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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
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
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
Glucose
glucose bending
bends
alpha-glucose
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
Rubber Toughening of PS
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
HOOC
COOH
HOCH2CH2OH
HOCH2CHCH2OH OH
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
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
C6H4(COOH)2
C6H4(COOH)2
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 .
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
PET Animation
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
Hydrogen Bonding
Condensation Polymers
Types of Polymerization
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.
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.
Initiation
Propagation
Termination by Coupling
Termination by Disproportionation
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).
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.
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.
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.
Effect of Composition
Flexible
Rigid
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
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
LDPE
What is the approximate bond angle of carbon atom in a) linear b) crosslinked polymer?
109.5o
poly(butylene terephthalate)
Which a) PMMA
higher
Tg
PMMA
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
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
Which a) Nylon
higher
Tm
Aramid
Which a) a-PS
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
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
Melamine Formaldehyde
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).
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):
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.
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
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.
Tie-chain molecules that act as connecting links between adjacent lamellae pass through these amorphous regions.
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