to form long molecular chains. A polymer is the long-chain molecule formed from monomer units.

Polymers
Polymers can be divided into 2 types : Naturally occurring polymers
Synthetic polymers

Natural Polymers
Polymers that exist in plants or animals
Examples of naturally occurring polymers: Protein : muscles Carbohydrates : cellulose Natural rubber : latex

Natural Polymers

Natural Polymer

Cotton fiber is mostly cellulose, and cellulose is made of chains of the sugar, glucose linked together a certain way.

Glucose
Structural formula. Straight chain glucose 1

Glucose
Two ring-shape versions

H-C=O |2 H-C-OH |3 HO-C-H | 4 H-C-OH |5 H-C-OH |6 CH2OH

Glucose
glucose bending

Used in making starch flips either way

bends

alpha-glucose

Glucose bends itself into 4 different shapes millions of times a second

Used in making cellulose

beta-glucose

Synthetic Polymers
Polymers made in industry from chemical substances Scientists are able to copy structures of natural polymers to produce synthetic polymers through scientific research

Synthetic Polymers
Many of raw materials for synthetic polymers are obtain from -> Petroleum Synthetic polymers
Plastics Fibers Elastomers

Homopolymer and Copolymers

Homopolymers: Polymer chain is made up of single repeating units. Example: AAAAAAAA Copolymers: Polymer chains made up of two or more repeating units.
Random copolymers: Different monomers randomly arranged in chains. e.g.:- ABBABABBAAAAABA Alternating copolymers: Definite ordered alterations of monomers. e.g.:- ABABABABABAB Block copolymers: Different monomers arranged in long blocks. Eg:AAAAA.BBBBBBBB Graft copolymers: One type of monomer grafted to long chain of another. e.g.: AAAAAAAAAAAAAAAAAAA B B B B B B

Rubber Toughening of PS

High-impact polystyrene, or HIPS for short

Polystyrene is a rather brittle material. But little polybutadiene spheres are rubbery, remember, and they can absorb energy under stress. This keeps the polystyrene from breaking.

Tacticity

Polypropylene (PP)

Polymers Why?
Polymers as a class of materials are lightweight and corrosion resistant with relatively low melting points. Polymers are relatively inexpensive. They can be readily formed into a variety of shapes Some polymers are transparent, some are good electrical conductors, some are good electrical insulators. Some have low coefficient of friction, e.g. lowstick cookware.

Characteristics of Polymers
Polymers can be very resistant to chemicals.
Consider all the cleaning fluids in your home that are packaged in plastic. Many of these chemicals are very corrosive and abrasive agents.

Characteristics of Polymers
Polymers can be both thermal and electrical insulators.

Consider all the appliances, cords, electrical outlets, and general wiring that are made of or covered with polymeric materials.
Thermal resistance is evident in the kitchen with pot and pan handles made of polymers.

Characteristics of Polymers
Generally, polymers are very light in mass with varying degrees of strength.

Consider the range of applications from a piggy bank to the frame structure of space stations,
or from delicate nylon fiber to Kevlar, which is used in bulletproof vests.

Applications
Toys, Home appliances, Structural and decorative items in the home, Coatings, paints, Adhesives, Foams, packaging, Automobile interiors and exteriors, etc.

Polymerization
Polymerization is the process used to join the small organic molecules into these huge molecules called polymers

Types of Monomer
a. AB type
HO COOH

b. AA (A2) and BB (B2) type

HOOC

COOH

HOCH2CH2OH

c. Three functional group for crosslinked polymers

HOCH2CHCH2OH OH

Functionality of monomer (f)

Number of covalent bonds that a monomer molecule or monomeric unit in a macromolecule or oligomer molecule can form with other reactants.

Functionality of monomer (f)

There are no monofunctional monomers. If f = 2, a linear chain macromolecule can be formed. If f > 2, a branch point can be formed leading to a branched macromolecule or a network. Ethene and ethylene glycol are examples of difunctional monomers, glycerol is an example of a trifunctional monomer, and divinylbenzene and pentaerythritol are examples of tetrafunctional monomers.

What is the Functionality of the following monomers in reaction with (i)styrene C6H5CH=CH2 and (ii) adipic acid HOOC(CH2)4COOH
1.
(i) 2 (ii) 0

2.
(i) 0 (ii) 2

3.
(i) 2 (ii) 0

Elementary Saturated Dicarboxylic Acids

Common name Oxalic acid Malonic acid Succinic acid Glutaric acid Adipic acid Pimelic acid Suberic acid Azelaic acid Sebacic acid IUPAC name Chemical formula

ethanedioic acid propanedioic acid butanedioic acid pentanedioic acid hexanedioic acid heptanedioic acid octanedioic acid nonanedioic acid decanedioic acid undecanedioic acid dodecanedioic acid

HOOC-COOH HOOC-(CH2)-COOH HOOC-(CH2)2-COOH HOOC-(CH2)3-COOH HOOC-(CH2)4-COOH HOOC-(CH2)5-COOH HOOC-(CH2)6-COOH HOOC-(CH2)7-COOH HOOC-(CH2)8-COOH HOOC-(CH2)9-COOH HOOC-(CH2)10-COOH

Elementary Aromatic Dicarboxylic Acids

Common name Phthalic acid IUPAC name benzene-1,2dicarboxylic acid (o-phthalic acid) benzene-1,3dicarboxylic acid (m-phthalic acid) benzene-1,4dicarboxylic acid (p-phthalic acid) Chemical formula C6H4(COOH)2

Isophthalic acid Terephthalic acid

C6H4(COOH)2

C6H4(COOH)2

Elementary Unsaturated Dicarboxylic Acids

Type Common name Chemical formula

Monounsaturated: Maleic acid (cis form) two isomeric and Fumaric acid (trans forms: form) cis and trans

HO2CCH=CHCO2H

Vinyl Polymers
Vinyl Monomers, CH2=CH-X

Vinylidene Polymers
Vinylidene Monomers, CH2=C(X)Y

Polymerization mechanisms
The synthetic process is Polymerization. Addition polymers are formed by covalently joining individual molecules without changing the chemistry of the reactants. Condensation polymers are produced when two or more types of molecules are joined by a chemical reaction that releases a by-product such as water.

Condensation Polymerization
This method (also known as step-growth) requires that the monomers possess two or more kinds of functional groups that are able to react with each other in such a way that parts of these groups combine to form a small molecule (often H2O) which is eliminated from the two pieces. The now-empty bonding positions on the two monomers can then join together .

Different Condensation Linkages

Condensation Reaction

Condensation Polymerization

PET

 Polyester is a copolymer. It is made from equal amounts of two different monomers. Polyester is used to make bottles and fabrics.

Polyester is made from the two monomers, terephthalic acid (note: ph is silent) and ethylene glycol (car antifreeze). This makes a popular plastic called PETE, which is short for Polyethylene Terephthalate. The synthesis is also a dehydration reaction because water is given off.
PETE

O H O C

ESTER groups formed

Hence the name POLYESTER

PET Animation

Tetramethylene dicarboxylic acid (adipic acid)

Hexamethylene diamine

methylene x 6 (hexa)

amine x 2 (di)

When these two monomers are in the same beaker, they combine and give off a molecule of water. This is called a dehydration reaction because we are taking away (de) water (hydra).

Back to Condensation

Aramid and Nylon

Nylon is a generic designation for a family of synthetic polymers known generically as polyamides.

Aramid is a shortened form of "aromatic polyamide".

Hydrogen Bonding

Why does nylon make such good fibers?

Intermolecular forces like hydrogen bonding

Condensation Polymers

Types of Polymerization

Ring Opening Polymerization

Ring Opening Polymerization

Propylene oxide

Poly(propylene oxide)

Nylon 6

Nylon Naming

Polyurethane
Polyurethanes are made from a dialcohol and diisocyanate monomers. The isocyanate compounds contain the functional group (O=C=N-). A rearrangement reaction leads to the formation of the urethane linkage. Technically polyurethane is not a condensation polymer since no molecules are lost, but the functional group does rearrange.

Polyurea and Polyurethane

a polyurethane

Spandex
One unusual polyurethane thermoplastic elastomer is spandex, which DuPont sells under the trade name Lycra. It has both urea and urethane linkages in its backbone. What gives spandex its special properties is the fact that it has hard and soft blocks in its repeat structure.

Addition Polymerization
Addition or chain-growth polymerization involves the rearrangement of bonds within the monomer in such a way that the monomers link up directly with each other. A chemically active molecule (called an initiator) is needed to start a chain reaction.

Review

High temperature or UV light can cause two of these shared (paired) electrons to become unshared (unpaired).
H TheseH unpaired electrons are eager to pair up with another electron. If this ethylene molecule bumps another ethylene C C molecule, the unpaired electrons will cause the one it bumped into to lend one of its H inner electrons. H

C
H

C
H
-

Another way to see the chain reaction. These are the carbon atoms with their double-bond (2 shared electrons each). The hydrogen atoms are not shown. A collision breaks the first bond.

Once the first double bond is broken, a chain reaction will occur. In about a second an entire chamber of compressed ethylene gas turns into the polymer, polyethylene.

Free Radical Polymerization

Initiator

Initiation

Propagation

Termination by Coupling

Termination by Disproportionation

Addition Polymerization Animation

Addition Polymerization (PE)

Addition Polymerization

Addition Polymerization

Addition Polymers
(PS)

(PMMA)

(PTFE)

(PVC)

Polymerization of Ethene
Polyethylene can be produced through radical polymerization, anionic addition polymerization, ion coordination polymerization or cationic addition polymerization. Ethene does not have any substituent groups that influence the stability of the propagation head of the polymer. Each of these methods results in a different type of polyethylene.

Classification of Polyethylene
Polyethylene is classified into several different categories based mostly on its density and branching.

Classification of Polyethylene
Ultra high molecular weight polyethylene (UHMWPE) Ultra low molecular weight polyethylene (ULMWPE or PEWAX) High molecular weight polyethylene (HMWPE) High density polyethylene (HDPE) High density cross-linked polyethylene (HDXLPE) Cross-linked polyethylene (PEX or XLPE) Medium density polyethylene (MDPE) Linear low density polyethylene (LLDPE) Low density polyethylene (LDPE) Very low density polyethylene (VLDPE)

A polymer made form just one monomer is polyethylene. It is the most common plastic.
It is used for bottles, buckets, jugs, containers, toys, even synthetic lumber, and many other things.

There are two types of polyethylene polymers (plastics). One is when the polyethylene exists as long straight chains. The picture here shows the chains of one carbon with two hydrogen atoms repeating. The chain can be as long as 20,000 carbons to 35,000 carbons. This is called high density polyethylene (HDPE).

When the chains get up to 500,000 carbons long, they are tough enough for synthetic ice, replacement joints, and bullet-proof vests.

There must be low density polyethylene (LDPE). It is made by causing the long chains of ethylene to branch. That way they cannot lie next each other, which reduces the density and strength of the polyethylene. This makes the plastic lighter and more flexible.

Low density polyethylene is used to make plastic bags, plastic wrap, and squeeze bottles, plus many other things.

Another polymer, which is almost the same as polyethylene, is PolyVinyl Chloride or PVC. The difference is that every other hydrogen is replaced with a chlorine atom (green sphere).

(CH2CHCl)n + O2 CO2 + CO + HCl + H2O

PVC pipes are used in our homes and they are even handy for making a table or chair. PVC is also used as insulation around electric wires in the home and the automobile.
PVC is quite safe until it burns. The chlorines in the PVC combine with the hydrogen atoms in the PVC to form hydrogen chloride gas (HCl). When this contacts water in lungs or mouth, it turns to hydrochloric acid (HCl(aq)).

There are many types of plastics. By controlling the length and the branching, one can control the final hardness or flexibility of the polymer plus qualities like resistance to solvents, acids, or heat.

The favorite properties of plastics are that they are inert. They also are durable and won't easily decay, dissolve, or break apart. But when one throws them away, they won't decompose.

Since they dont decompose, the answer is to recycle the plastics so they can be remade into something else.

The decks, fence, stepping stones, and the sweat shirt, were all made from recycled plastic.

Time for Litter to Biodegrade

Product Paper Wool socks Plastic coated paper milk cartons Plastic bags Time to biodegrade 2-5 months 1 to 5 years 5 years 10 to 20 years

Nylon fabric Aluminum cans

Plastic 6-pack holder rings Glass bottles Plastic bottles

30 to 40 years 80 to 100 years

450 years 1 million years Forever

Plastic Resin Identification Codes

Codes Descriptions
Polyethylene terephthalate (PET, PETE) is clear, tough, and has good gas and moisture barrier properties. Commonly used in soft drink bottles and many injection molded. Other applications include strapping and both food and non-food containers. Cleaned recycled PET flakes and pellets are in great demand for spinning fiber for carpet yarns, producing fiberfill and geo-textiles. High Density Polyethylene (HDPE) is used to make bottles for milk, juice, water and laundry products. Unpigmented bottles are translucent, have good barrier properties and stiffness, and are well suited to packaging products with a short shelf life such as milk. Because HDPE has good chemical resistance, it is used for packaging many household and industrial chemicals. Polyvinyl Chloride or PVC has excellent chemical resistance, good weatherability, flow characteristics and stable electrical properties. The vinyl products can be broadly divided into rigid and flexible materials. Bottles and packaging sheet are major rigid markets, but it is also widely used as pipes and fittings, siding, carpet backing and windows. Flexible vinyl is used in wire and cable insulation, film and sheet, floor coverings synthetic leather products, coatings, blood bags, medical tubing and many others.

Recycled products
Fiber, tote bags, clothing, film and sheet, food and beverage containers, carpet, strapping, fleece wear, luggage and bottles.

Bottles; pipe, buckets, crates, flower pots, garden edging, film and sheet, recycling bins, benches, dog houses, plastic lumber, floor tiles, picnic tables, fencing. Packaging, binders, decking, paneling, gutters, mud flaps, film and sheet, floor tiles and resilient flooring, cables, mats, cassette trays, electrical traffic cones, boxes, garden hose, mobile.

Plastic Resin Identification Codes

Codes Descriptions
Low Density Polyethylene (LDPE) used predominately in film applications due to its toughness, flexibility and relative transparency, making it popular for use in applications where heat sealing is necessary. LDPE is also used to manufacture some flexible lids and bottles and it is used in wire and cable applications. Polypropylene (PP) has good chemical resistance, is strong, and has a high melting point making it good for hot-fill liquids. PP is found in flexible and rigid packaging to fibers and large molded parts for automotive and consumer products.

Recycled products
Shipping envelopes, garbage can liners, film and sheet, furniture, compost bins, paneling, trash cans, landscape timber, lumber Automobile battery cases, signal lights, battery cables, brooms, brushes, oil bins, funnels, bicycle racks, trays pallets, sheeting. Light switch plates, vents, thermal insulation, desk trays, rulers, license plate frames, foam packing, foam plates, utensils Bottles, plastic lumber

Polystyrene (PS) is a versatile plastic that can be rigid or foamed. General purpose polystyrene is clear, hard and brittle. It has a relatively low melting point. Typical applications include protective packaging, containers, lids, cups, bottles and trays. Other. Use of this code indicates that the package in question is made with a resin other than the six listed above, or is made of more than one resin listed above, and used in a multi-layer combination.

Molecular Weight as a Function of Conversion

Very fast mechanism, full sized polymer formed instantaneously after initiation, thus polymer size is independent of reaction time Fast initiation process coupled with absence of termination reaction Average molecular weight builds up slowly and a high molecular weight is formed only when conversion is more than 98% n mer + monomer (n+1) mer n mer + m mer (n+ m) mer

Comparison of Step Growth and Chain Growth Polymerization

Effect of Structure on Properties

Physical properties affected by: Chemical composition Arrangement of chains Molecular weight

Effect of Molecular Weight

Effect of Composition

Flexible

Rigid

Effect of Side Chain Substitution, Crosslinking and Branching on PE

Comparison of Polymers

Polymer Behavior
1) Thermoplastic polymers can be formed at elevated temperatures, cooled and then reheated and reformed into another shape without changing the structure or properties of the polymer. These are obviously easily recycled. 2) Thermosetting polymers are network polymers often formed by condensation reactions. They are generally stronger than thermoplastic polymers but they can not be reprocessed easily or at all. 3) Elastomers or rubbers have an intermediate behavior with the ability to deform enormous amounts without permanent change in shape.

Thermoplastic vs Thermoset
Long chain molecules Cross-linked molecules

Heating and cooling cycle of thermoplastic

Heating and cooling cycle of thermosetting plastic

Elastomer
Elastomers or rubbers are polymers which include polyisoprene or natural rubber. Elastomers can be stretched to many times their original length, and can bounce back into their original shape without permanent deformation.

Molecular Shape
The angle between the singly bonded carbon atoms is ~109o carbon atoms form a zigzag pattern in a polymer molecule

Molecular Shape
Moreover, 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:

Molecular Shape
Molecular chains may thus bend, coil and kink Neighboring chains may intertwine and entangle Large elastic extensions of rubbers correspond to unraveling of these coiled chains Mechanical / thermal characteristics depend on the ability of chain segments to rotate

If you want to produce nylon 6,6 by condensation polymerization using hexamethylene diamine and adipic acid, what masses of these two components will be needed to yield 20 kg of completely linear nylon 6, 6?
We write down the molecular weights of the three substances and calculate their masses in the ratio of their molecular weights: MW(adipic acid) = 146 g/mol MW(hexamethylene diamine) = 116.21 g/mol MW of Nylon 6,6 Repeat unit = 226 g/mol Weight of polymer produced = 20 kg = 20000g n = m/MM Hence mass of adipic acid needed = 88.5 x 146 = 12921 g = 12.9 kg and mass of hexamethylene diamine needed = 88.5 x 116 = 10266 g = 10.26 kg

Which has a greater volume and a lower Tg a) HDPE b) LDPE, Why?

LDPE

What is the approximate bond angle of carbon atom in a) linear b) crosslinked polymer?

109.5o

Which will be more flexible a) poly(ethylene terephthalate) b) poly(butylene terephthalate), Why?

poly(butylene terephthalate)

Which a) PMMA

will have b) PBMA, Why?

higher

Tg

PMMA

Which will have higher a) isotactic PP b) atactic PP, Why?

Tg

isotactic PP

Which will be more permeable to gas at room temperature a) isotactic PP b) atactic PP, Why?

atactic PP

Which a) PMMA

will be b) PMA, Why?

more

flexible

PMA
The PMA chains are more flexible than PMMA chains due to the reason that bulkier methyl groups on PMMA hinder packing of chains and hence make it rigid. For reference see this table also
consult the literature (hard copy) provided in last lecture.
PMMA PMA

Flexible low Tm Rigid high Tm

Which a) Nylon

will have b) Aramid, Why?

higher

Tm

Aramid

What is the type of hydrogen bond present in globular protein?

Intramolecular hydrogen bond

Which a) a-PS

will be more b) Isotatic PP, Why?

transparent

a-PS

Thermoset
A thermosetting plastic, also known as a thermoset, is polymer material that in a soft solid or viscous state changes irreversibly into an hard, insoluble polymer network by curing (cross-linking). Curing can be induced by the action of heat or suitable radiation, or both. A cured thermosetting polymer is called a thermoset. E.g. Vulcanized rubber, Epoxy resin.

Natural Rubber

For a rubber component that, in its final form is to be vulcanized, should vulcanization be carried out prior or subsequent to the forming operation? Why?
Vulcanization of a rubber component should be carried out prior to the forming operation since, once it has been vulcanized, plastic deformation (and thus forming) is not possible since chain crosslinks have been introduced.

For the following pair of polymers, do the following: (1) state whether or not it is possible to decide if one polymer has a higher tensile strength than the other; (2) if this is possible, note which has the higher tensile strength and then cite the reason(s) for your choice. Syndiotactic polystyrene having a number-average molecular weight of 600,000 g/mol Isotactic polystyrene having a number-average molecular weight of 500,000 g/mol.
Yes, it is possible. The syndiotactic polystyrene has the higher tensile strength. Both syndiotactic and isotactic polymers tend to crystallize, and, therefore, we assume that both materials have approximately the same crystallinity. However, tensile modulus increases with increasing molecular weight, and the syndiotactic PS has the higher molecular weight (600,000 g/mol versus 500,000 g/mol for the isotactic material).

Epoxy Thermoset

3-D Network

Epoxide group

RT Curing of Epoxies

Epoxy Thermoset

Diglycidyl ether of bisphenol A

Thermoset Plastic Manufacturing

Thermoset plastic industrial process is identified by three stages: A, B and C. A-stage refers to the key raw materials uncured stage B-stage refers to the product produced when curing agent and resin are brought together and leave a dry semi-cured resin. C-stage refers to the fully cured stage".

Phenol Formaldehyde

Urea Formaldehyde Amino Resin

Melamine Formaldehyde

Unsaturated Polyester Curing

Phthalic anhydride increases flexibility by increasing spacing of crosslinks.

Extension and Curing of Polyurethane

Network Glyptal Resin

Preparation and Curing of Vinyl Ester

Typical Addition Polymers (Homopolymers)

Typical Condensation Polymers

Some High Performance Condensation Polymers

Examples of addition thermoplastics

Molecular Structure
1 Linear polymers: Van der Waals bonding between chains. Examples: polyethylene, nylon. 2 Branched polymers: Chain packing efficiency is reduced compared to linear polymers - lower density

Molecular Structure
3 Cross-linked polymers: Chains are connected by covalent bonds. Often achieved by adding atoms or molecules that form covalent links between chains. Many rubbers have this structure.

Molecular Structure
4 Network polymers: 3D networks made from trifunctional mers. Examples: epoxies, phenolformaldehyde

Isomerism
Two types of isomerism are possible: stereoisomerism and geometrical isomerism Stereoisomerism: atoms are linked together in the same order, but can have different spatial arrangement

Geometrical Isomerism
Two carbon atoms bonded by a double bond in a chain. H atom or radical R bonded to these two atoms can be on the same side of the chain (cis structure) or on opposite sides of the chain (trans structure).

cis-polyisoprene (Natural Rubber)

trans-polyisoprene (gutta percha)

Head/Tail Configuration
In vinyl polymers Normally linked in a head to tail configuration -substituents are separated by three carbon atoms In head to head configuration this separation is only by 2 carbon atoms The separation with tail to tail configuration is by 4 atoms

Degree of Polymerization
The polymerization reaction is often characterized by its degree of polymerization, given by,
Degree of polymeriza tion, DP molecular weight of polymer molecular weight of repeat unit

For example, Nylon 6,6 repeat unit 226 g/mol 120,000 g/mol 531 polymer we ight 120,000 DP 226

Molecular Weight
P1 P2

MW = DP X (MW)u

Broad MWD

T T T T

T T

Narrow MWD

Molecular Weight
Each MW can be represented as Mi Ni = number of molecules of MW = Mi wi = weight fraction of given system of chains with MW = Mi

Molecular Weight
Polydispersity can be measured by PDI (polydispersity index):

z = 1.03 or 1.05 is considered close to monodisperse

Impact of Molecular Weight on Material Properties

Increasing Degree of Polymerization, DP

Summary: Size Shape -Structure

Microscopic Properties (Intermolecular Interactions)

Chain entanglement amorphous Chain orderingCrystallinity, Liquid Crystalline Phase separations (microdomains) Morphology

Types of Intermolecular Forces

Macroscopic Properties (Physical Behavior)

Tensile and/or Compressive Strength Elasticity Toughness Thermal Stability Flammability and Flame Resistance Degradability Solvent Resistance Permeability Ductility (Melt Flow)

Polymer Crystallinity
Atomic arrangement in polymer crystals is more complex than in metals or ceramics (unit cells are typically large and complex).
Polyethylene

Polymer Crystallinity
Polymer molecules are often partially crystalline (semicrystalline), with crystalline regions dispersed within amorphous material.

Factors for Polymer Crystallinity

Rate of cooling during solidification: time is necessary for chains to move and align into a crystal structure Mer complexity: crystallization less likely in complex structures, simple polymers, such as polyethylene, crystallize relatively easily Chain configuration: linear polymers crystallize relatively easily, branches inhibit crystallization, network polymers almost completely amorphous, crosslinked polymers can be both crystalline and amorphous

Factors for Polymer Crystallinity

Isomerism: isotactic, syndiotactic polymers crystallize relatively easily - geometrical regularity allows chains to fit together, atactic difficult to crystallize Copolymerism: easier to crystallize if mer arrangements are more regular - alternating, block can crystallize more easily as compared to random and graft More crystallinity: higher density, more strength, higher resistance to dissolution and softening by heating

Polymer Crystallinity
Crystalline polymers are denser than amorphous polymers, so the degree of crystallinity can be obtained from the measurement of density:

c:

Density of perfect crystalline polymer a: Density of completely amorphous polymer s: Density of partially crystalline polymer that is analyzed

Polymer Crystals
Thin crystalline platelets grown from solution Chains fold back and forth: chain-folded model

Polyethylene single crystal

The average chain length is much greater than the thickness of the crystallite

Polymer Crystals
Spherulites: Aggregates of lamellar crystallites ~ 10 nm thick, separated by amorphous material. Aggregates approximately spherical in shape.

Photomicrograph of spherulite structure of polyethylene

Tie-chain molecules that act as connecting links between adjacent lamellae pass through these amorphous regions.

Number Eighty Eight

HUMAN APOLIPOPROTEIN A-I. the major protein component of high-density lipoprotein Biopolymers can be complex and nice

CHAPERONE/STRUCTURAL PROTEIN
D. Choudhury, A Thompson, V . Stojanoff, S. Langermann, J. Pinkner, S.J. Hultgren and S. D. Knight (1999). X-ray structure of the FimC-FimH chaperone-adhesin complex from uropathogenic Escherichia coli. Science, 285: 1061-1066.
Chaperones are proteins that assist the non-covalent folding or unfolding and the assembly or disassembly of other macromolecular structure.

Summary