MME 295: Engineering Materials II

Lecture 17

Polymeric Materials:
1. Introduction, structure and classification

Todays Topics

 Definition of polymers  Polymer structures  Generic polymers

Introduction
Definitions
Polymer: long molecule made up by the repetition of small units called mar. Synonym: macromolecule  High molecular weight (M)  e.g., polystyrene (PS) Monomer: molecule that combines with others (identical or different) to form a polymer  e.g., ethylene (PE polyethylene) Oligomer: low molecular weight polymer, constituted of at least two monomers

Introduction
Molecular forces in polymers
[1] Intramolecular forces: Forces between atoms in one chain; generally covalent bonds (strong) [2] Intermolecular forces: Forces between two chains; van der Waals forces (PE), hydrogen bridges (PS) [3] Entanglements (physical)
In the crystalline state, the van der Waals bonds are important. In the rubbery amorphous state, the entanglements are important.

Polymer Structure_1
Hydrocarbon molecules
z Most polymers are organic, and formed from hydrocarbon molecules z Each C atom has four e- that participate in bonds, each H atom has one bonding ez Unsaturated hydrocarbons contain double and triple bonds between C atoms (sharing of two or three electron pairs).

H H C H H
methane, CH4 Example of saturated hydrocarbon molecule (all bonds are single ones)

H H

H H

H C | C H
acetylene, C2H2 Unsaturated molecules are more reactive

C = C
ethylene, C2H4

Polymer Structure_2
Polymer molecules
z Polymer molecules are very large: they are macromolecules. z Most polymers consist of long and flexible chains with a string of C atoms as a backbone.

z z z z

C atoms are side-bonded to H atoms or radicals Double bonds are possible in both chain and side bonds A repeat unit in a polymer chain (unit cell) is a mer A single mer is called a monomer

Polymer Structure_3
Polymer molecules
 Even though the basic makeup of many polymers is carbon
and hydrogen, other elements can also be involved.
O, Cl, F, N, Si, P, and S are other elements found in the molecular makeup of polymers. E.g.,  Polyvinyl chloride (PVC) contains chlorine.  Nylon contains nitrogen.  Teflon contains fluorine.  Polyester and polycarbonates contain oxygen.

 There are also some polymers that, instead of having a carbon backbone, have a silicon or phosphorous backbone.
 These are considered inorganic polymers.  E.g., polysiloxanes (Silicones) and polyphosphazenes

Polymer Structure_4
Polymer molecules
Examples of Some Homopolymer H C H H C X n X=H X = CH3 X = Cl X= Polyethylene (PE) Polypropylene (PP) Polyvinylchloride (PVC) Polystyrene (PS)

When all mars are the same, the molecule is called homopolymer. When there are more than one mars, the molecule is called copolymer.

Polymer Structure_5
Polymer molecules

Poly(ethylene terephthalate) PET

Poly(carbonate)

Poly(acrylate) PAA Poly(methylmethacrylate) PMMA

Poly(dimethyl siloxane)

Polymer Structure_6
Polymer molecular shape

The angle between the singly bonded carbon atoms is }109 carbon atoms form a zigzag pattern in a polymer molecule. While maintaining the 109 angle between bonds polymer, chains can rotate around single C-C bonds (double, triple bonds are very rigid).

r = Pn
r = head-toe distance n = no. of steps P = length of step

Random kinks and coils lead to entanglement, like in the spaghetti structure

Polymer Structure_7
Polymer molecular structure
Branched polymers
z z

Inefficient chain packing causes reduced density Examples: LDPE

Linear polymers
Van der Waals bonding between chains. z Examples: polyethylene, nylon, HDPE.
z

Network polymers
z z

3D networks made from trifunctional mers. Examples: epoxies, phenolformaldehyde

Cross-linked polymers
z z

Chains are connected by covalent bonds. Example: rubbers.

Polymer Structure_8
Polymer molecular structure
HDPE

LDPE
Linear, unbranched polymer Linear, branched polymer

Cross-linked, unbranched polymer Cross-linked, branched polymer

Branching increases the volume and thus reduces the density of the polymer.

Polymer Structure_9
Polymer molecular weight, MW
z The average molecular weight can be obtained by averaging the masses with the fraction of times they appear (number-average molecular weight) or with the mass fraction of the molecules (weight-average molecular weight). Number average: Mn = xiMi Weight average: Mw = fiMi
Mi = the mean mol. wt. of range i fi = wt. fraction of chains of length i xi = no. fraction of chains of length i

z Final molecular weight (chain length) is controlled by relative rates of initiation, propagation, termination steps of polymerization.

Polymer Structure_10
Polymer molecular weight, MW
Example
We have a polyethylene sample containing 4000 chains with molecular weights between 0 and 5000 g/mol, 8000 chains with molecular weights between 5000 and 10,000 g/mol, 7000 chains with molecular weights between 10,000 and 15,000 g/mol, and 2000 chains with molecular weights between 15,000 and 20,000 g/mol. Determine both the number and weight average molecular weights.

Solution
First we need to determine the number fraction xi and weight fraction fi for each of the four ranges. We can then use the equations to find the molecular weights.

M n = x iM i M w = f iM i

Polymer Structure_11
Polymer molecular weight, MW

Polymer Structure_12
Polymer molecular weight, MW
z Melting / softening temperatures, and tensile strength increase with molecular weight (up to b100,000 g/mol) z At room temperature,
 short chain polymers (molar weight b100 g/mol) liquids or gases  intermediate length polymers (b 1000 g/mol) waxy solids  long chain polymers (104 - 107 g/mol) solid

Polymer Structure_13
Polymer Crystallinity
z Atomic arrangement in polymer crystals is complex. z Polymer molecules are often semicrystallined, with partially crystalline regions dispersed within amorphous material. crystalline region

Vc (VsVa) % Crystallinity = x100 Vs (VcVa)

Vc = density of perfect crystalline polymer Va = density of completely amorphous polymer Vs = density of partially crystalline polymer sample

amorphous region
z annealing causes crystalline regions to grow % crystallinity z Density, TS, E with crystallinity

z The degree of crystallinity depends on

1. Rate of cooling (faster cooling, less crystallinity) 2. Type of polymer (simple structure, more crystallinity

3. Linear polymer more easily form crystals.

The Generic Polymer_1

 There is a bewildering number of polymers and the number increases every year.  The four generic polymers are:
(1) Thermoplastics (or, plastics), which soften on heating (e.g., polyethylene) (2) Thermosets (or, resins), which harden when two components (resin and hardener) are heated together (e.g., epoxy) (3) Elastomers (or, rubbers), which are thermoplastics or lightly cross-linked thermosets and have more than 200 % elastic deformation (4) Natural polymers, which provide the mechanical basis of most plants and animal life (e.g., cellulose, lignin, protein)

Thermoplastics_1
 Often described as linear polymers i.e., chains are not cross linked (though may be branched occasionally).
 that is why they soften when heated  the secondary bond that binds the molecules to each other melts so that it flows like viscous fluid and allowing it to be formed

 Have a range of molecular weight.

 packed together in a variety of configurations - amorphous (polystyrene), semi-crystalline (polyethylene)  do not have a sharp melting point - viscosity falls over a range of temperature, like inorganic glass

Thermoplastics_2
 Made by adding together (i.e., polymerising) sub-units (monomers) to form long chains.  Many of them are made of the many repeated units of: H C H H C R

 The radical R may simply be H (as in polyethylene), or CH3 (polypropylene), or Cl (polyvinyl chloride).
 some are more complicated (e.g., nylon)

 Common classes of thermoplastics are listed in Table 1.

 besides these, the fibre and fibre-forming polymer polyacrylonitrile (PAN) and polyethylene terapthalate (PET) are also thermoplastics.

Thermoplastics_3
Table 1: Generic thermoplastics.

Thermoplastics_4
Table 1: Generic thermoplastics (contd ...)

Thermosets_1
 Made by mixing two components, a resin and a hardener, which react and harden, either at room temperature or on heating.  Resulting polymers are heavily cross-linked, so thermosets are sometimes referred to as network polymers.
 cross-link forms during polymerisation of liquid resin and hardener  the structure is almost always amorphous

 During reheating of thermosets

    additional secondary bond melts, and modulus drops but cross-link prevents true melting or viscous flow thus thermosets cannot be hot worked further reheating causes thermosets to decompose

Thermosets_2
Table 2: Generic thermosets.

Thermosets_3
Table 2: Generic thermosets.

Elastomers_1
 Almost linear polymers, with occasional cross-link.  The secondary bonds already melted at room temperature.  Cross-link provides the memory of material, so that it returns to its original shape on unloading.  Common elastomers are based on the single structure with the position R occupied by H, CH3, Cl. H C H C H C R H C H n

Elastomers_2
Table 3: Generic elastomers.

Elastomers_3
Table 3: Generic elastomers.

Natural Polymers_1
 Common natural polymers include:
 natural rubber (e.g., polyisoprene)  cellulose and lignin (main component of wood and straw)  protein (wool or silk)

Natural Polymers_1
Table 4: Generic natural polymers.
Natural polymer Cellulose Composition Applications Framework of all plant life, as the main structural component in cell walls The other main component in cell walls of all plant life Gelatin, wool, silk C O n

( C 6 H 9 O 6 )n
Amorphous R NH C H

Lignin Protein

Next Class

Lecture 18

Polymeric Materials:
2. Synthesis and Processing