Chapter 1

Polymer Process Engineering
Introduction
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Chapter 1. Primer/introduction
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
Type gas liquid solid NG Crude Coal C 3 6 14 6 6 6.8 H 1 1 1 1 1 1 O 0 0 0 5.3 8 3
Renew- cellulose able Hemicellulose lignin 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 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
Very few commercial products are pure MWD molecular weight distribution additives
WHAT IS IN A COMMERCIAL PRODUCT?

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
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
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 adhesive coatings
composites elastomers fibers foams plastics
General product requirements Strong surface forces; epoxy, superglue Film-forming; LDPE with good impact
Structural materials; epoxy + fibers Large deformation and recovery; rubber in tire and seals High strength/area; polyacrylonitrile Light weight, low thermal conductivity; polyurethane Stable deformation under static load; HDPE, PP, PVC
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Commodity plastics
Polymer LDPE HDPE PP PVC PS Major uses Packaging film, wire and cable insulation, toys, flexible bottles, housewares, coatings Bottles, drums, pipe, conduit, sheet, film, wire and cable insulation Automobile and appliance parts, rope, cordage, webbing, carpeting, film Construction, rigid pipe, flooring, wire and cable insulation, film, sheet 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).
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)

Unsaturated polyester (UP) Epoxy (EP)
Similar to the above; textile coatings and sizings

Construction, vehicle parts, boat hulls, marine accessories, corrosion-resistant ducts, pipes and tanks, business equipment 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)
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.
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
Elastomer polymers
Polymer family Styrene-butadiene Polybutadiene Ethylene-propylene Polychloroprene description Copolymers with a range of constitutions; SBR styrenebutadiene rubber Cis-1,4-polymer EPD ethylene-propylene-diene monomer; the small amounts of diene provide unsaturation Poly(2-chloro-1,3-butadiene); this polar elastomer has excellent resistance to non-polar organic solvents (gasoline, diesel)
Polyisoprene
Nitrile rubber Butyl rubber Silicon rubber Urethane rubber
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Poly(cis-1,4-isoprene); synthetic natural rubber

Copolymer of acrylonitrile and butadiene Copolymer of isobutylene and isoprene Rubber based on polysiloxanes Elastomer with polyethers linked via urethane groups
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Synthetic fibers
Fiber type Cellulosic acetate rayon viscose rayon Non-cellulosic Polyester Nylon Olefin Acrylic Mostly poly(ethylene terephthalate) Nylon 6,6; nylon 6, nylon 10; other aliphatic, aromatic polyamides Polypropylene; copolymers of vinyl chloride + acrylonitrile, vinyl acetate, vinylidene chloride > 80% acrylonitrile; modacrylic = acrylonitrile + vinyl chloride or vinylidene chloride Cellulose acetate regenerated cellulose description
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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
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

a
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
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 unspecified statistical random alternating periodic block graft Connective -co-stat-ran-alt-per-block- (-b-) -graft- (-g-) Example Poly(A-co-B) Poly(A-stat-B) Poly(A-ran-B) Poly(A-alt-B) Poly(A-per-B-per-C) Poly(A-b-B) or Poly A-block-poly B Poly(A-g-B) or Poly A-graft-poly B
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Source-based name polyethylene polypropylene polyisobutylene polystyrene Poly(vinyl chloride) Poly(vinylidene chloride) polytetrafluoroethylene Poly(vinyl acetate) Poly(vinyl alcohol) Poly(methyl methacrylate) polyacrylonitrile polybutadiene polyisoprene polychloroprene
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Structure-based name polymethylene Poly(propylene) Poly(1,1-dmethylethylene) Poly(1-phenylethylene) Poly(1-chloroethylene) Poly(1,1-dichlorethylene) Poly(difluoromethylene) Poly(1-acetoxyethylene) Poly(1-hydroxyethylene) Poly(1-methoxycarbonyl-1methylethylene) Poly(1-cyanoethylene) Poly(1-butenylene) Poly(1-methyl-1-butenylene) Poly(1-chloro-butenylene)
Trade name, abbreviation PE, LDPE, HDPE, LLDPE PP PIB Styron, Styrofoam PVC Saran Teflon PVAC PVAL PMMA; Lucite, Plexiglass PAN; Orlon, Acrilan fibers BR rubber NR rubber Neoprene
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Polymers with other backbones

Source-based name polyformaldehyde Poly(ethylene oxide) Poly(ethylene glycol adipate) Poly(ethylene terephthalate) Poly(hexamethylene adipamide) Poly(e-caprolactam) polyglycine Structure-based name Poly(oxymethylene) Poly(oxyethylene) Poly(oxyethylene oxyadipoyl) Poly(oxyethylene oxy-terephthaloyl) Trade name, abbreviation POM PEO Polyester 2,6 PET; Dacron
Poly(iminoadipoyl imino-hexamethylene) Nylon 6,6 Poly(imino[1-oxohexamethylene]) Poly(imino[1-oxoethylene]) Nylon 6 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?

Chemical bonding in polymers

Most primary bonds along the backbone are covalent Secondary valence bonds
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
Dispersion Dipole-dipole Dipole-induced dipole Hydrogen bond
Bond energy, kcal/mol

0.1-5.0 0.5-5.0 0.05-0.5 1.0-12
Range of action, Angstrom

3-5 (r-6) 1-2 (r-3) 1-2 (r-6) 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?

Typical effects of molecular weight distributions

Homopolymers with different molecular weight distributions may be insoluble in each other
# carbon atoms 1-4 5-11 9-16 16-25 25-50 1000-3000 State Gas Low viscosity liquid Medium viscosity liquid High viscosity liquid Crystalline solid Plastic solid (crystalline + amorphous) Use Gaseous fuel gasoline kerosene Oil, grease Paraffin wax polyethylene 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
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
Mn
n M
i i
n
i
Mw
w M n M
i i i i
2 i
w
i
n M
i i
PD
Mw Mn
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In-class exercise
HOW DOES CHAIN LENGTH AFFECT PROCESSING?

In-class exercise
HOW DOES CHAIN LENGTH AFFECT PERFORMANCE?

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?

Five regions of viscoelasticity

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

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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Chapter 1

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Polymer Process Engineering

HOW DO YOU BUILD A MOLECULE?

Renew- cellulose able Hemicellulose lignin protein

Multiple building blocks

Several copolymer configurations

Structure chemical, configuration solid performance (mechanical + thermal properties) other

HOW DO WE CLASSIFY POLYMERS?

WHAT IS IN A COMMERCIAL PRODUCT?

Polymers vs. metals

Polymerization Formulation Fabrication

HOW DO WE MAKE A PART?

Additives can change:

Overview of the polymer industry

Urea-formaldehyde resins (UF)

Similar to the above; textile coatings and sizings

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

HOW DO WE NAME POLYMERS?

Polymers with other backbones

Poly(iminoadipoyl imino-hexamethylene) Nylon 6,6 Poly(imino[1-oxohexamethylene]) Poly(imino[1-oxoethylene]) Nylon 6 Nylon 2

WHY ARE LONG CHAIN MOLECULES SOLIDS?

Chemical bonding in polymers

Secondary valence forces

Bond energy, kcal/mol

Range of action, Angstrom

WHAT ARE TYPICAL CHAIN LENGTH DISTRIBUTIONS?

Typical effects of molecular weight distributions

HOW DOES CHAIN LENGTH AFFECT PROCESSING?

HOW DOES CHAIN LENGTH AFFECT PERFORMANCE?

WHAT ARE IMPORTANT THERMAL TRANSITIONS?

Five regions of viscoelasticity

POLYMER SCIENCE DIRECTIONS

Cells feel their environment

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