Science of Materials
Science of Materials C
Dr. Andres Marquez
POLYMERS
Many types of polymers/Wide range of applications/
Several formation-production techniques
Numerous applications(all over the world).
Natural polymers: cellulose(wood), rubber, cotton, wool,
silk, proteins, enzymes, DNA, RNA.
Most under study are synthetic.
Plastics materials tend to be significantly stable (very slow
degradation).
POLYMERS
Can be combined/part of other materials:
Composites: fiber glass (glass dispersed in a polymer; for
insulation, reinforcement of structural components),
carbon fiber-reinforced polymer composite (aircrafts,
golf clubs, tennis racket).
RECEN TREND: Produce Bio-degradable polymers for
making plastics.
Currently, some plastics materials take about 100+ years
(argument over others that take even 200-400yrs) to
degrade in nature (even at soil/sea conditions!).
POLYMERS
Polymer(macromolecule):
Combination of small molecules (monomers), usually in long chains
of structural entities called repeat units.
(chain-like large molecular structures)
Many polymers: synthesized organic compounds; based on C, H and
other nonmetallic elements (O, N, Si, F, others).
Example: Polyethylene
Monomer: ethylene
CH2=CH2
Repeat unit
Polyethylene
-(CH2- CH2)n-
n: number of repeat units
POLYMERS
Others:
Polyvinyl Chloride (PVC): monomer vinyl chloride CH2=CHCl
Polypropylene (PP): monomer propylene CH2=CHCH3
Polystyrene (PS): monomer styrene CH2=CHØ (Ø: benzene ring)
Polytetrafluoroethylene (PTFE): monomer CF2=CF2
POLYMERS
Others (more complex):
Polycarbonate (PC): from bisphenol A and phosgene
Polyethyleneterephthalate (PETE or PET):
Homopolymer: same repeat unit.
Copolymer: two or more. Example: vinyl chloride and vinyl acetate
POLYMERS
Classification: different criteria
According to molecular structure:
Linear, branched, cross-linked, network.
According to their macrostructure:
Amorphous (lack of order).
Semi-crystalline (both amorphous and crystal regions):
According to Temperature effects:
Thermoplastic, Thermosetting
According to their use (Types of polymers):
Plastics
Elastomers (Rubbers)
Fibers
Others: Coatings, Adhesives, Films, Foams, Advanced
Polymeric Materials.
POLYMERS
According to molecular structure:
Linear Branched
HDPE: average density (ρ) = 0.96 g/cm3 LDPE: average density (ρ) = 0.93 g/cm3
Cross-linked Network
Many polymers have combinations
POLYMERS
According to their macrostructure:
Amorphous (lack of order).
Semi-crystalline (both amorphous and crystal regions-called crystallites). They are also
called crystalline (have some % crystallinity).
Crystallinity: packing of molecular chains
Polymers are not 100% crystallines.
Several polymers have high values of crystallinity: example PE
HDPE (80%-90% crystallinity)-more linear.
LDPE (50%-70%)-more branched (special case: LLDPE-Linear Low Density PE).
UHDPE (Ultra-High Density PE, or UHMWPE): can be 95% (or higher) crystalline.
Usually: Density (& Mw) of a more semi-crystalline polymer is greater than for a more
amorphous one; also, linear polymers tend to have more crystal regions than branched
ones (moreover, linear/branched more semi-crystallinity than cross-linked/network) .
POLYMERS
According to Temperature effects:
Depending on their response to (applied) stress
Thermoplastics and Thermosets:
Thermoplastics
Relatively soft; ductile;
Heating (at high Temperatures): softened, then hardened after cooling.
Can be re-heated/re-shaped (reversible process) w/o significant change in
properties.
Mostly linear/branched.
Easier to recycle.
Examples :
Commodities: PE (HDPE, LDPE), PVC, PS, PP.
Engineering: polyamide, polycarbonate, polyesters (PETE)
POLYMERS
According to Temperature effects:
Depending on their response to (applied) stress
Thermosets (thermosetting polymers/plastics) :
Hard (permanently “set/cured”, from fabrication); brittle;
When heated at high Temperature: do not soften/cannot be re-shaped,
will degrade/decompose.
Highly cross-linked & network structures.
Very difficult to recycle (sometimes cannot be recycled).
Examples:
Commodities: phenolics, unsaturated polyesters, ureas.
Engineering: silicones, polyurethanes, epoxies, melamines.
POLYMERS
Types of polymers (according to their use):
Plastics: largest number of polymeric materials.
Mostly rigid under load/stress.
Some degree of crystallinity.
Wide variety/combination of properties (some exhibit
outstanding/special properties).
Can be:
Linear, branched, cross-linked, network.
Thermoplastics or Thermosets.
Examples (out of Thousands of materials/applications):
HDPE, LDPE, PVC, PP, PS, PTFE (Teflon), PETE (or PET)
Teflon: extremely resistant to chemical attacks (even at
high Temp.); low coefficient of friction; as coating for
nonstick cookware.
POLYMERS
Types of polymers (according to their use):
Elastomers (Rubbers):
Deform easily, elastically (Long elongation/de-
elongation).
Cross-linked/network.
Examples:
Natural rubber(NR): latex. Polyisoprene
Synthetic rubber:
Styrene-Butadiene-Rubber (SBR): TIRES.
Nitrile-Butadiene-Rubber (NBR): Gloves. Other
applications: where oil resistance is desirable.
POLYMERS
Types of polymers (according to their use):
Fibers:
Mostly, made into filaments.
100:1 ratio length-to-diameter.
High strength.
Uses: textiles, nets, parachutes, ropes, cords.
Example: NYLON (a polyamide).
Polymer Additives to fabricate Plastics
Additive can be solid or liquid. Mainly, they are:
Stabilizers, Fillers, Plasticizers, Colorants, Flame Retardants.
They can also act as:
Property modifiers: promoters of
Strength/toughness/ductility/flexibility/hardness.
Binders.
Stabilizers
Prevent degradation/counteract deterioration of material (by exposure to
sun light – UV- , to environment).
Some absorb UV light.
Others react with O2 or O3(ozone); minimize oxidation.
Can be one of the factors that causes plastics to be highly stable-difficult to
degrade, with a very long life time.
Polymer Additives to fabricate Plastics
Fillers:
Mostly solids.
Enhance some properties (yield strength, TS, toughness,
thermal stability).
Low cost; act as substitutes of original/fresh/raw polymer.
Common filler materials employed:
Clay, silica (sand, glass), talc, wood flour, other polymers.
Plasticizers:
Mostly liquids (low vapor pressure, low Mw).
Enhance flexibility/ductility/toughness; decrease
hardness/stiffness;
Some applications: thin sheets films, curtains, tubing, raincoats.
Colorants:
Dyes/pigments; impart specific color.
Can dissolve in polymer in some cases (dyes).
POLYMERS
Flame Retardants: : Very important additive.
Must reduce/minimize fire promotion/extension/spread.
Must be added to lower Temperature of combustion.
Most polymers are flammable at ambient conditions (except, for
instance: PVC, Teflon; contain halogens: chlorine, fluorine).
For example (out of many): in
Toys
Textiles
Electrical wire insulation
Flammability in Polymers: some factors to consider related to fire safety:
- Ease of ignition/Ease of extinguishing (important, e.g., clothing).
- Rate of flame travel/Rate of flame penetration/Rate of heat
release (buildings)
- Smoke evolution/Toxic gas evolution (many applications; depend
on the polymer used; some more poisonous than others).
POLYMERS
Applications/Properties of Thermoplastics.
Commodities
Polyethylene-PE: most produced/used (relatively low cost/many applications).
HDPE:
density = 0.95 – 0.96 g/cm3. Modulus of elasticity (Young’s) = 1.08 GPa
Yield strength (YS) = 26.2 -33.1MPa . Tensile strength (TS) = 22.1 - 31.0 MPa.
%EL (ductility) = 10-120. Maximum (no load) Temperature of use = 80-120 ᵒC
80%-90% crystallinity – mostly linear. Chain structure
Applications (some):
Bottles of detergent/bleach/shampoo/milk/juice/motor-oil, caps, ice trays, crates,
toys, bowls, battery parts, appliance parts, house wares.
Properties for all are determined at room Temperature
POLYMERS
Applications/Properties of Thermoplastics.
Commodities
Polyethylene-PE: most produced/used (relatively low cost/many applications).
UHMWPE (UHDPE): high chemical attack/impact/wear/abrasion resistance, good
sound damping/energy absorption/electrical characteristics.
density = 0.94 g/cm3. Modulus of elasticity (Young’s) = 0.69 GPa
Yield strength (YS) = 21.4 - 27.6MPa . Tensile strength (TS) = 38.6 - 48.3 MPa.
%EL (ductility) = 350-525. Maximum (no load) Temperature of use = 90 ᵒC
95% (or higher) crystallinity – linear.
Applications (some):
Bulletproof vests, military helmets, fishing line, golf ball cores, biomedical prostheses.
Blood filters, bushings, pump impellers, valve gaskets.
Properties for all are determined at room Temperature
POLYMERS
Applications/Properties of Thermoplastics.
Commodities
Polyethylene-PE: most produced/used (relatively low cost/many applications).
LDPE: density = 0.92 – 0.93 g/cm3. Modulus of elasticity (Young’s)=0.172-0.282 GPa
Yield strength (YS) = 9.0 – 14.5MPa . Tensile strength (TS) = 8.3 – 31.4 MPa.
%EL (ductility) = 100-650. Maximum (no load) Temperature of use = 82-100 ᵒC
(50%-70%) crystallinity -mostly branched. Chain structure
LLDPE: density = 0.922 – 0.926 g/cm3. Modulus of elasticity (Young’s) = 120-200 MPa
Yield strength (YS) = 11 MPa . Tensile strength (TS) = 12.4 – 20.0 MPa.
%EL (ductility) = 600-800. Maximum (no load) Temperature of use = 60 ᵒC
(60%-75%) higher crystallinity – linear, little branching. Chain structure:
Applications (some):
Thin films (wrapping /packaging).
Plastic bags (garbage/garments/groceries).
Caps, coffee can lids, electrical wire insulation.
POLYMERS
Applications/Properties of Thermoplastics.
Commodities:
Polyvinyl chloride - PVC: second most produced/used.
Properties:
density = 1.30 – 1.58 g/cm3. Modulus of elasticity (Young’s)= 2.41 – 4.14 GPa
Yield strength (YS) = 40.7 – 44.8 MPa. Tensile strength (TS) = 40.7 – 51.7 MPa.
%EL (ductility) = 40-80. Maximum (no load) Temperature of use = 110 ᵒC (rigid)
Mostly amorphous. Brittle.
High solvent/chemical attack/flame resistance (due to Cl presence).
Tow main products: rigid and flexible PVC resins.
Applications (some):
PIPES.
Electrical wire insulation.
Doors, windows, floor coverings, garden hose, furniture.
POLYMERS
Applications/Properties of Thermoplastics.
Commodities:
Polypropylene - PP: third? most produced/used.
Properties:
density = 0.900 – 0.910 g/cm3. Modulus of elasticity (Young’s)= 1.14 – 1.55 GPa
Yield strength (YS) = 31.0 – 37.2 MPa. Tensile strength (TS) = 31.0 – 41.4 MPa.
%EL (ductility) = 100-600. Maximum (no load) Temperature of use = 107- 150ᵒC
Good hardness (surface).
Good chemical attack/moisture/heat resistance.
Used as a copolymer.
One product: high-impact PP.
Applications (some):
Caps, crates.
House ware/lab ware.
Sterilizable bottles, other bottles.
TV cabinets, luggage.
Tape, rope, cups, packaging, packaging films, electrical wire insulation, sacks.
POLYMERS
Applications/Properties of Thermoplastics.
Commodities:
Polystyrene - PS: fourth? most produced/used.
Properties:
density = 1.05 g/cm3. Modulus of elasticity (Young’s)= 2.28 – 3.28 GPa
Yield strength (YS) = 25.0 – 69.0 MPa. Tensile strength (TS) = 35.9 – 51.7 MPa.
%EL (ductility) = 1.2-2.5. Maximum (no load) Temperature of use 75 ᵒC
Virtually inflexible (room Temperature). Rigid. Brittle.
Good electrical/heat insulating properties.
Adequate mechanical properties.
Sensitive to chemical/organic solvents/oils attack.
Also used as a copolymer.
Some PS products: rubber-modified, impact-resistant, expandable.
Applications (some):
Toys.
Foam, foam cups(food, hot/cold drinks).
Hard/clear plastic cups,
Wall tile, battery cases, indoor panels, appliance housings, eating utensils.
POLYMERS
Applications/Properties of Thermoplastics.
Engineering:
Polyamide: e.g. Nylon (6,6): textiles, bearings, packaging, covers, wires/cables jackets.
Properties: highly crystalline, high strength, good chemical attack resistance/flexibility.
density = 1.14 g/cm3. Modulus of elasticity (Young’s)= 1.59 – 3.79 GPa
Yield strength (YS) = 44.8 – 82.8 MPa. Tensile strength (TS) = 75.9 – 94.5 MPa.
%EL (ductility) = 15-300. Maximum (no load) Temperature of use ᵒC
Polycarbonate: cellphone cases, helmets, lenses, photographic film, safety shields.
Properties: good electrical insulation/creep resistance/transparency.
density = 1.20 g/cm3. Modulus of elasticity (Young’s)= 2.38 GPa
Yield strength (YS) = 62.1 MPa. Tensile strength (TS) = 62.8 – 72.4 MPa.
%EL (ductility) = 110-150. Maximum (no load) Temperature of use ᵒC
Polyesters: e.g. PETE: clear plastic bottles (drinks), beverage containers, food product
bottles, textiles, clothing, magnetic recording tapes.
Properties:
density = 1.35 g/cm3. Modulus of elasticity (Young’s)= 2.76 – 4.14 GPa
Yield strength (YS) = 59.3 MPa. Tensile strength (TS) = 48.3 – 72.4 MPa.
%EL (ductility) = 30-300. Maximum (no load) Temperature of use ᵒC
POLYMERS
Applications/Properties of Thermosets:
Commodities:
Phenolics(with formaldehyde): motor housings, telephones, electrical fixtures, auto
distributors.
Properties: high cross-linking/hardness/strength, good heat/electrical insulation, good
chemical attack resistance.
density = 1.28 g/cm3. Modulus of elasticity (Young’s)= 2.76 – 4.83 GPa
Yield strength (YS) = – . Tensile strength (TS) = 34.5 – 62.1 MPa.
%EL (ductility) = 1.5-2.0. Maximum (no load) Temperature of use ᵒC
Unsaturated Polyesters: helmets, fiberglass boats, auto body components, chairs,
fans.
Properties:
density = 1.04 - 1.46 g/cm3. Modulus of elasticity (Young’s)= 2.06 – 4.41 GPa
Yield strength (YS) = – . Tensile strength (TS) = 41.4 – 89.7 MPa.
%EL (ductility) < 2.6. Maximum (no load) Temperature of use ᵒC
Ureas: dinnerware, adhesives, doorknobs, Toilet Seats, electrical components.
POLYMERS
Applications/Properties of Thermosets:
Engineering:
Silicones: medical applications, such as surgical instruments, cosmetic surgery.
Polyurethanes: adhesive, FOAMS (CUSHION)-mattress, furniture, bedding, textiles,
dashboard, desktops appliances.
Epoxies: adhesives (some types of glues), electrical molding, sinks, high-voltage
insulators, protective coatings (such as Corrosion Resistance Coatings).
Properties: good adhesion/mechanical strength/chemical attack resistance.
density = 1.11-1.40 g/cm3. Modulus of elasticity (Young’s)= 2.41 GPa
Yield strength (YS) = – . Tensile strength (TS) = 27.6 – 90.0 MPa.
%EL (ductility) = 3.0-6.0. Maximum (no load) Temperature of use ᵒC
Melamines: dinnerware, tableware, Toilet Seats, kitchen utensils, bathroom
accessories, electrical components.
Some properties (comparison)
POLYMERS
Recycling of plastic materials: one classification
Codes: 1 to 7 (arrows indicate recycling)
To facilitate the identification of the polymer(s) in the
plastics to be recycled.
Worldwide: NOT ENOUGH RECYCLING! (still serious
environmental concerns).
POLYMERS
Recycling of plastic materials: typical end uses(some)
liquid-soap/detergent/soft drink bottles, paint brushes.
soft-drink bottle caps, trash cans/recycling bins, toys.
floor mats, pipes, hoses.
grocery/multipurpose bags, garbage can liners.
paint buckets, fast-food trays, car battery parts.
license plate holders, desktop accessories, flowerpots.
SYNTHESIS OF POLYMERS
Polymerization reactions: different methods; usually:
• Step-growth (or condensation) polymerisation.
– Step-wise molecular chemical reactions.
– May involve copolymerization.
– Repeat unit chemical structure different from monomers.
– Simple chemical structure by-product is obtained (e,g., water)
– Example: PETE
• Addition (or chain-growth) polymerisation.
– Chain-like molecular chemical reaction.
– Usually, one monomer involved (there are cases of copolymerization).
– Linear-like resulting polymer.
We will focus only on addition polymerisation.
SYNTHESIS OF POLYMERS
Addition (or chain-growth) polymerisation.
- Polymer grows in a chain-like fashion, by adding on both sides of the
chain repeating units.
- Main types of addition polymerisation, depending on the nature of the
initiator:
* Free radical.
* Ionic: anionic and cationic.
- Three stages: initiation, propagation, and termination
- Initiator: molecule/compound that divides itself (into a free radical or an
ionic species) and generates active centres on a monomer.
- Polymer product has the same chemical composition than the starting
monomer.
- Examples: for PE, PP, PS, PVC.
POLYMERS
Transition Temperatures:
Temperatures at which polymers transform from solids into melt/liquid.
Melting (point) Temperature (Tm) and Glass transition Temperature (Tg):
Define the upper (Tm) and lower (Tg) limits of polymeric materials for many applications.
Glass transition Temperature (Tg): upon heating
A polymer transforms from a rigid solid/ordered material into a rubbery material.
Depends on Mw, composition, size, shape of polymer.
Abrupt properties changes occur at Tg: stiffness, thermal properties.
Most amorphous materials usually are cross-linked/network (Tg > linear/branched).
Examples:
HDPE: Tg = -90 ᵒC;
LDPE: Tg = -110 ᵒC;
PP: Tg=-18ᵒC;
PVC: Tg =87 ᵒC;
PS: Tg=100ᵒC;
PETE: Tg= 69ᵒC;
PTFE: Tg = -97ᵒC;
POLYMERS
Transition Temperatures:
Temperatures at which polymers transform from solids into melt/liquid.
Melting (point) Temperature (Tm): upon heating
Transformation from a rubbery material to a (highly) viscous liquid polymer with a random
structure.
For polymers: usually a Temperature range (made of many molecules; average Mw)
Depends on cooling/heating rate; Mw, composition, size, shape of polymer.
Reported: commonly a higher value .
HDPE: Tm = 137 ᵒC;
LDPE: Tm = 115 ᵒC
PP: Tm= 175 ᵒC ;
PVC: Tm = 212 ᵒC;
PS: Tm = 240 ᵒC;
PETE: Tm = 265 ᵒC;
PTFE: Tm = 327ᵒC;
POLYMERS
Transition Temperatures:
Specific Volume vs. Temperature : line C (100% crystal) shown only for illustration purposes.
POLYMERS
Fabrication Processes of Plastics materials:
Processing of plastic materials; transforming polymers plus additives into
plastics.
Depending on the type (Thermoplastic or Thermoset); some similarities with
metals and ceramics processing.
Also depend on material to be produced, raw polymer used (Tg /Tm).
Temperatures of operation are carefully monitored.
For Thermoplastics:
Molding: most common process; plastics forced to assume shape of a
mold/cavity.
Compression and transfer molding (less common).
Injection molding (most common).
Extrusion molding (most common).
Blow molding (similar to blowing glass bottles).
Thermoplastics are easier to recycle; easily re-melted & re-formed into new
shapes.
POLYMERS
Fabrication Processes of Plastics materials:
For Thermosets:
Several processes such as compression-transfer (more common) &
injection molding, pultrusion molding (continuous process to form
composites materials such a fiber glass), casting, others.
Casting: like metal casting , forming process in which a molten material is
poured into a cast/mold/cavity.
For both thermoplastic & thermosets.
Thermosets are difficult to recycle/can not be recycled; do no re-melt
easily/degrade at higher Temperatures; usually more chemically inert.
POLYMERS
Fabrication Processes of Plastics materials:
Thermoplastics:
Compression molding: heated mixture is placed in mold, then pressed; time
consuming, expensive. More used for thermosets.
POLYMERS
Fabrication Processes of Plastics materials:
For Thermoplastics:
Injection molding: mixture is placed on top, then injected (by pressure) into heated
chamber, passed though nozzle, and finally molded, where it solidifies quickly; rapid
process (cycles between 10 s to 30 s).
POLYMERS
Fabrication Processes of Plastics materials:
For Thermoplastics:
Extrusion molding: mixture is placed on top, then passed through a heated
chamber (by a turning screw), and finally forced though shaping die, where it comes out
and solidifies by blowers- water spray - or water bath. Continuous process; specially for
continuous lengths/constant cross-sectional geometries materials (rods, tubes, sheets,
filaments, hose channels).
POLYMERS
Fabrication Processes:
Blow Molding: similar to the one for blowing glass bottles
For polymers, air or steam is blown into the hollow piece. Temperature is carefully
monitored.
POLYMERS
Pictures of some resins
HDPE LDPE PVC
PS PP PETE (PET)
Science of Materials
Dr. Andres Marquez
[email protected]
MYELEARNING
Office Hours
Mondays: 9:00 a.m. – 11:30 a.m.
Tuesdays: 2 :00 p.m. – 5:00 p.m.
Location: 1st floor, chemical engineering, block 13
(open door policy; if available)
