CPE 309 COMPOSITE AND POLYMER ADDITIVES

Outline

General introduction
Various reinforcing agents and properties
Various matrix resins – thermoplastics and thermosets and their properties
Various additives and properties
Fabrication of composites using thermoplastic matrix
Fabrication of Composites using thermoset matrix
Factors affecting strength and fatigue behavior
Measurement of mechanical properties of composites
Applications of composite materials

Introduction

A composite material is a combination of two or more material (reinforcing elements, fillers, and
composite matrix binder) and in which the individual components retain their individual separate
identities. This means that the individual component do not dissolve or merge completely into one
another, although they act in concert. A composite material has properties different from those of
individual component because when the two components are combined, the physical properties are
improved. Thus, the main interest is to achieve mechanical properties superior to those of individual
components. Composite usually have a reinforcing fiber ; e.g. glass, carbon, aramid fibres, etc. The fibers
are stronger and stiffer than the matrix resin. The reinforcing agent must have a substantial volume
fraction more than 10%.

Composites can be divided into various classes depending on the type of reinforcement, i.e. particulate
reinforced, fibre-reinforced or laminar composites.

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Fiber reinforced can be further subdivided into two categories; discontinuous or continuous fiber
reinforced composites.

Particulate reinforced composites: These include those rteinforced by spheres, rods, flakes, and many
other shapes of roughly equal axes. However there are also materials usually polymers that extend
rather than reinforcing the material. These materials are known as “fillers” and are incorporated for the
purpose of cost reduction rather than reinforcement. They are non-particulate but in some cases they
reinforce the material as well.

Fiber reinforced composites: Fiber reinforced composites may be continuous or discontinuous. In either
case, the length of the fibre is much greater than the sectional dimension. A discontinuous fiber
reinforced composite is also known as short fiber reinforced composite. Thus its properties are varied
with fibre length . The material is considered continuous fiber reinforced or long-fiber reinforced
composite whern the length of the fiber is long and the increase in length is no longr affct th elastic
modulus of the composite.

Classification

Classification Example
Natural composite materials Wood
Bone
Bamboo
Muscle and other tissue
Microcomposite materials Metallic alloys, e.g. steels
Toughened thermoplastics, e.g. ABS

Macrocomposites Galvanized steel

Reinforced concrete beams
Helicopter blades

Benefits of Composites
THE BENEFITS OF COMPOSITES

Year by year, more and more designers and engineers recognize the values of composites over
other traditional materials like metal alloys, plastics etc. This is because composite material
systems result in performance unattainable by their individual constituents. Fiber reinforced
(FRP) products are more reliable, more durable, easy and safe to use, more economic to produce,
and individually solve many problems and offer many benefits. As a result, manufacturers are
abandoning old materials and fabricating methods and turn to composites. Composites are no
longer just the privilege of aerospace, defence and high priced products. They are rapidly
becoming a way of achieving high structural performance at a low cost. They are found in most

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of the cars we drive, in all busses and trains, boats, and recreation and sports equipment such as
skis or canoes we use on the weekends.

Composites offer many advantages:

- Higher mechanical properties like strength and stiffness

- Lighter weight, higher performance

- Energy savings

- Durability, fatigue resistance and longer service life

- Impact resistance

- Dimensional stability

- Anisotropic properties

- Good chemical properties, corrosion resistance

- Fire retardance

- High temperature service

- Sevier environment outdoor service

- Low maintenance requirements

- Low thermal conductivity

- Low or custom thermal expansion

- Tailored energy conductivity, (e.g. can be used to amplify or dump vibration)

- Tailored transparency to radio frequency (reflection or dumping properties)

- Tailored electric properties (insulation or conduction capability)

- Tailored electromagnetic transparency

- Tailored properties make composite products irreplaceable for both

telecommunication and stealth technologies

- Flexible, tailor design, part consolidation and freedom of shape

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- Combination of many materials and inserts

- Lower capital investment for FRP manufacturing facilities

- FRP products are simpler, having fewer and larger parts

- Relatively low energy consumption to produce raw materials

Various Reinforcing Agents

The fiber reinforcement provides the structural performance required of the final part. The fibers
or filaments come in many chemical types and forms and are the primary contributor to the
stiffness, strength and other properties of the composite. The dominant chemical types of
commercially available fibers are: fiberglass, aramid, carbon, polyester and vectran. Other fiber
types may be suitable for special applications. The dominant forms that fibers are sold include:
Strands (or roving or tow or yarn. Many fibers or filaments stranded together in a bundle, wound
in a spool or reel,) woven fabrics (flattened strands of filaments woven in a variety of weaves to
a type of fabric or cloth,) unidirectional (strands laid side by side and stitched or held together by
other means, forming a kind of fabric that bares reinforcement only in the fill direction,)
multiaxials (unidirectional woven fabrics stitched together in a combination of orientations,) and
chopped strand mat (chopped strands held together with some kind of glue or “binder” in the
form of a non-woven fabric.) All fibers designated for use in composites undergo chemical
treatments and are coated with some kind of “sizing”. Sizing is a chemical that binds the
filaments together, reduces abrasion, facilitates impregnation and acts like a coupling agent that
enhances compatibility with one or more types of resin.
Selection of reinforcement type greatly influences costs. This is not only because of the quality
and cost of the material itself, but also because higher cost material usually requires highly
skilled personnel, more sophisticated production facilities and often more labour hours.

Various compositions of mineral glasses may b used to produce fibers. Fiberglass really is made
of glass, similar to windows or the drinking glasses in the kitchen. The glass is heated until it is
molten, then it is forced through superfine holes, creating glass filaments that are very thin – so
thin they are better measured in microns. These threads can then be woven into larger swatches
of material, or left in the somewhat less structured although more familiar puffy substance used
for insulation or soundproofing. This will depend on whether the extruded strands were made
longer or shorter, and the quality of the fiberglass. For some applications, it is important for the

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glass fibers to have fewer impurities, which involves additional steps in the manufacturing
process.
The types of glass fiber most commonly used are:

E-glass (alumino-borosilicate glass with less than 1% w/w alkali oxides, mainly used for glass-
reinforced plastics

A-glass (alkali-lime glass with little or no boron oxide)

E-CR-glass (alumino-lime silicate with less than 1% w/w alkali oxides, has high acid
resistance),

C-glass (alkali-lime glass with high boron oxide content, used for example for glass staple fibers)

D-glass (borosilicate glass with low dielectric constant),

R-glass (alumino silicate glass without MgO and CaO with high mechanical requirements), and
S-glass (alumino silicate glass without CaO but with high MgO content with high tensile
strength)

Manufacturing

The basic raw materials for fiberglass products are a variety of natural minerals and
manufactured chemicals. The major ingredients are silica sand, limestone, and soda ash. Other
ingredients may include calcined alumina, borax, feldspar, nepheline syenite, magnesite, and
kaolin clay, among others. Silica sand is used as the glass former, and soda ash and limestone
help primarily to lower the melting temperature. Other ingredients are used to improve certain
properties, such as borax for chemical resistance. Waste glass, also called cullet, is also used as a
raw material. The raw materials must be carefully weighed in exact quantities and thoroughly
mixed together (called batching) before being melted into glass.

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Melting

 1 Once the batch is prepared, it is fed into a furnace for melting. The furnace may be
heated by electricity, fossil fuel, or a combination of the two. Temperature must be
precisely controlled to maintain a smooth, steady flow of glass. The molten glass must be
kept at a higher temperature (about 2500°F [1371°C]) than other types of glass in order to
be formed into fiber. Once the glass becomes molten, it is transferred to the forming
equipment via a channel (forehearth) located at the end of the furnace.

Forming into fibers

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  2 Several different processes are used to form fibers, depending on the type of fiber.
Textile fibers may be formed from molten glass directly from the furnace, or the molten
glass may be fed first to a machine

that forms glass marbles of about 0.62 inch (1.6 cm) in diameter. These marbles allow the
glass to be inspected visually for impurities. In both the direct melt and marble melt
process, the glass or glass marbles are fed through electrically heated bushings (also
called spinnerets). The bushing is made of platinum or metal alloy, with anywhere from
200 to 3,000 very fine orifices. The molten glass passes through the orifices and comes
out as fine filaments.

Continuous-filament process

 3 A long, continuous fiber can be produced through the continuous-filament process.

After the glass flows through the holes in the bushing, multiple strands are caught up on a
high-speed winder. The winder revolves at about 2 miles (3 km) a minute, much faster
than the rate of flow from the bushings. The tension pulls out the filaments while still
molten, forming strands a fraction of the diameter of the openings in the bushing. A
chemical binder is applied, which helps keep the fiber from breaking during later
processing. The filament is then wound onto tubes. It can now be twisted and plied into
yarn.

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Staple-fiber process

 4 An alternative method is the staplefiber process. As the molten glass flows through the
bushings, jets of air rapidly cool the filaments. The turbulent bursts of air also break the
filaments into lengths of 8-15 inches (20-38 cm). These filaments fall through a spray of
lubricant onto a revolving drum, where they form a thin web. The web is drawn from the
drum and pulled into a continuous strand of loosely assembled fibers. This strand can be
processed into yarn by the same processes used for wool and cotton.

Chopped fiber

 5 Instead of being formed into yarn, the continuous or long-staple strand may be chopped
into short lengths. The strand is mounted on a set of bobbins, called a creel, and pulled
through a machine which chops it into short pieces. The chopped fiber is formed into
mats to which a binder is added. After curing in an oven, the mat is rolled up. Various
weights and thicknesses give products for shingles, built-up roofing, or decorative mats.

Carbon Fibres

What is commonly referred to as carbon fiber is a material consisting of very thin filaments of
carbon atoms. When bound together with plastic polymer resin by heat, pressure or in a vacuum
a composite material is formed that is both strong and lightweight. It is is a material consisting
of fibers about 5–10 μm in diameter and composed mostly of carbon atoms.

Manufacturing

To produce carbon fiber, the carbon atoms are bonded together in crystals that are more or less
aligned parallel to the long axis of the fiber as the crystal alignment gives the fiber high strength-
to-volume ratio (making it strong for its size). Several thousand carbon fibers are bundled
together to form a tow, which may be used by itself or woven into a fabric.

he process for making carbon fibers is part chemical and part mechanical. The precursor is drawn
into long strands or fibers and then heated to a very high temperature with-out allowing it to
come in contact with oxygen. Without oxygen, the fiber cannot burn. Instead, the high
temperature causes the atoms in the fiber to vibrate violently until most of the non-carbon atoms
are expelled. This process is called carbonization and leaves a fiber composed of long, tightly

The fibers are coated to protect them from damage during winding or weaving. The coated fibers
are wound onto cylinders called bobbins.
inter-locked chains of carbon atoms with only a few non-carbon atoms remaining.

Here is a typical sequence of operations used to form carbon fibers from polyacrylonitrile.

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Here is a typical sequence of operations used to form carbon fibers from polyacrylonitrile.

Spinning

 1 Acrylonitrile plastic powder is mixed with another plastic, like methyl acrylate or
methyl methacrylate, and is reacted with a catalyst in a conventional suspension or
solution polymerization process to form a polyacrylonitrile plastic.
 2 The plastic is then spun into fibers using one of several different methods. In some
methods, the plastic is mixed with certain chemicals and pumped through tiny jets into a
chemical bath or quench chamber where the plastic coagulates and solidifies into fibers.
This is similar to the process used to form polyacrylic textile fibers. In other methods, the
plastic mixture is heated and pumped through tiny jets into a chamber where the solvents
evaporate, leaving a solid fiber. The spinning step is important because the internal
atomic structure of the fiber is formed during this process.
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  3 The fibers are then washed and stretched to the desired fiber diameter. The stretching
helps align the molecules within the fiber and provides the basis for the formation of the
tightly bonded carbon crystals after carbonization.

Stabilizing

 4 Before the fibers are carbonized, they need to be chemically altered to convert their
linear atomic bonding to a more thermally stable ladder bonding. This is accomplished by
heating the fibers in air to about 390-590° F (200-300° C) for 30-120 minutes. This
causes the fibers to pick up oxygen molecules from the air and rearrange their atomic
bonding pattern. The stabilizing chemical reactions are complex and involve several
steps, some of which occur simultaneously. They also generate their own heat, which
must be controlled to avoid overheating the fibers. Commercially, the stabilization
process uses a variety of equipment and techniques. In some processes, the fibers are
drawn through a series of heated chambers. In others, the fibers pass over hot rollers and
through beds of loose materials held in suspension by a flow of hot air. Some processes
use heated air mixed with certain gases that chemically accelerate the stabilization.

Carbonizing

 5 Once the fibers are stabilized, they are heated to a temperature of about 1,830-5,500° F
(1,000-3,000° C) for several minutes in a furnace filled with a gas mixture that does not
contain oxygen. The lack of oxygen prevents the fibers from burning in the very high
temperatures. The gas pressure inside the furnace is kept higher than the outside air
pressure and the points where the fibers enter and exit the furnace are sealed to keep
oxygen from entering. As the fibers are heated, they begin to lose their non-carbon atoms,
plus a few carbon atoms, in the form of various gases including water vapor, ammonia,
carbon monoxide, carbon dioxide, hydrogen, nitrogen, and others. As the non-carbon
atoms are expelled, the remaining carbon atoms form tightly bonded carbon crystals that
are aligned more or less parallel to the long axis of the fiber. In some processes, two
furnaces operating at two different temperatures are used to better control the rate de
heating during carbonization.

Treating the surface

 6 After carbonizing, the fibers have a surface that does not bond well with the epoxies
and other materials used in composite materials. To give the fibers better bonding
properties, their surface is slightly oxidized. The addition of oxygen atoms to the surface
provides better chemical bonding properties and also etches and roughens the surface for
better mechanical bonding properties. Oxidation can be achieved by immersing the fibers
in various gases such as air, carbon dioxide, or ozone; or in various liquids such as
sodium hypochlorite or nitric acid. The fibers can also be coated electrolytically by
making the fibers the positive terminal in a bath filled with various electrically
conductive materials. The surface treatment process must be carefully controlled to avoid
forming tiny surface defects, such as pits, which could cause fiber failure.

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Sizing

 7 After the surface treatment, the fibers are coated to protect them from damage during
winding or weaving. This process is called sizing. Coating materials are chosen to be
compatible with the adhesive used to form composite materials. Typical coating materials
include epoxy, polyester, nylon, urethane, and others.
 8 The coated fibers are wound onto cylinders called bobbins. The bobbins are loaded into
a spinning machine and the fibers are twisted into yarns of various sizes.

Organic Reinforcing Fibre

Aramid fibre

Aramid was invented by DuPont in 1960’s (“Kevlar” is the registered trade name of Dupont
aramid) as a result of research on nylon (polyamide) fibers. It was firstly introduced in the
market in the 1970’s as tire reinforcement and like fiberglass, as an asbestos substitute. The
chemical structure of aramid shows the aromatic benzene rings along the polymeric backbone.
The word aramid is a contraction of its chemical description–aromatic polyamides. Strength and
modulus of aramid are very good, density very low, UV resistance low and compression and
shear strength are similar to E glass. Its value comes from excellent toughness and resistance to
impact, damage, abrasion and heat (up to 500 o C.)
The superior toughness of aramid is an outcome of the energy consuming failure mechanism of
its fibers. This energy absorbing failure mechanism makes it ideal for use in armor, military and
ballistic applications, like helmets and bullet-proof vests. Among many other very important
uses, it is used for firefighting protection, on the underside of airplanes (protection against stone
hits during take off and landing) and the under side of race cars. It is used generally in important
structures whenever impact, abrasion and/or heat is anticipated. It also blends very well and
works together with other fibers, like glass and carbon. Carbon-aramid “hybrid” constructions
bare the high strength and stiffness of carbon and the impact protection of aramid. Processing
aramid in composite fabrication is somewhat more difficult than fiberglass and carbon.
Toughness makes fabrics difficult to cut with conventional methods. Fiber wetout is more
difficult than fiberglass and carbon. Orthophthalic polyester resin will not adhere well to aramid
(isophthalic polyester is much better). Post fabricating aramid components, e.g. trimming off the
edges is also difficult. Quality cutting tools are recommended..

Aramid fibers share some general characteristics that distinguish them from other synthetic
fibers:

 High strength
 Good resistance to abrasion
 Good resistance to organic solvents
 Non-conductive
 No melting point
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  Low flammability
 Good fabric integrity at elevated temperatures

These unique characteristics derive from the combination of having stiff polymer molecules with
a strong crystal orientation as well as close interaction between the polymer chains due to the
hydrogen bonds.

High modulus polyester

HMP and Diolen are high strength polyester fibers. Such fibers have been used in industrial
applications for many decades, in a wide field of applications like tire reinforcement, safety
belts, ropes and nets. Recognition of their value in composite applications for aerospace, defense,
marine and transportation has come in the late years. They are used both as primary
reinforcement and in hybrid arrangements with fiberglass and aramid. Toughness makes them
ideal for use on the outside layers of composite construction for impact protection. Placed on the
outside layers they also protect aramid and glass from moisture (and blistering) and being
smooth, they reduce print-through. At the same time, their very low density also makes them
ideal for use in the middle layers, where working as a core material, they add stiffness to the
structure. Other attractive features include good impact and fatigue resistance, and potential for
vibration damping. Generally, properties of Diolen resemble the properties of aramid at lower
level, but its reasonable price and reliability make it attractive. Diolen performance at elevated
temperature falls off. It should not be used in above 200 o F applications. Processing is easier than
this of aramid, but not as easy as fiberglass and carbon.

Liquid crystal polymer

Vectran is the outcome of 30 years research on liquid crystal polymer (LCP) fibers. 100% of
world production is now owned by one company, Kuraray Co., Ltd. Annual production is only
600 tons in 2007, but is growing at a rate of about 10% a year. This fiber is formed by melt
extrusion of LCP through fine diameter capillaries. It is used in aerospace composites and many
other high value industry applications. It exhibits high strength and modulus, excellent creep
resistance, high abrasion resistance, excellent flex/fold characteristics, minimal moisture
absorption, excellent chemical resistance, high dielectric strength, outstanding cut resistance,
high impact resistance, outstanding vibration damping characteristics, very good property
retention at high/low temperatures (melting point of 330 °C, with progressive strength loss from
220 °C.) They have gold color, similar to aramid, but are usually painted in other colors for
cosmetic purposes. Vectran also adheres to resins better than aramid. Among others, it should be
used in applications where weight and impact resistance are important.

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