Polymer Process Engineering

Introduction

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Fundamental concepts + language

Nomenclature
Chemical bonding, chemical interactions, entanglements
Molecular weight
Thermal transitions

PRIMER

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Berzelius (1883) Poly (many) + mer (unit)

Polystyrene polymerized in 1938; polyethylene glycol made in 1860s
Early polymer products were based on cellulose- gun cotton = nitrated
cellulose

WHAT IS A POLYMER?

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A polymer is
Long chain molecule, often based on organic
chemical building blocks (monomers)
Long molecules (Mw ~100,000 Da) have solidlike properties
The chain may be amorphous (no regular
structure), crystalline (a regular repeating
structure), crosslinked,
Dendrimers and oligomers have different
properties
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Chemical structure
Chain morphology constitution, configuration, conformation
Degree of polymerization = number of repeating units
Building block sources hydrocarbons, renewable materials

HOW DO YOU BUILD A MOLECULE?

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Building blocks
5% of petroleum goes
into polymers
Sustainable use is
possible
Energy recovery is
possible if solid
polymers are
combusted

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Type

gas

NG

liquid

Crude

solid

Coal

14

Renew- cellulose
able

5.3

Hemicellulose

lignin

6.8

protein

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Building methods
Chain (addition)
Example polyethylene (PE)
from ethylene
Small number of reacting
chains at any one time,
which can grow into long
molecules prior to
termination
Long reaction times needed
to achieve high conversions

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Step (condensation)
Example poly(ethylene
terephthalate) (PET) from
terephthalic acid and
ethylene glycol
Endgroups react to build the
chain; long reaction times
needed to achieve high
polymer

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Multiple building blocks

Copolymers, terpolymers,
Using multiple building blocks leads to
polymers with intermediate properties or
unique properties compared to the
homopolymers

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Several copolymer configurations

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Chain configurations
Linear repeating units are aligned
sequentially
Branched large segments branch off the
main chain/carbon backbone
Crosslinked/network chemical crosslinks
between chains add mechanical strength
EXAMPLES?

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Multiphase systems
Composites
Structural
Random
Other
Nanocomposites

Blends
Dispersed lamellae, cylinders, spheres

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Structure chemical, configuration

solid performance (mechanical + thermal properties)
other

HOW DO WE CLASSIFY POLYMERS?

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Mechanical + Thermal
Thermoplastic solidified by cooling and
reheated by melting
Thermosets retain their structure when
reheated after polymerization (usually
crosslinked)
Elastomers rubbers, deform readily with
applied force
Thermoplastic elastomers
other
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Very few commercial products are pure

MWD molecular weight distribution
additives

WHAT IS IN A COMMERCIAL
PRODUCT?
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Polymers vs. metals

Why do we use
polymers?

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Polymeric materials
Compete well on a strength/weight basis
Easy to form into 3D shapes
Creep under load is usually poor; this behavior
is usually corrected by adding fillers or fibers
Low corrosion in the environment compared
to metals
Generally good solvent resistance

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Thermoplastics
Commodities: 75% of the polymer volume
used is with 4 polymer families, polyethylene,
polystyrene, polypropylene and poly(vinyl
chloride) [low cost]
Intermediate: higher heat deflection
temperatures
Engineering plastics: can be used in boiling
water
Advanced thermoplastics: extreme properties
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Thermosets
High moduli, high flex strengths, high heat
deflection temperatures
Shape is retained during thermal cycling
Often made with step/condensation
polymerization systems
Crosslinking is usually used

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Polymerization
Formulation
Fabrication

HOW DO WE MAKE A PART?

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Formulation
Additives are used to modify properties
and/or lower costs
Additives: heat stabilizer, light stabilizer,
lubricant, colorant, flame retardant, foaming
agent, plasticizer
Reinforcement: particulate minerals, glass
spheres, activated carbon, fibers
Blends, alloys, laminates
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Additives can change:

Processing properties
Performance properties
Composites: polymers with fiber fillers
Packaging: multiple layers often used

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Formulation operations
Thermoplastics: melting or solvent processing
Thermosets: additive addition to monomers
or to prepregs

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Fabrication
Varies by industry sector
Adhesive
Coating
Elastomer
Plastic
fiber

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Overview of the polymer industry

Industry

General product requirements

adhesive

Strong surface forces; epoxy, superglue

coatings

Film-forming; LDPE with good impact

composites

Structural materials; epoxy + fibers

elastomers

Large deformation and recovery; rubber in tire and seals

fibers

High strength/area; polyacrylonitrile

foams

Light weight, low thermal conductivity; polyurethane

plastics

Stable deformation under static load; HDPE, PP, PVC

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Commodity plastics
Polymer

Major uses

LDPE

Packaging film, wire and cable insulation, toys, flexible bottles,

housewares, coatings

HDPE

Bottles, drums, pipe, conduit, sheet, film, wire and cable

insulation

PP

Automobile and appliance parts, rope, cordage, webbing,

carpeting, film

PVC

Construction, rigid pipe, flooring, wire and cable insulation,

film, sheet

PS

Foam and film packaging, foam insulation, appliances,

housewares, toys

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Film blowing
High strength films are achieved by
orienting the crystallites. The film is
biaxially oriented; the wind-up rolls
stretch the film in the machine direction
and the expansion of the film radially
provides a hoop stress force.

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Wire coating

Wire coating speeds can be high, and process start-up is challenging. Metal wires may need sizing,
or wetting agents in the polymer melt for good adhesion.

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Calendaring

Thin and thick section calendaring is used to make wide sheets (8-12 ft).
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Bottle blowing
The parison is inflated,
developing biaxially
orientation similar to that of
blown film. The sides of the
mold provide cooling, quickly
freezing in the orientation
developed during the
blowing process. When this
process is used to make soda
bottles of PET, the
orientation is critical to
achieving low carbon dioxide
permeation rates (and long
bottle shelf life).

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Compression molding

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Thermoset applications
Polymer

Major uses

PhenolElectrical equipment, automobile parts, utensil handles,

formaldehyde resins plywood adhesives, particleboard binder
(PF)

Urea-formaldehyde
resins (UF)

Similar to the above; textile coatings and sizings

Unsaturated
polyester (UP)

Construction, vehicle parts, boat hulls, marine accessories,

corrosion-resistant ducts, pipes and tanks, business equipment

Epoxy (EP)

Protective coatings, adhesives, electrical parts, industrial

flooring, highway paving materials, composites

MelamineSimilar to UF resins; decorative panels, counter and table tops,

formaldehyde resins dinnerware
(MF)
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Elastomers
The polymers used for elastomers usually have
very low heat deflection and melt temperatures
Solids with good mechanical properties are made
by crosslinking polymer chains together
The molecular weight of elastomer parts is the
size of the object
Vulcanization of rubber uses sulfur to provide
crosslinks between the C=C bonds of natural
rubber.
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Fibers
Fibers are based on highly crystalline polymers
that can be oriented axially to have great
strength. Orientation (cold drawing) develops
crystal structure in the solid.
Most natural fibers from biomass are based
on cellulose; spider silk has different
compositions and is based on a set of
copolymers
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Elastomer polymers
Polymer family

description

Styrene-butadiene

Copolymers with a range of constitutions; SBR styrenebutadiene rubber

Polybutadiene

Cis-1,4-polymer

Ethylene-propylene

EPD ethylene-propylene-diene monomer; the small amounts

of diene provide unsaturation

Polychloroprene

Poly(2-chloro-1,3-butadiene); this polar elastomer has excellent

resistance to non-polar organic solvents (gasoline, diesel)

Polyisoprene

Poly(cis-1,4-isoprene); synthetic natural rubber

Nitrile rubber

Copolymer of acrylonitrile and butadiene

Butyl rubber

Copolymer of isobutylene and isoprene

Silicon rubber

Rubber based on polysiloxanes

Urethane rubber

Elastomer with polyethers linked via urethane groups

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Synthetic fibers
Fiber type

description

Cellulosic
acetate rayon

Cellulose acetate

viscose rayon

regenerated cellulose

Non-cellulosic
Polyester

Mostly poly(ethylene terephthalate)

Nylon

Nylon 6,6; nylon 6, nylon 10; other aliphatic, aromatic

polyamides

Olefin

Polypropylene; copolymers of vinyl chloride + acrylonitrile, vinyl

acetate, vinylidene chloride

Acrylic

> 80% acrylonitrile; modacrylic = acrylonitrile + vinyl chloride or

vinylidene chloride

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Coatings
Coatings. Major area for expansion; solar cells,
windows, Supplier base is highly
fragmented.
Paints. Major area for expansion; vehicles,
Materials supplier base is clustered; painting
systems base is clustered; user base is
fragmented

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Adhesives
Highly fragmented market.

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Foams
Major area: insulation
for housing, sound
control,
Materials:
polystyrene,
polyurethanes,
Reaction injection
molding example
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Composites
Thermosets and thermoplastics
Sheet molding compounds
Filament winding

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Polymer nomenclature is widely varied.

Trademarks and common names may be industry-sector specific.
Nomenclature: Polymer Handbook. Chapter 1.

HOW DO WE NAME POLYMERS?

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Source-based names
Source-based name when the polymer is derived
from a single (original or hypothetical) monomer;
or random co-/ter-polymers

Poly(vinyl alcohola)
Poly(styrene-co-butadiene)
Polyformaldehyde (not polyoxymethylene)b
Poly(ethylene oxide) (not poly(ethylene glycol)b

when the name is long, parentheses are used to

separate the name from poly
b - actually the second name is quite common
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Structure-based names
Structure-based name when the
constitutional repeating unit (CRU) has several
components
The CRU is independent of the monomers and
polymerization methods
Poly(hexamethylene adipamide)
Poly(ethylene terephthalate)

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copolymers
Type

Connective

Example

unspecified

-co-

Poly(A-co-B)

statistical

-stat-

Poly(A-stat-B)

random

-ran-

Poly(A-ran-B)

alternating

-alt-

Poly(A-alt-B)

periodic

-per-

Poly(A-per-B-per-C)

block

-block- (-b-)

Poly(A-b-B) or Poly A-block-poly B

graft

-graft- (-g-)

Poly(A-g-B) or Poly A-graft-poly B

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Source-based name

Structure-based name

Trade name, abbreviation

polyethylene

polymethylene

PE, LDPE, HDPE, LLDPE

polypropylene

Poly(propylene)

PP

polyisobutylene

Poly(1,1-dmethylethylene)

PIB

polystyrene

Poly(1-phenylethylene)

Styron, Styrofoam

Poly(vinyl chloride)

Poly(1-chloroethylene)

PVC

Poly(vinylidene chloride)

Poly(1,1-dichlorethylene)

Saran

polytetrafluoroethylene

Poly(difluoromethylene)

Teflon

Poly(vinyl acetate)

Poly(1-acetoxyethylene)

PVAC

Poly(vinyl alcohol)

Poly(1-hydroxyethylene)

PVAL

Poly(methyl methacrylate)

Poly(1-methoxycarbonyl-1methylethylene)

PMMA; Lucite, Plexiglass

polyacrylonitrile

Poly(1-cyanoethylene)

PAN; Orlon, Acrilan fibers

polybutadiene

Poly(1-butenylene)

BR rubber

polyisoprene

Poly(1-methyl-1-butenylene)

NR rubber

polychloroprene

Poly(1-chloro-butenylene)

Neoprene

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Polymers with other backbones

Source-based name

Structure-based name

Trade name, abbreviation

polyformaldehyde

Poly(oxymethylene)

POM

Poly(ethylene oxide)

Poly(oxyethylene)

PEO

Poly(ethylene glycol adipate)

Poly(oxyethylene oxyadipoyl)

Polyester 2,6

Poly(ethylene terephthalate)

Poly(oxyethylene oxy-terephthaloyl)

PET; Dacron

Poly(hexamethylene
adipamide)

Poly(iminoadipoyl imino-hexamethylene) Nylon 6,6

Poly(e-caprolactam)

Poly(imino[1-oxohexamethylene])

Nylon 6

polyglycine

Poly(imino[1-oxoethylene])

Nylon 2

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Bonding along the backbone is not extraordinary.

With long chains, secondary valence forces, integrated over the entire
chain, provide considerable bonding forces.
Chain entanglements provide physical linkages.

WHY ARE LONG CHAIN MOLECULES

SOLIDS?
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Chemical bonding in polymers

Most primary bonds along the

backbone are covalent
Secondary valence bonds

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Much smaller forces than the

covalent bonds, but become
significant when integrated over the
entire chain
Consider the forces acting on this
macromolecule as it is pulled
through the tube surrounding its
structure in three dimensional space
As each chain segment moves, it
must overcome the local
interactions at the tube surface
Longer chains will have more
resistance to motion

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Secondary valence forces

Secondary valence forces affect the glass transition, the
melting temperature, crystallinity, melt flow,
They include: nonpolar dispersion, polar dipoles, polar
induction, and hydrogen bonds
Secondary bond

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Bond energy,
kcal/mol

Range of action,
Angstrom

Dispersion

0.1-5.0

3-5 (r-6)

Dipole-dipole

0.5-5.0

1-2 (r-3)

Dipole-induced
dipole

0.05-0.5

1-2 (r-6)

Hydrogen bond

1.0-12

2-3 (r-2)

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Few synthetic polymers are monodisperse, i.e., have one chain length.
Many biological polymers do have specific molecular weights, e.g., proteins,
DNA,
The molecular weight distribution has critical effects on polymer properties
in the melt and solid states.

WHAT ARE TYPICAL CHAIN LENGTH

DISTRIBUTIONS?
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Typical effects of molecular weight

distributions
Homopolymers with different molecular weight distributions may be
insoluble in each other
# carbon atoms

State

Use

1-4

Gas

Gaseous fuel

5-11

Low viscosity liquid

gasoline

9-16

Medium viscosity
liquid

kerosene

16-25

High viscosity liquid

Oil, grease

25-50

Crystalline solid

Paraffin wax

1000-3000

Plastic solid
(crystalline +
amorphous)

polyethylene

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Linear
alkane
properties

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MWD - oligomer
Poly(a-olefin); PAO6
Synthetic base oil
vehicle use
Trimer, tetramer,
pentamer, hexamer,
heptamer
Based on 1-decene
Ionic polymerization
Differential distribution
by size exclusion
chromatography
PeakFit used for curve
deconvolution
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Two polyethylenes

Weight frequency, differential

distributions
Number-average molecular
weights are the same
Weight-average molecular
weights are different

Narrow MWD PD ~ 5.7

Broad MWD PD ~ 15
Differences in flow, tensile and
appearance properties

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n M
i

Mn

PD

w M n M
i

Mw

w
i

2
i

n M
i

Mw

Mn

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In-class exercise

HOW DOES CHAIN LENGTH AFFECT

PROCESSING?
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In-class exercise

HOW DOES CHAIN LENGTH AFFECT

PERFORMANCE?
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Thermal properties are often key criteria used to select polymers for specific
applications.
Five regions of viscoelastic behavior (many polymers have all five): < glass
transition, power law region, rubbery plateau, rubbery flow, fluid flow
Other crystalline solids, crosslinked elastomers

WHAT ARE IMPORTANT THERMAL

TRANSITIONS?
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Five regions of viscoelasticity

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Use amorphous polymers below Tg

Use crystalline polymers below Tm
Crosslinked elastomers at G
Melt processing between B and C

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Typical G vs T plots

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regions
Viscoelasticity: most polymers creep(slow flow) under long-term stress.
Creep may not be recoverable, i.e., the sample may not recoil to its
original dimensions. Over short periods of time, polymers are elastic.
Solid yield and fracture: elasticity for e < 0.1%; PS is brittle and fails at low
elongations. PE yields, and then undergoes cold drawing to > 300%
elongation.

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BUILDING A GLOSSARY

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Medical applications are a

rich applications area for
polymers.
Local variations in surface
roughness at the nanoscale
can induce strains in cell
membranes, leading to the
growth of F-actin stress
fibers that span the length
of the cell.
W.E. Thomas, D. E. Discher, V. P. Shastri,
Mechanical regulation of cells by materials
and tissues, MRS Bulletin, 35 (2010), 578583.

POLYMER SCIENCE DIRECTIONS

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Cells feel their environment

Tissues are hydrated natural polymers with controlled
elasticity
Most animals cells require adhesion to a solid to be
viable
Tissue elasticity (~ kPas) is important for regulating cell
growth, maturation and differentiation. Brain 0.2 < E <
1 kPa; fat 2 < E < 4 kPa; muscle 9 < E < 15 kPa;
cartilage 20 < E < 25; bone 30 < E < 40 kPa
Nanoroughness seems to affect a number of cell
processes
3D scaffolding is important
Mechanotransduction: cells adhere to surfaces via
adhesive proteins attached to adaptor proteins, to the
actomyosin cytoskeleton.

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