INTRODUCTION TO

POLYMERS AND FIBERS

By
Ray Liang, Ph.D.
Constructed Facilities Center

November 14, 2001

 ACKNOWLEDGMENTS

This presentation is based on the material included in the

“Tutorial on Polymer Composite Molding” developed by Prof.
Giuseppe R. Palmese, Center for Composite Materials,
University of Delaware through the Michigan State University
Intelligent Systems Lab under the NSF Technology
Reinvestment Program in 1999.

Dr. Liang appreciate the Tutorial for providing a good definition

of fundamental concepts of polymer science and engineering,
excellent description of liquid, injection, and compression
molding of plastics and composites, and the relative
advantages of various materials and techniques.

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 OVERVIEW

Concepts. Definitions. Technical terms

Polymer vs. Composite

Polymer
• Thermoplastics vs. Thermosets
• Chemistry (polymerization, crosslinking)
• Physics (glass transition, stress-strain curve)

Fibers
• Types
• Fabric forms
• Selection tips

Composite Properties
• Rule of mixtures

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POLYMER

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 COMPOSITE
- A heterogeneous combination of two or more materials
• reinforcing elements such as fibers, fillers
• binders such as resins or polymers
- These materials differ in form or composition on a macroscale.
- There exists interface between these materials.

Role of Fibers and Resins in FRP Composites

Fiber:
• Load-bearing component.
Resin:
• Dissipate loads to the fiber network
• Maintain fiber orientation
• Protect the fiber network from damaging environmental conditions
such as humidity and high temperature
• Dictates the process and processing conditions

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 POLYMER CONFIGURATIONS
Linear: long, linear chains, e.g. most thermoplastics, such as HDPE
Branched: long chains with arms coming from branch points, e.g., LDPE
Network: long chains linked together by crosslinking arms to form a
network of chains, e.g., cured thermosets, such as vinyl ester

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 THERMOPLASTIC POLYMERS

Thermoplastic polymers: soften, melt and flow upon heating, e.g., LDPE,
HDPE, PP, PS, PVC, Nylon, PMMA, PC, ABS, PET

Characteristics: PP
• Linear or branched structure
• Easy to process with application of heat
• Heat sensitive properties
• Individual polymer molecules are held together by weak secondary
forces:
– Van der Waal’s forces
– Hydrogen bonds
– Dipole-dipole interactions

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 THERMOPLASTIC POLYMERS (cont’d)

Advantages:
• Unlimited shelf life -won't undergo reaction during storage
• Easy to handle (no tackiness)
• Shorter fabrication time
• Recyclable - they undergo melt and solidify cycles
• Easy to repair by welding, solvent bonding, etc.
• Postformable
• Higher fracture toughness and better delamination resistance
under fatigue than epoxy

Disadvantages:
• Poor creep resistance
• Poor thermal stability
• Poor melt flow characteristics (high viscosity ~ 1,000,000 cP)

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 THERMOSET POLYMERS

Thermosets: do not flow upon reheating, e.g. unsaturated polyesters,

vinyl esters, epoxies, phenol formaldehyde, urethane

Characteristics:
• Upon application of heat, liquid resin becomes cured / rigid
• End polymer is less temp. sensitive than thermoplastics
• Crosslinked network structure (formed from chemical bonds,
i.e. primary forces) exists throughout the part
• Crosslinking provides thermal stability such that polymer will
not melt or flow upon heating.

Polyester

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 THERMOSET POLYMERS (cont’d)

Advantages:
• Low resin viscosity (~20 – 500cP)
• Good fiber wet-out
• Excellent thermal stability once polymerized Epoxy
• Chemically resistant
• Creep resistant

Disadvantages:
• Brittle (low strain-at-break)
• Long fabrication time in the mold
• Limited storage life at room temperature before curing
• Non-recyclable via standard techniques
• Molding in the shape of a final part - not postformable

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 POLYMERIZATION REACTIONS
Thermoplastics: polymerized prior to molding the final part
Thermosets: polymerized during the molding process

Polymers formed Polymers formed

via chain reaction: via step reaction:
Polyethylene Nylon
Polypropylene Polycarbonate
Polystyrene Polyethylene terephthalate
Polyvinyl chloride Epoxy
Polymethyl methacrylate Phenol formaldehyde
Acrylonitrite-butadiene-styrene Urethane
Unsaturated polyesters
Vinyl esters
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CHAIN (OR ADDITION) POLYMERIZATION

Initiators /Catalysts
Benzoyl peroxide (BPO) Dicumyl peroxide (DCP)
Methyl ethyl ketone peroxide (MEKP)
Upon heating, these peroxides dissociate to form two radicals which
attack the monomer double bonds and add to them (addition). This
forms a reactive radical center which can propagate to form a polymer.

Inhibitors and Retarders

Used to suppress polymerization in order to improve processability
Inhibitors stop all radical polymerization until consumed.
Retarders stop only a portion of the radicals from propagating.

Promoters and Accelerators

Used to help initiate cure at room temperature, e.g. Cobalt
naphthenate, DMA

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 STEP (OR CONDENSATION)
POLYMERIZATION
No special activation needed to allow a monomer to react with
any nearby monomer.
Condensation: water liberated when the polymer bonds form.
Polyester formation: The acid groups in diacids react with the alcohol
groups in diols to form ester linkages.
Curing Agents
Importance of curing agents (also called crosslinking agents,
hardeners, or catalysts):
• determines the type of curing reaction
• influences the processing cycle: viscosity versus time, gelation
• affects properties of the cured system: Tg, modulus, strength

Examples of curing agents for epoxies:

aliphatic amine (DETA), aromatic amine (MPDA), cyclic anhydrides (NMA)

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 CROSSLINKING IN STEP
POLYMERIZATION
Crosslinks are formed with the use of monomer of multi functional groups

Functionality (f): the number of reactive groups of monomer.

f equal to 2: linear polymer
f greater than 2: branched or crosslinked polymer
Thermosets cured via this process include
Epoxies Phenol formaldehyde Urethane

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 CROSSLINKING IN CHAIN
POLYMERIZATION
Monomers with two or more double bonds (for example, divinyl monomers)
may lead to crosslinking.
Examples of this type of systems: unsaturated polyesters, vinyl esters

• Vinyl ester with unsaturations is formed via step polymerization;

• The unsaturated sites are reacted with styrene to produce crosslinked
structure via chain reaction with using peroxide initiator.
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 CURE OF THERMOSETTING RESINS

A thermosetting system is set to cure when a crosslinked network of

polymer chains is formed.

Gel point: The onset of gelation when the material won’t flow, i.e.
molecular weight approaches infinity.

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 TYPICAL VINYL ESTER AND
POLYESTER RESIN FORMULATION
Resin/ pre-polymer- 40 to 100% (typically (55-65%)
• Provides polymer properties, including modulus, toughness, glass
transition temperature, and durability.

Reactive diluent or monomer (styrene commonly)- 0-60% (typically 35-45%)

• Viscosity control
• Lower cost
• Improve wetting behavior

Initiator (catalyst)--1 to 3%
• Peroxide necessary to begin chemical reaction

Inhibitors--less than 100 ppm

• Aid in processing
• Improve shelf life

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 GLASS TRANSITION TEMPERATURE
T < Tg: Glassy state - brittleness,
stiffness, and rigidity
T >Tg: Rubber state - softening
and flow

Molecular Interpretation:
In glassy state
• No large scale molecular
motions
• Atoms move against restraint
of secondary bond forces
At glass transition temperature
• Onset of liquid-like motion of
long molecular segments
• More free volume

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TENSILE STRESS-STRAIN
RELATIONSHIPS

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MECHANICAL PROPERTIES OF
POLYMERS

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 GLASS FIBERS

“E” glass fibers: high electrical insulating properties

low susceptibility to moisture
high mechanical properties
“S” glass: higher strength, heat resistance and modulus
AR glass (alkali resistant): improved chemical resistance
Glass fibers offer many advantages such as:
• Low cost
• High tensile strength
• High chemical resistance
• Relatively higher fatigue resistance
• Excellent insulating properties
The limitations of glass fibers are:
• Low tensile modulus
• Relatively high specific gravity
• Sensitivity to abrasion with handling
• High hardness

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 CARBON FIBERS

PAN based fibers offer good strength and modulus up to 85-90 Msi. They
also offer excellent compression strength, to 1 Msi.
Pitch fibers have extremely high moduli (up to 140 Msi) and favorable
coefficient of thermal expansion.
Carbon fibers offer the following advantages:
• High tensile strength-to-weight ratio
• High tensile modulus-to-weight ratio.
• Very low coefficient of linear thermal expansion.
• High fatigue strength.
Some of the disadvantages of carbon fibers are:
• High cost
• Brittle, reducing the impact resistance
• Electrical conductive, which limits their application potential.

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 PREFORM -RANDOM MATS

A preform is the assembly of reinforcing fibers that is preshaped and

oriented by placement in a mold to its near-net configuration, prior to
introduction of resin.

Advantages
• High permeability
• Easy infusion
• Easy handling
• High degree of structural
• Good integrity

Disadvantages
• Poor stiffness
• Limited strength
• Limited fiber volume fractions

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 UNIDIRECTIONAL FABRIC

Unidirectional Fabric consists of parallel filaments held loosely in place

by stitches in a plane:

Advantages
• High stiffness and strength in
filament direction

Disadvantages
• Poor integrity - "fiber wash" may occur
• Anisotropic flow and performance

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 TWO-DIMENSIONAL WOVEN FABRICS

Weaves can be classified according to the spacing between the tows.

Weaves with big open spaces between the tows are termed open
weaves, while weaves with no space between the tows are termed
closed weaves.

Advantages
• Balanced properties in the plane of fabric
• Good impact resistance
• Good conformability

Disadvantages
• Fiber undulation
• Asymmetry
• Trimming / Handling

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OTHER FABRIC ARCHITECTURES

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FIBER ARCHITECTURE SELECTION

Processing Issues Performance Issues

•Permeability •Moduli, strengths, etc.

(X,Y, Z directions)
•Durability
•Compressibility
•Compressibility
•Drapeability (Fiber volume fraction)

•Ease of Handling •Drapeability

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 COMPOSITE PROPERTIES

Given the properties of the fiber and resin which comprise a composite
material, it is possible to estimate the properties of the composite.

Specifically, the overall objective in estimating composite properties

is to use:
• Properties of components
• Volume fraction of components
• Reinforcing geometry
• Orientation of fibers

To predict:
• Young's Modulus
• Shear modulus
• Poisson's Ratio
• Thermal expansion coefficient

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 MODELS FOR UNIDIRECTIONAL
CONTINUOUS FIBER COMPOSITES

RULE OF MIXTURES

The composite property is

estimated as the sum of the
responses of the composite
components weighted by the
component volume fractions.

The composite property is

estimated as a reciprocal sum of
the responses of the composite
components weighted by the
component volume fractions.

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