POLYMERS

ISSUES TO ADDRESS...
Overview of bonding and materials What are polymers? How are polymers manufactured and processed?

Polymers
What is a polymer? Poly
many
repeat unit repeat unit

mer
repeat unit
repeat unit

H H H H H H C C C C C C H H H H H H
Polyethylene (PE)

H H H H H H C C C C C C H Cl H Cl H Cl
Polyvinyl chloride (PVC)

H C H

H H C C CH3 H

H H C C CH3 H

H C CH3

Polypropylene (PP)

Adapted from Fig. 14.2, Callister 7e.

Ancient Polymer History

Originally natural polymers were used Wood Rubber Cotton Wool Leather Silk Oldest known uses Rubber balls used by Incas Noah used pitch (a natural polymer) for the ark

Chemistry of Polymers
Free radical polymerization
H H R + C C H H monomer (ethylene) H H + C C H H H H R C C H H initiation

free radical H H R C C H H

H H H H R C C C C H H H H dimer propagation

Initiator: example - benzoyl peroxide

H H H 2 H H C O H
5

C O O C

=2R

Chemistry of Polymers
Adapted from Fig. 14.1, Callister 7e.

Note: polyethylene is just a long HC - paraffin is short polyethylene

6

Bulk or Commodity Polymers

MOLECULAR WEIGHT
Molecular weight, Mi: Mass of a mole of chains.
Lower M higher M

total wt of polymer Mn total # of molecules

M n x i M i M w w i M i
Mw is more sensitive to higher molecular weights

Adapted from Fig. 14.4, Callister 7e.

10

Molecular Structures
Covalent chain configurations and strength:

secondary

bonding

Linear

Branched

Cross-Linked

Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 7e.

11

Tacticity
Tacticity stereoregularity of chain
isotactic all R groups on same side of chain
H H H H H H H H C C C C C C C C H R H R H R H R H H H R H H H R C C C C C C C C H R H H H R H H H H H H H R H H C C C C C C C C H R H R H H H R
12

syndiotactic R groups alternate sides

atactic R groups random

Copolymers
two or more monomers polymerized together random A and B randomly vary in chain alternating A and B alternate in polymer chain block large blocks of A alternate with large blocks of B graft chains of B grafted on to A backbone A B
random

Adapted from Fig. 14.9, Callister 7e.

alternating block

graft
13

Characteristics, Applications & Processing of Polymers

ISSUES TO ADDRESS...
What are the tensile properties of polymers and how are they affected by basic microstructural features? Hardening, anisotropy, and annealing in polymers. How does the elevated temperature mechanical response of polymers compare to ceramics and metals? What are the primary polymer processing methods?

14

Mechanical Properties
i.e. stress-strain behavior of polymers
brittle polymer

FS of polymer ca. 10% that of metals

plastic elastic modulus less than metal elastomer

Strains deformations > 1000% possible (for metals, maximum strain ca. 10% or less)

Adapted from Fig. 15.1, Callister 7e.

15

Tensile Response: Brittle & Plastic

Near Failure

(MPa)

x brittle failure
onset of necking

fibrillar structure

plastic failure

near failure

Initial

x
unload/reload

aligned, networked crosscase linked case

crystalline regions slide semicrystalline case amorphous regions elongate crystalline regions align

Stress-strain curves adapted from Fig. 15.1, Callister 7e. Inset figures along plastic response curve adapted from Figs. 15.12 & 15.13, Callister 7e. (Figs. 15.12 & 15.13 are from J.M. Schultz, Polymer Materials Science, PrenticeHall, Inc., 1974, pp. 500-501.) 16

Tensile Response: Elastomer Case

(MPa)
x brittle failure
Stress-strain curves adapted from Fig. 15.1, Callister 7e. Inset figures along elastomer curve (green) adapted from Fig. 15.15, Callister 7e. (Fig. 15.15 is from Z.D. Jastrzebski, The Nature and Properties of Engineering Materials, 3rd ed., John Wiley and Sons, 1987.)

plastic failure

elastomer

x
final: chains are straight, still cross-linked

initial: amorphous chains are kinked, cross-linked.

Deformation is reversible!

Compare to responses of other polymers:

-- brittle response (aligned, crosslinked & networked polymer) -- plastic response (semi-crystalline polymers)
17

Thermoplastics vs. Thermosets

Thermoplastics:
-- little crosslinking -- ductile -- soften w/heating -- polyethylene polypropylene polycarbonate polystyrene

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

Tm Tg

crystalline solid

partially crystalline solid

Thermosets:

-- large crosslinking Jr., Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc., 1984.) (10 to 50% of mers) -- hard and brittle -- do NOT soften w/heating -- vulcanized rubber, epoxies, polyester resin, phenolic resin
18

Adapted from Fig. 15.19, Callister 7e. (Fig. 15.19 is from F.W. Billmeyer,

Molecular weight

T and Strain Rate: Thermoplastics

Decreasing T...

(MPa)
80 4C 60 40 20 0 60C 0 0.1 0.2 20C 40C to 1.3 0.3
Data for the semicrystalline polymer: PMMA (Plexiglas)

-- increases E -- increases TS -- decreases %EL

Increasing strain rate...

-- same effects as decreasing T.

Adapted from Fig. 15.3, Callister 7e. (Fig. 15.3 is from T.S. Carswell and J.K. Nason, 'Effect of Environmental Conditions on the Mechanical Properties of Organic Plastics", Symposium on Plastics, American Society for Testing and Materials, Philadelphia, PA, 1944.)

19

Melting vs. Glass Transition Temp.

What factors affect Tm and Tg?
Both Tm and Tg increase with increasing chain stiffness Chain stiffness increased by 1. Bulky sidegroups 2. Polar groups or sidegroups 3. Double bonds or aromatic chain groups Regularity effects Tm only

Adapted from Fig. 15.18, Callister 7e. 20

Polymer Additives
Improve mechanical properties, processability, durability, etc. Fillers Added to improve tensile strength & abrasion resistance, toughness & decrease cost ex: carbon black, silica gel, wood flour, glass, limestone, talc, etc. Plasticizers Added to reduce the glass transition temperature Tg commonly added to PVC - otherwise it is brittle

21

Polymer Additives
Stabilizers Antioxidants UV protectants Lubricants Added to allow easier processing slides through dies easier ex: Na stearate Colorants Dyes or pigments Flame Retardants Cl/F & B

22

Back to the Beginning

Early in the course, we tried several ways to categorize polymers, such as condensation vs. addition, etc. From a processing point of view, the main classes are: Thermoplastic: the resin is heated to make a viscous liquid and then processed into a usable object without much additional chemistry. Example: polyethylene, polystyrene. Thermoset: upon heating, further reaction occurs to make molecules set up into a useful product. Chemistry occurs, so these are sometimes called reactive polymers. The resin may be provided as either small molecules or prepregspartially polymerized stuff. Example: polyurethanes, phenolformaldehyde, melamine-formaldehyde, epoxy glue.

Polymer Types
Coatings thin film on surface i.e. paint, varnish To protect item Improve appearance Electrical insulation Adhesives produce bond between two adherands Usually bonded by:
1. Secondary bonds 2. Mechanical bonding

Films blown film extrusion Foams gas bubbles in plastic

24

Advanced Polymers
Ultrahigh molecular weight polyethylene (UHMWPE) Molecular weight ca. 4 x 106 g/mol Excellent properties for variety of applications
bullet-proof vest, golf ball covers, hip joints, etc.
Adapted from chapteropening photograph, Chapter 22, Callister 7e.

UHMWPE

25

Biomaterials

A biomaterial is "any substance (other than drugs) or combination of substances synthetic or natural in origin, which can be used for any period of time, as a whole or as a part of a system which treats, augments, or replaces any tissue, organ, or function of the body". Biocompatibility The ability of a material to perform with an appropriate host response in a specific application Host Response The response of the host organism (local and systemic) to the implanted material or device.

Some Commonly Used Biomaterials

Material Applications Silicone rubber Catheters, tubing Dacron Vascular grafts Cellulose Dialysis membranes Poly(methyl methacrylate) Intraocular lenses, bone cement Polyurethanes Catheters, pacemaker leads Hydogels Opthalmological devices, Drug Delivery Stainless steel Orthopedic devices, stents Titanium Orthopedic and dental devices Alumina Orthopedic and dental devices Hydroxyapatite Orthopedic and dental devices Collagen (reprocessed) Opthalmologic applications, wound dressings

An Interdisciplinary Field
Bioengineers Material Scientists Immunologists Chemists Biologists Surgeons

A Little History on Biomaterials

Romans, Chinese, and Aztecs used gold in dentistry over 2000 years ago, Cu not good. Ivory & wood teeth Aseptic surgery 1860 (Lister) Bone plates 1900, joints 1930 Turn of the century, synthetic plastics came into use WWII, shards of PMMA unintentionally got lodged into eyes of aviators Parachute cloth used for vascular prosthesis 1960- Polyethylene and stainless steel being used for hip implants

Uses of Biomaterials
Replace diseased part dialysis Assist in healing sutures Improve function contacts Correct function spinal rods Correct cosmetic nose, ear Aid dx probe Aid tx catheter Replace rotten amalgam Replace dead - skin

Intraocular Lens
3 basic materials - PMMA, acrylic, silicone

Vascular Grafts

Second generation implants

engineered implants using common and borrowed materials developed through collaborations of physicians and engineers built on first generation experiences used advances in materials science (from other fields)

Examples Second generation implants

titanium alloy dental and orthopaedic implants cobalt-chromium-molybdinum orthopaedic implants UHMW polyethylene bearing surfaces for total joint replacements heart valves and pacemakers

Artificial Hip Joints

http://www.totaljoints.info/Hip.jpg

bioengineered implants using bioengineered materials few examples on the market some modified and new polymeric devices many under development

Third generation implants

Example - Third generation implants

tissue engineered implants designed to regrow rather than replace tissues Integra LifeSciences artificial skin Genzyme cartilage cell procedure some resorbable bone repair cements genetically engineered biological components (Genetics Institute and Creative Biomolecules BMPs)

Substitute Heart Valves

Drug Delivery Devices

Skin/cartilage

Polymers
Orthopedic screws/fixation

Ocular implants Bone replacements Heart valves

Metals

Synthetic BIOMATERIALS

Ceramics

Dental Implants

Dental Implants

Implantable Microelectrodes

Semiconductor Materials

Biosensors