Properties of polymers

Md. Hedayatullah.
M.Tech I (G.E.T) 2nd Sem. Reg. No. 12307003 GETY524 Waste to energy conversion E-mail [email protected].

What is a polymer?

A long molecule made up from lots of small molecules called monomers.

Difference in properties of polymers

Different polymers differs in their physical & chemical properties this is mainly due to their conformation and strength of bonding . 1. Strength of attractive forces between chains = stronger the chain, less flexible the polymer. 2. Ability of Chains to slide past each other = more flexible polymer. 3. Presence of different groups in their structure. eg. Hydrophobic or Hydrophilic group.

Properties of polymers.
Properties of polymers Physical. Chemical.

Physical properties of polymers

Matterial Properties.
Density Electrical Conductivity.

Mechanical Properties.
Elasticity Rubber-glass transitions Yielding Point Viscoelasticity (Flow Property)..

Physical properties of polymers

Thermal Behavior:
Melting point. Glass Transition Temperature (Tg)
Crystalline melting temperature. (Tm) Co-efficient of thermal expansion

Solubility. Surface and interface properties

Surface dynamics Surface energies

Material properties.
1.Density:- The ratio of mass to volume of a
material. Generally Polymers are Low density molecules. (in compare to metals and ceramics) It depends upon the Degree of Polymerisation., Cross linkage between the chains of polymer and Crytallinity in the Polymer.
Density

Crystallinity , Cross linkage, DP

2. Electrical conductivity:Polymers are generly non-conducting electrically except Polyacetylene.

Mechanical Properties.
1.Elasticity:- Low modulus of elasticity (stiffness)

E is two or three orders of magnitude lower than metals and ceramics

2. Tensile strength:- Low tensile strength

TS is about 10% of the metal

3. Much lower hardness than metals or ceramics 4. Greater ductility on average

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

Figure 8.11 - Relationship of mechanical properties, portrayed as deformation resistance, as a function of temperature for an amorphous thermoplastic, a 100% crystalline (theoretical) thermoplastic, and a partially crystallized thermoplastic

Thermal behaviour.
1. Free volume of polymers varries with temperatue. 2. Much higher coefficient of thermal expansion Roughly five times the value for metals and 10 times the value for ceramics 3. Much lower melting temperatures

Specific heats two to four times those of metals and ceramics Thermal conductivities about three orders of magnitude lower than those of metals Insulating electrical properties

Glass Transition Temperature (Tg)

The temperature at which amorphous polymers undergo a transition from a rubbery, viscous amorphous liquid, to a brittle, glassy amorphous solid is called the Glass Transition temperature of that polymer. It is denoted by Tg. The glass transition temperature may be engineered by altering the degree of branching or crosslinking in the polymer or by the addition of plasticizer.

Chemical properties of polymers.

1. Molecular weight 2.Degree of polymerisation. 3.Polydispersity Index. 4.Conformation of chain in space. 5.Configuration of the chain (Microstructure)

MOLECULAR WEIGHT
Molecular weight, M:

Mass of a mole of chains.

LOW M

high M
Polymers can have various lengths depending on the number of repeat units. During the polymerization process not all chains in a polymer grow to the same length, so there is a distribution of molecular weights. There are several ways of defining an average molecular weight. The molecular weight distribution in a polymer describes the relationship between the number of moles of each polymer species and the molar mass of that species. 13

MOLECULAR WEIGHT DISTRIBUTION

M n x i Mi M w w i Mi
Mn = the number average molecular weight (mass) Mi = mean (middle) molecular weight of size range i xi = number fraction of chains in size range i wi = weight fraction of chains in size range i
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Degree of Polymerization, DP
DP = average number of repeat units per chain

Mn DP m where m repeat unit molecular weight

Ex. problem 4.1b,

for PVC: m = 2(carbon) + 3(hydrogen) + 1(Clorine)

(from front of book)

= 2(12.011) + 3(1.008) + 1(35.45) = 62.496 g/mol

DP = 21,150 / 62.496 = 338.42

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Polymer Chain Lengths

Many polymer properties are affected by the length of the polymer chains. For example, the melting temperature increases with increasing molecular weight. At room temp, polymers with very short chains (roughly 100 g/mol) will exist as liquids. Those with weights of 1000 g/mol are typically waxy solids and soft resins. Solid polymers range between 10,000 and several million g/mol. The molecular weight affects the polymers properties (examples: elastic modulus & strength).

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Polymers Molecular Shape

Straight (b) and twisted (c) chain segments are generated when the backbone carbon atoms (dark circles) are oriented as in the figure above. Chain bending and twisting are possible by rotation of carbon atoms around their chain bonds. Some of the polymer mechanical and thermal characteristics are a function of the chain segment rotation in response to applied stresses or thermal vibrations.

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Chain End-to-End Distance, r

Representation of a single polymer chain molecule that has numerous random kinks and coils produced by chain bond rotations; it is very similar to a heavily tangled fishing line. r is the end to end distance of the polymer chain which is much smaller than the total chain length.

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Molecular Structures for Polymers

secondary
bonding

Linear

Branched

Cross-Linked

Network

The physical characteristics of a polymer depend also on differences in the structure of the molecular chains (other variables are shape and weight). Linear polymers have repeat units joined end to end in single chains. There may be extensive van der Waals and hydrogen bonding between the chains. Examples: polyethylene, PVC, nylon.

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Molecular StructuresBranched
Linear Branched Cross-Linked Network

Where side-branch chains have connected to main chains, these are termed branched polymers. Linear structures may have side-branching. HDPE high density polyethylene is primarily a linear polymer with minor branching, while LDPE low density polyethylene contains numerous short chain branches. Greater chain linearity and chain length tend to increase the melting point and improve the physical and mechanical properties of the polymer due to greater crystallinity.

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Molecular Structures Cross-linked, Network

secondary bonding

Linear

Branched

Cross-Linked

Network

In cross-linked polymers, adjacent linear chains are joined to one another at various positions by covalent bonding of atoms. Examples are the rubber elastic materials. Small molecules that form 3 or more active covalent bonds create structures called network polymers. Examples are the epoxies and polyurethanes.

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Thermoplastics and Thermosets

The response of a polymer to mechanical forces at elevated temperature is related to its dominant molecular structure. One classification of polymers is according to its behavior and rising temperature. Thermoplastics and Thermosets are the 2 categories. A thermoplastic is a polymer that turns to a liquid when heated and freezes to a very glassy state when cooled sufficiently. Most thermoplastics are high-molecular-weight polymers whose chains associate through weak Van der Waals forces (polyethylene); stronger dipole-dipole interactions and hydrogen bonding (nylon).

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Thermoplastic polymers differ from thermosetting polymers (Bakelite, vulcanized rubber) since thermoplastics can be remelted and remolded. Thermosetting plastics when heated, will chemically decompose, so they can not be recycled. Yet, once a thermoset is cured it tends to be stronger than a thermoplastic. Typically, linear polymers with minor branched structures (and flexible chains) are thermoplastics. The networked structures are thermosets.
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Thermoplastics and Thermosets

Examples of Thermoplastics

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More Examples of Thermoplastics

Polymer

PTFE

Specific Thermoplastic Properties

Thermoset data

Thermoset Properties

Specific Elastomeric Properties

Elastomers, often referred to as rubber, can be a thermoplastic or a thermoset depending on the structure. They are excellent for parts requiring flexiblity, strength and durability: such as automotive and industrial seals, gaskets and molded goods, roofing and belting, aircraft and chemical processing seals, food, pharmaceutical and semiconductor seals, and wire and cable coatings.

Thermoplastic vs Thermoset
Thermoplastics:

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

--little cross linking --ductile --soften with heating --polyethylene polypropylene polycarbonate polystyrene
Thermosets:

Tm

Tg

crystalline solid

Molecular weight

--large cross linking (10 to 50% of mers) --hard and brittle --do NOT soften with heating --vulcanized rubber, epoxies, polyester resin, phenolic resin
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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

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Crystal Structures

Fe3C iron carbide orthorhombic crystal structure

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.

Polymer Crystallinity
Polymers are rarely 100% crystalline crystalline

Difficult for all regions of all chains to become aligned

region

Degree of crystallinity

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

amorphous region

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Thank you..