MODULE-3 POLYMER MATRIX COMPOSITE
Polymer matrix composites (PMC) : thermoset, thermoplastic and
elastomeric polymers, properties, characteristics and applications
as matrix materials, processing of polymer matrix composites:
hand methods, Lay up method, spray up method, moulding
methods, pressure bagging and bag moulding methods,
Autoclave-based processing with prepregs, pultrusion and filament
winding process.
History
• The earliest man-made composite materials were straw and mud combined to form
bricks for building construction.
• Concrete is also a composite material, and is used more than any other man-made
material in the world. It consists of a binder (cement) and a reinforcement (gravel).
• Composite materials occur in nature. Wood is a natural composite consisting of
cellulose as the fiber and lignin as the matrix. In bone, the collagen acts like the resin
and the HAP mineral crystals act like the reinforcment.
• The first artificial fiber reinforced plastic was bakelite (thermosetting phenol
formaldehyde resin) which dates to 1907.
What is a polymer ?
A long molecule made up of lot of small molecules
called monomers
Polymers
Polymers are structurally much more complex than metals or ceramics.
They are cheap and can be easily processed.
Polymers have lower strength and modulus and lower use temperature limits.
Prolonged exposure to ultraviolet light and some solvents can cause the degradation
of polymer properties.
Due to covalent bonding, polymers are generally poor conductors of heat and
electricity.
Polymers are generally more resistant to chemicals than metals.
Structurally, polymers are giant chain like molecules (hence the name
macromolecules) with covalently bonded carbon atoms forming the backbone of the
chain.
Monomers all same type (A)
A+A+A+A -A–A–A–A–
Example : Poly ethene
Poly chloroethene
PVC
Monomers of two different types (A) + (B)
A+B+A+B -A–B–A–B–
Example : Polyamides
Polyesters
Addition polymerisation
In this process monomers join to form a polymer
without producing any by-product.
Addition polymerization is generally carried out in the
presence of catalysts
Monomers containing C = C Bonds
Double bond opens to (link) bond to next monomer
molecule
Chain forms when same basic unit is repeated over and
over again
Step 1 : Free radical formation
Step 2 : Bonding with the monomer
Step 3 : Chain growth
Step 4 : Further chain growth
Step 5 : Termination
Condensation polymerization
In this process a stepwise reaction of molecules
occurs and in each step a molecule of a simple
compound, generally water, forms as a by-product.
Copolymerisation
When more than one monomer is used
An irregular chain structure will result
Example :
Propene/Ethene/Propene/Propene/Ethene
Different types of copolymers
Amorphous structure
Crystalline structure
Different molecular chain configurations: (a) linear, (b) branched, (c) cross-linked,
(d) ladder
Thermoplastics
Thermosetting plastics
Rubbers
Vulcanization
• Cross linking
• reinforcement
Common Polymeric Matrix Materials
Thermosets and thermoplastic polymers are common matrix materials.
Common Thermoset Matrix Materials
Among the common polymer matrices used with continuous fibers are polyester
and epoxy resins
EPOXY
This is one of the major thermoset matrix materials. An epoxy is a polymer that
contains an epoxide group (one oxygen atom and two carbon atoms) in its chemical
Structure.
Various additives can be used to modify the characteristics of epoxies. For example,
diluents are used to reduce the viscosity. Flexibilizing agents are used to make the
epoxy flexible. Other agents are used for protection against ultraviolet radiation. An
accelerator, if added, can speed up the curing process. In general, characteristics such as
stiffness, strength, and glass transition temperature increase with increased
cross-linking, but toughness decreases.
Chemical structure of
the epoxy group
Generalized representation of an epoxy polymer
Epoxy resins are more expensive than polyesters, but they have better moisture
resistance, lower shrinkage on curing, a higher maximum use temperature and
good adhesion with glass fibers. Many proprietary formulations of epoxies are
available, and a very large fraction of high-performance polymer matrix composites has
thermosetting epoxies as matrices.
POLYESTER
An unsaturated polyester resin contains a number of C=C double bonds. Diluents such
as styrene are used to reduce the viscosity of polyester. Hardening and curing agents
and ultraviolet absorbents are usually added. Frequently, a catalyst such as an organic
peroxide is added to initiate the curing action. One can hasten the curing process by
raising the temperature; this increases the decomposition rate of the catalyst. This can
also be accomplished by using an accelerator such as cobalt napthalate. Unsaturated
polyester has adequate resistance to water and a variety of chemicals, weathering,
aging, and, last but not least, it is very cheap. It can withstand temperatures up to about
80 C and combines easily with glass fibers.
Step 1 : Monomers react
Step 2 : New molecule react with new monomers
Step 3 :
Polymerization of a typical polyester
Polyimides
Polyimides are thermosetting polymers that have a relatively high service temperature
range, 250–300 C. However, like other thermosetting resins, they are brittle. Their
fracture energies are in the 15–70 J/m2 range.
A major problem with polyimides is the elimination of water of condensation and
solvents during processing.
There is a considerable interest in developing polymeric materials that can withstand
high temperatures.
Polyimides represent a class of resins that can have a higher service temperature than
epoxies.
Common Thermoplastic Matrix Materials
Thermoplastics are characterized by linear chain molecules and can be repeatedly
melted or reprocessed.
It is important to note that in this regard the cool-down time affects the degree of
crystallinity of the thermoplastic.
This is because the polymer chains need time to get organized in the orderly pattern of
the crystalline state; too quick a cooling rate will not allow crystallization to occur.
Although repeated melting and processing are possible with thermoplastics, it should be
recognized that thermal exposure (too high a temperature or too long a dwell time at a
given temperature) can degrade the polymer properties such as impact properties.
Thermoplastic matrix materials can have failure strains ranging from 30 to 100
%,while the thermosets typically range from 1 to 3 %.
The large range of failure strains in thermoplastics stems from the rather large
variations in the amount of crystallinity.
Common thermoplastic resins used as matrix materials in composites include
some conventional thermoplastics such as polypropylene, thermoplastic
polyesters (PET, PBT), and polycarbonates.
Common Thermoplastic Matrix Materials
Chemical structure of (a) PPS, (b) polyaryl
sulfone, and (c) polyetherether ketone (PEEK)
Processing of Thermoset Matrix Composites
Hand layup (contact moulding)
• Once lamination has been completed, the
structure is left to crosslink at room temperature.
• Demoulding is done in a few hours
• Advantage:
• Low capital cost
• Possibility for marking
• Products of geometric complexity
• Products
• Storage tanks
• Vehicle components
• Wind mill blades
• Bathroom interiors
Top coat
Laminate
Surface mat or fabric
Gelcoat
Mold release agent
Mold
Protective layer
Load bearing layer
Protective layer
Lay up sequence common in wet hand lay up
In spray-up, resin and fibers (chopped) are sprayed together onto the mold surface
Pultrusion
• The term is combining "pull" and "extrusion".
1. Continuous roll of reinforced fibers/woven fiber mat
2 - Tension roller
3 - Resin impregnator
4 - Resin soaked fibre
5 - Die and heat source
6 - Pull mechanism
7 - Finished hardened fibre reinforced polymer
(a)Schematic of the pultrusion process. (b) A helicopter windshield post made of
carbon fibers/vinyl ester resin by pultrusion
Product from Pultrusion process
Drumsticks made with a pultruded Kevlar core and a thermoplastic injection-molded cover
Micrograph of carbon fiber/epoxy laminated composite made in
an autoclave
Filament winding
• Filament winding is a fabrication technique for
manufacturing composite material, usually in the form of
cylindrical structures.
• The process involves winding filaments under varying
amounts of tension over a male mould or mandrel. The
mandrel rotates while a carriage moves horizontally, laying
down fibers in the desired pattern. The most common
filaments are carbon or glass fiber and are coated with
synthetic resin as they are wound.
• Once the mandrel is completely covered to the desired
thickness, the mandrel is placed in an oven to solidify (set)
the resin. Once the resin has cured, the mandrel is removed,
leaving the hollow final product
Filament winding
Schematic of filament winding process. (b) Schematic of a filament wound pressure
vessel with a liner; helical and hoop winding
Filament winding
A filament wound pipe (diameter ¼ 2 m) made for irrigation purposes in Ecuador.
Products made form filament winding process
Prepreg
Generally, a prepreg is in the form of a thin sheet or lamina of unidirectional (or
occasionally woven) fiber/polymer composite protected on both sides with easily
removable separators.
Prepregs thus represent an intermediate stage in the fabrication of a polymeric
composite component. The prepreg generally has the resin in a partially cured state with
a moderately self-adhesive tack, the tack in the prepreg can be achieved by the addition
of liquid rubbers or resins.
A typical unidirectional prepreg is in the form of a long roll, 300 to 500mm wide roll
and 0.125mm thick. The length of the roll can be anything, but it is generally 50–250m.
The fiber content, by volume, in a unidirectional prepreg is typically about is about
65 %. It is not uncommon to use 50 or more such plies or laminae in an autoclave
processed composite.
Schematic of prepreg manufacturing.
Prepregs can be made by a number of techniques. In a process called solution dip, the
resin ingredients are dissolved in a solvent to 40–50 % solids level. The fiber (in the
form of a yarn or a fabric) is passed through the solution, and it picks up an amount of
solids that depends on the speed of throughput and the amount of solids in the solution.
In another process, solution spray, a specified amount of solid resin is sprayed onto the
fiber yarn or fabric. In both solution dip and solution spray, the impregnated fiber is put
through a heat cycle to remove the solvents and the chemical reaction in the resin
proceeds to give the desired tack.
In direct hot-melt, the resin formulation is incorporated as a high temperature coat on
the fiber. At high temperature, the viscosity is low enough for coating the fiber directly.
Prepreg (preimpregnated fibers)
prepreg
Setup in an autoclave to make a laminated composite
Layup of plies with different fiber orientations
Moulding Methods
Matched die moulding
Forming method employing Vacuum
Open mould forming methods
Bag Moulding (Vacuum forming)
Autoclave moulding
Pressure bagging
Pressure-Bag Molding
APPLICATIONS OF PMCs
Glass fiber reinforced polymers are used in a wide variety of industries: from sporting goods to
civil construction to aerospace.
Tanks and vessels (pressure and nonpressure) in the chemical process industry, as well as process
and effluent pipelines, are routinely made of glass fiber reinforced polyester resin.
S-2 glass fibers and aramid fibers are used in the storage bins and floorings of civilian aircraft.
Other aircraft applications include doors, fairings, and radomes. Aramid fiber is also used in light
load-bearing components in helicopters and small planes.
Drumsticks made with a pultruded core containing Kevlar aramid fibers and a thermoplastic
injection molded cover.
Military applications vary from ordinary helmets to rocket engine cases.
A very important application of PMCs is in the use of natural gas for transportation.
The use of compressed natural gas as a vehicle fuel requires on-board storage of gas at high
pressure (~200 kPa).
Woven fabrics made of fibers than can deform under impact make an essential constituent of
modern ballistic protection systems
It can be said without any exaggeration that Boeing 787 aircraft represents a watershed event in
the use of composites in the civilian aerospace industry.
This aircraft has major structural components such as fuselage, wings, floor beams, etc. made of
composite materials
Fan blade of GEnx engine (Boeing 787 and 747)
are made of carbon fiber/epoxy composites