Manufacturing of Composites

ME-511

Sunny Zafar 1
 Course contents
• Introduction to Composites
• Properties and testing composites
• Thermoset composite manufacturing processes
• Thermoplastic composite manufacturing processes
• Metal and Ceramic Matrix Composites
• Secondary Manufacturing Techniques for Composites
• Process modelling in Composite Manufacturing

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 Course reference, evaluation and lecture schedule
➢ Reference books:
❖ Strong AB. Fundamentals of composites manufacturing: materials, methods and
applications. Society of manufacturing engineers; USA, 2008.
❖ Mallick PK. Fiber-reinforced composites: materials, manufacturing, and design. CRC
press; 2007.

➢ Evaluation
▪ Mid semester exam: 30% (First week of October 2023)
▪ End semester exam: 50%
▪ Case study presentation (10 slides) and report: 20% (As per schedule shared)

➢ Lecture schedule

Day Time
Tuesday 4 PM
Thursday 4 PM

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Introduction

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 Manufacturing
➢ Manufacturing is concerned with making products.
➢ A manufactured product may itself be used to make several other
products
➢ Technologically, manufacturing is the application of physical and
chemical processes to alter the geometry, properties, and/or
appearance of a given starting material to make parts or products;
manufacturing also includes assembly of multiple parts to make
products.

Fig: Manufacturing in technical sense Fig: Manufacturing in economic sense

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Engineering Materials

Fig: Evolution of engineering materials 6

 Engineering Materials
Engineering materials

Metals Plastics Ceramics Composites

Oxides PMCs
Nitrides MMCs
Ferrous Non-ferrous Thermoplastics Thermosets Elastomers Carbides CMCs
Glasses
Glass
Cast iron Aluminum Arcylics Epoxies Rubbers ceramics
Steels Copper ABS Phenolics Silicones Graphite
Stainless Titanium Nylons Polyamides Polyurethanes Diamond
steels Tungsten Polyethylenes others
Tool and others PVC
die others
steels

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 Manufacturability of materials
➢ Representative strengths of various categories of materials

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Examples of composite applications

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 Composites
➢ A composite material is made by combining two or more materials to give a
unique combination of properties.
➢ The above definition is more general and can include metals alloys, plastic co-
polymers, minerals, and wood.
➢ Composite material systems result in a performance unattainable by the
individual constituents, and they offer the great advantage of a flexible design.
➢ One can, in principle, tailor-make the material as per specifications of an
optimum design.

Fig: Some naturally occurring composites

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 What is a composite?
➢ The term composite materials refers to all solid materials composed of more
than one component wherein those components are in separate phases.
➢ This definition includes a wide assortment of materials, such as:
➢ Fiber reinforced plastics
➢ Regular and steel reinforced concrete
➢ Particle filled plastics
➢ Rubber reinforced plastics
➢ Wood laminates
➢ Ceramic mixtures
➢ Some alloys
➢ Composite materials are those solid materials composed of a binder or matrix
that surrounds and holds in place reinforcements.

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Why composites?

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Pros and Cons of Composite Materials

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Matrix vs. reinforcement

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 Classification of composites
Composites

Particulate Fiber

Random Particulate Single layer Multi layer

orientation

Long and Short and Laminate Hybrid

continuous fibers discontinuous fibers laminate

Unidirectional Bi-directional

Random Preferred
orientation orientation 15
 Fibers vs Bulk
Table: Comparison of fibre properties and bulk properties

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Building blocks of FRC

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Matrices and their properties

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Estimation of properties of composites : Rule of
mixtures [on board]

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 Matrices
➢ Matrix materials
➢ Metal
➢ Ceramic
➢ Polymer (80%)

➢ Difference in polymer/resin and plastic

➢ Polymer: consists of repeating units monomers to form a long chain like
structure. Monomers have a specific and consistent grouping.
➢ Short polymers (with few monomer units) is known as oligomers (also
prepolymers
➢ Resin refers to polymer materials not yet In their final form and shape. Resins
are liquids. (originated from Greek word meaning tree sap)
➢ Plastics refer to polymeric materials that have been finally shaped (Greek word:
plastickos meaning form or mold)
➢ Resin changes to plastic by forming/curing.
➢ Resin or polymer can be natural or synthenic
➢ Plastic is synthetic always
➢ Plastics is associated with low cost composites and resin with high cost
composites 20
 Matrices
Introduction
➢ Matrix surrounds the fibers and thus protects those fibers against chemical and
environmental attack. For fibers to carry maximum load, the matrix must have a
lower modulus and greater elongation than the reinforcement.
➢ Matrix selection is performed based on chemical, thermal, electrical,
flammability, environmental, cost, performance, and manufacturing
requirements.
➢ The matrix determines the service operating temperature of a composite as well
as processing parameters for part manufacturing.
➢ Types of matrix materials
➢ Polymers (both thermosets and thermoplastics)
➢ Metals
➢ Ceramics

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 Matrices
Classification
Matrices

Polymer Metal Ceramic

Thermosets Thermoplastics

Epoxies Nylons
Aluminium and its alloys, Aluminium oxide (Al2O3)
Polyesters Thermoplastic polyesters (such as
Titanium alloys, Carbon
Vinyl esters PET, PBT),
Magnesium alloys, Silicon Carbide (SiC),
Phenolics Polycarbonate (PC)
Copper-based alloys, Silicon Nitride (Si3N4)
Polyimides Polyacetals (PA)
Nickel-based superalloys,
Polybenzimidazoles (PBI), Polyethylene (PE)
Stainless Steels
polyphenylquinoxaline (PPQ) Poly proplyne (PP)
Cyanate ester Polyamide-imide (PAI),
Polyether ether ketone (PEEK)
Polysulfone (PSUL)
Polyphenylene sulfide (PPS)
Polyetherimide (PEI)

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 Matrices
➢ Polymerization and its
types
➢ Process to link small
units into long chain is
polymerization.
➢ Commonly
polymerization: addition
or condensation
➢ Addition polymerization:
reactions begins with
activation of some
molecule (usually
peroxide) that forms free
radical (FR). Free radical
have unpaired electron.
➢ Heating of peroxide
required to form FR.
Unpaired electron will
couple to form pair with
another electron to form
bond.

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 Matrices
➢ Condensation polymerization: Two different monomers with active end groups, X
and Y.
➢ Condensation monomers is that the active end group, X, of one monomer must
react with the active end group, Y, of another to form a linkage element, L, which
joins the two monomers (M1 and M2) into a linked molecule. A condensation by-
product or condensate, C, is also formed (Step 1).

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 Matrices
➢ Polymerization reaction usually conducted at elevated temperatures and in high
monomer concentrations to improve reaction efficiencies.
➢ The mixture can be cooled to stop the reaction when the desired chain length is
reached.
➢ It is also possible to quench the reaction by the addition of end-termination
molecules.

➢ NAMING OF POLYMERS: Addition of poly before the name of monomer. For e.g.
Polypropylene

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 Add. Vs. Cond. Polymers
➢ Addition polymerization often result in the formation of relatively few but very
long-chain polymers.
➢ This is because of the low concentration of initiating free-radical used (hence
only a few chains are initiated) and the highly reactive nature and rapidity of the
chain-growth steps.

➢ Condensation polymerization usually results in fewer and shorter molecules.

Many chains begin in condensation polymerizations because any two monomers
can react to begin new chains, thus creating a large number of chains, each
competing for new monomers to add.

➢ Length of the chain is usually characterized by a quantity called molecular

weight, which is a measure of the number of monomer units in the chain.
➢ Generally, mechanical properties, like stiffness, abrasion resistance, hardness,
toughness, increase with molecular weight
➢ For composite, thermal properties and toughness is dependent on molecular
weight of matrix

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 Thermal Properties of Polymers
➢ Concept of liquid and solid, forces of attraction etc.

➢ The temperature at which the molecules lock in place and the material becomes
a solid is called the freezing point mass of polymer molecules varies so greatly in
length, there is no single, sharply defined temperature that can be called the
melting point or freezing point.
➢ Broadness of the melting/freezing point is especially true if the molecules are
highly entangled and randomly arranged. Such polymers are said to be
amorphous.
➢ Upon heating, vibrational and rotational increase with increased lateral and
translational movements
➢ Melting point is directly proportional to molecular weight
➢ decomposition point is another important thermal transition in polymers. At the
decomposition temperature, sufficient heat has been put into the polymer so that
the motions of the atoms (vibrations and translations) are great enough to break
the

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Thermal Properties of Polymers

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 Thermal Properties of Polymers
➢ Concept of glass transition temperature

➢ This thermal transition occurs in the solid phase and marks a change from a rigid
solid to one that is more pliable.
➢ The motions of the atoms in a rigid, solid material below the Tg are generally
simple vibrations in rigidly fixed positions. Above Tg but still below the melting
point, the vibrations and rotations are more expansive and the atoms may move
laterally for short distances.
➢ However, they are still locked into relatively fixed positions because of continued
entanglements. Hence, between the Tg and the melting point, the material
becomes somewhat pliable, although still a solid.

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 Glass Transition Temperature
➢ Mechanical properties depend strongly on both the ambient temperature and
the loading rate.
➢ Glass transition temperature (Tg) is the temperature in which the polymer
changes from a hard, sometimes brittle (glass-like) material to a soft, tough
(leather like) material.
➢ Over a temperature range around Tg, its modulus is reduced by as much as five
orders of magnitude.
➢ Near this temperature, the material is also highly viscoelastic.
➢ The mechanical characteristics of a polymeric solid depend on the ambient
temperature relative to the glass transition temperature of the polymer.
➢ If the ambient temperature is above Tg, the polymeric solid exhibits low surface
hardness, low modulus, and high ductility.

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Glass Transition Temperature

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 Thermal Properties of Polymers
➢ Heat Distortion Temperature (HDT):
➢ Deflection temperature underload test.
➢ HDT is a convenient measure of the maximum use temperature for a polymer.

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 Thermosets and thermoplastics
➢ Interaction of molecules in dependent on intermolecular attraction between
different polymer molecules and have major effect on key properties of polymers
➢ Interactive bonds between polymer molecules is called as crosslinks. They have
approximately same strength as the bonds between the atoms of polymer
molecule itself.

➢ Thermoplastics are solids at room temperature, have no crosslinks. They are

melted or softened by heating and molding when they reach the molten stage.
Ex. Injection molding, blow molding, thermoforming.
➢ Examples of thermoplastics: polyethylene, polypropylene, nylon, polycarbonate,
polyethylene terephthalate (PET), polyvinyl, chloride (PVC), acrylic, and acetal
➢ Service temperature of thermoplastics need to be considered as they become
moldable (plastic) with heat.

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 Thermosets and thermoplastics

Fig: Schematic representation of (a) thermoplastic polymer and (b) thermoset polymer.

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 Thermosets and thermoplastics
➢ Thermosets are usually liquids at room temperature. They are solidified into
desired shape by heating, which creates crosslinks between polymer molecules.
➢ The crosslinks change basic nature of the material. After heating upon after
crosslinks are formed, materials is said to be cured.
➢ Because of curing, thermosets can’t be remelted. Therefore, thermosets become
set (fixed) with heat. Ex: hand lay-up, spray-up, compression molding, filament
winding, resin transfer molding, and pultrusion.
➢ Examples of thermosets: unsaturated polyester, vinyl ester, epoxy, polyimide,
phenolic, and cyano-acrylate.
➢ Upon formation of crosslinks, they restricts the movement of polymer molecules
with temperature even greater than the intermolecular attraction.

➢ Also Tg increases with crosslinks. So more heat is needed to increase movement

of molecules. So examination of Tg is preferred way to know the extent of
polymerization.

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 Thermosets and thermoplastics
➢ Upon crosslinking, the molecular weight of the polymer molecule increases so
large value, such that its melting point increases beyond its decomposition
temperature.
➢ Therefore, upon heating, the thermoset polymer decomposes before melting.

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 Thermosets and thermoplastics
➢ Viscosity standpoint comparison
➢ On a double x-axis graph showing time/temperature (as both increase together)
and viscosity on y-axis.
➢ For thermoplastic, initial viscosity is above the solid/liquid line (i.e. it’s a solid at
room temperature). As temperature increases, viscosity drops due to motion of
molecules. This leads to melting and viscosity drops below the solid/liquid line.
But as crosslinks are absent, at any point if temperature is reversed, the viscosity
will increase. (represented by double direction arrow on the plot)
➢ For thermoset, initial viscosity is just below the solid/liquid line. As temp
increases, viscosity y drops for thermosets due initial low molecular weight. It
then reaches a minimum, then increases rapidly to a position substantially
above the liquid solid line. Two separate phenomena occur. Thermoset thinning
and gelation

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 Thermosets and thermoplastics
➢ Viscosity standpoint comparison

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Chemical Structure of Polymer Matrices

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 Chemical Structure of Polymer Matrices
➢ Aromatic group because it contains strong order
➢ Six carbon atoms attached with one hydrogen (also known as Benzene ring).
➢ If hydrogen is replaced when aromatic structure is attached to other molecules
➢ Because of physical nature of aromatic group, they impart special properties
➢ Very stable
➢ Resistant to chemical attacks
➢ Shape (flat and stiff) imparts strength and stiffness
➢ More the number of aromatic groups., more the properties
➢ Attachment of benzene can be as pendent, backbone or arrangement
➢ Some polymers have no aromatic groups at all. These polymers are said to be
aliphatic. “Aliphatic” simply means the absence of aromatic

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Properties of Matrices

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Properties of Matrices

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 Properties of Matrices
➢ Crystallinity in polymers
➢ Resistance to solvents and water
➢ Permeability and resistance to gases
➢ Fire resistance
➢ Electrical properties
➢ Toughness
➢ Wet out of fiber

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 Crystallinity in Polymers

➢ Regions of close packing are crystalline regions, that held together using
secondary bonds. These increase the melting point.
➢ Thermoplastics have crystalline regions
➢ Crosslinks in thermosets interfere with periodic packing of atoms.
➢ Molecular motion is missing in the crystalline region, so no Tg for that part.
➢ Presence of aromatic content increases the melting point of most polymers

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 Resistance to Solvents and Water

➢ This resistance depends on chemical nature of matrix and solvent

➢ More the nature of polymer resembles with environmental chemical, more the
effect.
➢ Chemical polarity is most important aspect.
➢ Polar solvent can react with polar polymer molecule
➢ Raising the temperature swells the polymer and allows the solvent molecules to
penetrate, thus increasing the reaction.
➢ Water is a strong polar molecule which makes unsaturated polyesters more
susceptible to water attack
➢ Thermoplastic polymers are resistant to solvent attacks due to their tightly
packed atoms with several intermolecular interactions.

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 Permeability and resistance to gases

➢ Gas reactions render the polymer degraded. Effect is much like effect of
solvents.
➢ Oxygen is most important reactive gas that degrades the polymers.
➢ Antioxidants are added in polymer concentration in small concentrations i.e. 1-
2%.
➢ Permeability is the ability of gas to pass into or through a material. This tendency
increases if chemical nature of gas and polymer is same.
➢ Small gases can pass through space between long polymer chain molecules.
➢ Crosslinking and crystallinity decrease permeability.

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 Fire resistance

➢ Aliphatic polymers burn fast compared to Aromatic polymers.

➢ Char formation in aromatic polymers resists further burning.
➢ Common method to enhance fire resistance is to mix compounds with halogen
atoms (F, Cl, Br, I).
➢ Halogens create a dense gas environment that smothers the flame.
➢ Halogens can also be added as fillers like, MgCl or CaBr.
➢ Other than this, non-halogentated fillers can also be added, like Alumina,
hydrated alumina as flame retardants.

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 Electrical properties

➢ Most polymers are non-conductive and have high electrical resistance.

➢ Alumina can increase arcing resistance inline with flame retardant properties.
➢ To increase the electrical conductivity metallic powders as fillers or electrically
conductive reinforcement can be added. For e.g. airplane skins for protecting
against lightening strikes.

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 Toughness

➢ It is the ability to absorb energy.

➢ Toughness is dependent on combination of both matrix and reinforcement.
➢ For composite structures, impact toughness is important, which is the ability to
absorb an impact, such as falling or striking object.
➢ Matrix should quickly diffuse energy of the impact.
➢ If the matrix is able to elongate, it can stretch when force is applied.
➢ Aliphatic polymers with few secondary bonds are suitable
➢ Aromatic polymers with pendant configuration are suitable.
➢ Sometimes, toughening agents can be added to.
➢ Reducing crosslinks can help to increase toughness

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 Wet out of Fiber

➢ Viscosity of the resin strongly depends on wet-out and both are inversely
correlated.
➢ Viscosity increases with the molecular weight of the polymer.
➢ Thermoplastics don’t change their molecular weight as they don’t under go
crosslinking, so wetting of fiber is difficult. Therefore, thermoplastics are difficult
to process with their composites.

➢ Thermosets, due to their low molecular weight, are ideal to be used in

composites. This fact has let to overwhelming use of thermosets in long fiber
composites.

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 Additional materials added in matrices
➢ ADDITIVES
➢ FILLERS
➢ PIGMENTS
➢ VISCOSITY CONTROL AGENTS,
➢ SURFACE AGENTS

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 Additives
Introduction and Application
➢ Additives are the materials added to the basic composite materials (resin
system and reinforcements) to improve some specific property.
➢ Most additives are present in only small concentrations; although one, fillers,
can be a major component of the mixture.
➢ Additives include flame-retardant materials, such as halogen-containing resins
or special fillers, electrical property enhancers, UV, inhibitors, and tougheners.

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 Fillers
Introduction and Application
➢ Fillers are solid materials ground to fine powders and added to the resin mix to
reduce overall cost and, occasionally, to impart some other beneficial property.
➢ The most common fillers are common minerals, such as limestone and talc,
which have been purified and ground.
➢ Fillers usually have no particular length-to-width ratio and are not, therefore,
fibers, but are, instead, particles.
➢ Fillers usually cost much less than the resin and therefore any combination of
the resin and filler will be less costly in terms of total weight or total volume than
the pure resin itself.
➢ Cost reduction is usually the most important reason to use fillers in composite
materials.
➢ The effect on mechanical properties of adding reasonably low concentrations of
fillers to the resin mixture is generally not large, especially in the presence of
fiber reinforcements; although some increased stiffness or reduced strength and
reduced elongation is common.
➢ Fillers can also impart some special benefits such as fire retardation, color, or
dimensional control (called low profile and discussed in the section on molding
compounds in the polyester chapter).
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 Pigments and Dyes
Introduction and Application
➢ The color of a composite is affected by the way light is absorbed or diffracted by
either the polymer, fibers, or additives in the material.
➢ Additives that cause specific light to be absorbed are called colorants.
➢ The colorants can be organic, based on carbon containing molecules, in which
case they are also known as dyes.
➢ Alternately, the materials can be ground, inorganic powders called pigments.
Dyes and pigments are available in a wide range of colors and shades.
➢ Generally, dyes are more subtle in color than pigments but pigments are more
intense (vibrant).
➢ Pigments are also more stable at high temperatures.

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 Viscosity Control Agents
Introduction and Application
➢ Viscosity control is important for the proper molding of resin mixtures to make
composite parts.
➢ For instance, if the viscosity is too low, the material might run down the side of
the mold or drip off the fibers.
➢ Fillers might be added to thicken the mixture; but sometimes they cannot be
used or, alternately, even with fillers the material is still too thin.
➢ In these cases, a thixotrope can be used to significantly increase the viscosity of
the mixture with the addition of only a small amount.
➢ A common material of this type is fumed silica, which can give a significant
increase in viscosity either by itself or with the addition of special thixotrope
enhancers.
➢ This is accomplished because there is some secondary bonding induced
between the polymer chains.
➢ These secondary bonds will decompose with heat and are therefore not
important in the final product, but during processing they add considerable
viscosity to the resin mixture.

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 Surface Agents
Introduction and Application
➢ Surface energy and charge is the tendency of some surfaces to not be wetted
by the resin mixture.
➢ Often, this problem can be solved by adding a surfactant to the resin mixture.
➢ The surfactant changes the charge or energy of the surface to be coated and
facilitates wetting by the resin.
➢ Surfaces that might have this problem include molds and fibers

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 Anti-foaming Agents
Introduction and Application
➢ Some resins have a tendency to foam, thus complicating their application
especially with spraying.
➢ Hence, additives are available that reduce the tendency of materials to foam.
➢ These additives usually work by changing the charge or the energy on the
surface of the resin or filler particles in the mixture.
➢ Silicones are materials that can serve as anti-foaming agents of this type

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Fibers and their properties

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 Fibers
➢ Fibers are the principal constituents in a fiber-reinforced composite material.
➢ They occupy the largest volume fraction in a composite laminate and share the
major portion of the load acting on a composite structure.
➢ Proper selection of the fiber type, fiber volume fraction, fiber length, and fiber
orientation is very important.
➢ Following characteristics of a fibers are of interest for composite laminates:
1. Density
2. Tensile strength and modulus
3. Compressive strength and modulus
4. Fatigue strength as well as fatigue failure mechanisms
5. Electrical and thermal conductivities
6. Cost

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 Fibers
Table: Some commercially available fibres

Fibre Density Tensile strength Young’s modulus Elongation

(g/cc) (MPa) (GPa) at failure
(%)
Flax 1.45 500-900 50-70 1.5-4.0
Hemp 1.48 350-800 30-60 1.6-4.0
Jute 1.3 300-700 20-50 1.2-3.0
Bamboo 1.4 500-740 30-50 2
S-glass 2.5 4585 83 5.7
E-glass 2.5 1200-1800 72 2.5
Carbon 1.4 ~4000 235 2
Kevlar 1.44 3600-4000 130 2.8
Aramid 1.4 3400-3600 83-186 2.0-4.0
Boron (on W) 2.5 3447 386 0.9
Steel 7.8 1000 200 30
Aluminium 2.8 483 70 20
Titanium 4.5 1145 172 30
Magnesium 1.8 276 48 15
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 Fibers vs Matrix vs Composite

Fig: Stress–strain curves of the kenaf sheet, the PLLA film and the kenaf/PLLA composite with the fiber
content of 70 vol%. 61
Fibers

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Fibers

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 Glass Fibers
Manufacturing Process
➢ The raw materials used for making are silica sand, limestone, fluorspar, boric
acid, and clay. Silica accounts for more than 50% of the total ingredients.
➢ By varying the amounts of raw materials and the processing parameters, other
glass types are produced.
➢ The raw materials are mixed thoroughly and melted in a furnace at 2,500 to
3,000 °F.
➢ The melt flows into one or more bushings containing hundreds of small orifices.
The glass filaments are formed as the molten glass passes through these
orifices and successively goes through a quench area where water and/or air
quickly cool the filaments below the glass transition temperature.
➢ The filaments are then pulled over a roller at a speed around 50 miles per hour.
The roller coats them with sizing.
➢ The amount of sizing used ranges from 0.25 to 6% of the original fiber weight.
All the filaments are then pulled into a single strand and wound onto a tube.
➢ Sizing is lubricant material that prevents wear and tear of the fibers

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 Glass Fibers

Table: Approximate chemical compositions of some glass fibers (wt.%)

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 Glass Fibers

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Fig: Schematic representation of marble melt process for production of continuous filament fiberglass
 Glass Fibers

Fig: Glass fiber is available in a variety of forms: (a) chopped strand, (b) continuous yarn, 67
(c) roving, (d) fabric [courtesy of Morrison Molded Fiber Glass Company]
 Glass Fibers
Applications
➢ Boat hulls
➢ Light rail cars
➢ Building roof structures, housings and cabinets for appliances
➢ Tub and shower units,
➢ Wall and bathroom panels,
➢ Automobile bodies
➢ Ducts for the air conditioning and heating
➢ Vaulting poles, bows and arrows, surfboards, snowboards, and skateboards.
➢ Snowmobile housings are usually FRP

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 Carbon Fibers

➢ The demand for reinforcement fibers with strength and stiffness higher than
those of glass fibers has led to the development of carbon or graphite fibers.
➢ The mechanical properties of carbon fibers have steadily increased through
improvements in starting materials and manufacturing methods.
➢ Today, carbon fiber has among the highest specific strength and highest specific
modulus of any material.

Fig: Woven carbon fiber (Source: https://system.eu2.netsuite.com/core/media/media.nl?id=4687&c=3937524&h=77cae10da5ae902f62fb)

69
 Carbon Fibers
Manufacturing Process
➢ The raw materials used for making carbon fibers are polyacrylonitrile (PAN) or
pitch.
➢ All of these materials have high carbon concentrations relative to other atoms
and all can be converted into a graphite material.
➢ PAN-based fibers have good properties with relatively low costs for standard
modulus products.
➢ Pitch-based fibers have high modulus and good thermal conductivity.
➢ Stabilization step(oxidation step) involves stretching of the fibers, they become
stabilized. This is done with moderate heat and in an air atmosphere.

These rings are

crucial for
formation of
graphite

Fig: Structural changes of PAN-based carbon fiber during the stabilization step of the manufacturing process

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 Carbon Fibers
Manufacturing Process
➢ Carbonization (This step is sometimes also called pyrolization): during this step
the fibers are heated to higher temperatures in a nitrogen atmosphere and the
tension on the fibers is maintained. Hydrogen molecules attached to the
interconnected rings are removed by the heat and the chains of rings merge
together to form plates.

Fig: Structural changes of PAN-based carbon fiber during the carbonization step of the manufacturing
process.

➢ Because of material loss, fiber diameter reduces to half of its original diameter.

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 Carbon Fibers
Manufacturing Process
➢ Graphitization. In this step, the nitrogen atoms present in the rings are
eliminated and the ring structure is further consolidated.
➢ The carbon content of the fibers after graphitization is generally above 99%. The
differences in modulus and strength of the fibers are largely dictated by the
conditions present during graphitization.
➢ Higher-modulus fibers are processed at higher temperatures and for longer
times

Fig: Structural changes of PAN-based carbon fiber during the graphitization step of the manufacturing
process.
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 Carbon Fibers
Manufacturing Process
➢ The fibers are cleaned in an electrolytic bath. This bath removes debris that
might have been formed during the heating processes and oxidizes the surface
of the fibers.

Fig: Manufacturing process for making carbon fibers.

➢ Sometimes, hydroxyl groups are added on the surface to improve the bonding
on the surface of the carbon fiber.
➢ Whiskerization or vapour-phase deposition of pyrolitic carbon on the fiber
surface is also done to improve bonding with matrix. But these are generally
expensive are successful on laboratory scale.
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 Carbon Fibers
Structure

Fig: Three-dimensional representation of the carbon fiber structure. 74

 Carbon Fibers
Properties
➢ C/F have high strength, high stiffness, high toughness, and low weight.
➢ C/F have a negative CTE indicating that as the temperature goes up, the
sample gets smaller.
➢ C/F have one of the highest thermal conductivities, even surpassing that of
most metals.
➢ These fibers can be used as radiators (heat pipes) to transmit heat away from the heat source.
➢ Carbon fibers are elastic to failure at normal temperatures (meaning that they
do not deform before failure), which renders them creep resistant and not
susceptible to fatigue.
➢ They are chemically inert except in strongly oxidizing environments or when in
contact with certain molten metals.
➢ C/F have excellent damping characteristics as well

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 Carbon Fibers
Applications
Representative applications based upon strength, stiffness, and low weight
include the following:
➢ Aircraft control surfaces and, increasingly, full fuselages;
➢ Helicopter rotor blades and wind turbine blades;
➢ Aircraft structural parts such as door and landing gear assemblies;
➢ Automotive drive shafts and leaf springs;
➢ Racing car bodies and frames;
➢ Spacecraft, rockets, and missiles; and
➢ High-precision tooling

76
 Carbon Fibers
Applications
These applications are based on thermal properties:
➢ Heat shields for missiles and rockets; brakes
➢ Aerospace antennas (because of the low coefficient of thermal expansion)
➢ Space structures such as telescope mounts
➢ Housings for computers, small motors and electrical control panels.

The following applications are based on chemical inertness:

➢ Storage tanks (especially when weight a consideration such as the waste tanks
on airplanes)
➢ Ridge structures (which will not corrode and have good seismic resistance)
➢ Uranium enrichment centrifuge in the nuclear industry

Applications based upon fatigue resistance and self-lubrication:

➢ Textile machine components
➢ Air-slide valves
➢ Compressor blades
➢ Artificial limbs
77
 Aramid Fibers
➢ Aramid fiber is a generic term for a class of synthetic organic fibers called
aromatic polyamide fibers.
➢ Well-known commercial names of aramid fibers include Kevlar and Nomex (Du
Pont) and Twaron (Teijin Aramid).
➢ Kevlar has para-oriented aromatic rings, i.e., its basic unit is a symmetric
molecule, with bonds from each aromatic ring being parallel, while Nomex is
meta-oriented, with bonds at 120-degree angles to each other.
➢ They are widely used for ballistic protection and then as a reinforcement for
high-performance composites.
➢ The fibers have also found applications in high-strength cloth, such as that used
for sails on racing boats and protective clothing and gloves

78
Fig: Woven Kevlar fiber (Source: https://system.eu2.netsuite.com/core/media/media.nl?id=4687&c=3937524&h=77cae10da5ae902f62fb)
 Aramid Fibers
Manufacturing Process
➢ The raw materials used for making aramid fibers are para-phenylenediamine
and terephthaloychloride.

Because high aromaticity, and intermolecular

bonding, the polymer is difficult to dissolve

Fig: Synthesis of aramid and its intermolecular bonding

79
 Aramid Fibers
Manufacturing Process
➢ The solution is then forced though a plate (spinneret) into which many small
holes have been drilled.
➢ The material emerges as continuous fibers.
➢ The fibers are then washed, collected, dried, and wound onto spools.
➢ As indicated by the inherent rod-like nature and high crystallinity of the fibers,
the molecules are already aligned in the long direction as they are formed.

80
Fig: Manufacturing process for aramid fibers.
 Aramid Fibers
Properties
➢ Aramid fibers are less dense than fiberglass and carbon fibers, and intermediate
in strength fibers and stiffness between glass and carbon fibers.
➢ As indicated by the inherent rod-like nature and high crystallinity of the fibers,
the molecules are already aligned in the long direction as they are formed.
➢ During failure (tension), the fibers break into small fibrils, which are like fibers
within the fiber.
➢ Similar to failure of cable and solid rod.
➢ But these have poor compression resistance, rarely used in those applications
➢ The thermoplastic nature of aramids means that the fibers are sensitive to heat
and sunlight (UV light).
➢ Excellent resistance to chemicals (retention of tensile strength).

81
 Aramid Fibers
Properties

Fig: Impact toughness of aramid and carbon fiber composite pressure bottles.

82
 Aramid Fibers
Applications
Advantage are because of combination of light weight, strength, modulus, and
especially toughness.
➢ Ballistic protection- body armor like bullet proof vests.
➢ Armor for ships and motorized combat vehicles such as tanks and personnel
carriers.
➢ Battlefield shelters
➢ Leading edges of aircraft wings and other structures where impact damage
might be expected
➢ High-performance pressure vessels (high hoop stress and control of impact
damage)

83
 UHMWPE Fibers
➢ Ultra-high-molecular-weight Polyethylene (UHMWPE) Fiber
➢ Traditional polyethylene is not, however, used as a textile fiber because of
durability (cracking) problems.
➢ UHMWPE fibers have molecular weights that are orders of magnitude higher
than traditional polyethylenes.

Fig: UHMWPE fiber (Source: https://system.eu2.netsuite.com/core/media/media.nl?id=4687&c=3937524&h=77cae10da5ae902f62fb)

84
 UHMWPE Fibers
Manufacturing Process
➢ The techniques for polymerizing UHMWPE have been known for many years.
➢ Manufacturing process stretching of the fiber molecules in the fiber direction so
that the normal folding of the polyethylene molecules does not occur
➢ Extending the molecules creates rod-like structures.
➢ These rods have a high degree of molecular orientation (95–99%) and high
crystallinity (60–85%)

Raw
Solvent removed,
material: Powder dissolved in Solution forced
fibers dried and
UHMWPE a solvent. through spinneret
are drawn
powder
So that the normally The molecules
intertwined are aligned as they
molecules are free to pass through the
move completely spinneret
independent of other holes.
molecular chains.

85
Fig: Manufacturing process for UHMEPE fibers.
 UHMWPE Fibers
Manufacturing Process

Fig: Manufacturing process for UHMEPE fibers using Gel spinning process.

86
 UHMWPE Fibers
Properties
➢ High strength, toughness and stiffness, but less than glass and aramid fibers).
➢ But UHMWPE has major advantage—it weighs less for the same level of
protection as Aramid fibers.
➢ Poor bonding, but it may actually improve impact resistance. This is because
slippage along the matrix-fiber bonds uses energy and therefore improves
impact strength.
➢ The resistance to solvents and most acids (even better than aramid).
➢ UHMWPE fibers are prone to higher creep (extension at load less the break
load at elevated temperature).
➢ Therefore, not used in structural applications

87
 UHMWPE Fibers
Applications
➢ UHMWPE fibers are used for sailcloth and other fabrics and applications, like
ropes, where toughness and possibly light weight are important.
➢ Protective clothing, for example protective gloves.
➢ Light weight and excellent bullet-stopping capability give these fibers a strong
position in the ballistic protection market.

88
 Boron and SiC Fibers
➢ Boron and silicon carbide (SiC) are high modulus reinforcements.
➢ Total production volume of these materials is small compared to other fibers.
➢ Boron and SiC excellent properties suited to some specialized and important
applications.

W filament

Boron
deposits

Fig: Boron fiber

89
 Boron and SiC Fibers
Manufacturing Process
➢ Both boron and SiC fibers are made by the chemical vapor deposition (CVD)
process.
➢ Filament: W → for B fibers; C→ for SiC fibers

To remove
any lubricants or other
surface contaminants

Deposition gas
1. For B fibers, BCl3 and H2
2. For SiC fibers, SiH4
Chamber (Silane) and H2

For resistance heating of the

substrate filament

90
Fig: Manufacturing process for UHMEPE fibers.
 Boron and SiC Fibers
Manufacturing Process
➢ The time required to make the vapor-deposited fibers is usually long because
there needs to be time for the deposition buildup to occur.
➢ Typical reaction time inside the deposition chamber is generally from 30
seconds to a few minutes.
➢ CVD process conditions for making boron fibers can be modified to improve
temperature resistance, tensile strengths (by eliminating defects), and
wettability by a metal matrix.
➢ A minor change in the gas flows inside the chamber when making SiC fibers
creates a different SiC crystalline structure on the outside of the fiber.
➢ This change improves the adhesion of the SiC fibers to metal matrices

91
 Boron and SiC Fibers
Applications of Boron Fibers
➢ Boron fibers are unique among the high performance fibers because they
combine the usual good tensile properties with good compressive properties.
➢ The typical compressive strength for boron fibers is 1,000 ksi (6,895 MPa).
➢ Boron fibers are sold as prepreg tapes with epoxy as the matrix. These
prepregs have been used to make the aerospace products.
➢ Sports and recreation products such as rackets for tennis, racquetball, squash,
and badminton; fishing rods; skis; and golf club shafts.
➢ One principal application for boron fibers in an aluminum matrix is as tubular
struts in the frame and rib truss members and frame stabilizing members in the
space shuttle.

92
 Boron and SiC Fibers
Applications of SiC Fibers
➢ Silicon carbide fibers are often sold as reinforcements for metals and ceramics.
➢ Some applications for SiC fibers in an aluminum matrix include aircraft wing
structural elements, elements for movable military bridges, and missile body
casings.
➢ SiC fibers have been placed in a titanium matrix for drive shafts to give
increased stiffness over other candidate materials.
➢ Fan blades also have been made of titanium with SiC reinforcement.
➢ Ceramic armor reinforced with SiC fibers has become a major product and has
a bright future.

93
 Natural Fibers
Why we need natural fibers?
➢ Environmental reasons
➢ Renewable resources
➢ Thermally recyclable, biodegradable, CO2 neutral
➢ Low energy consumption (which means low CO2 and low “carbon footprint”)
➢ Cost: potentially low cost
➢ Health and safety: less abrasive and safe to handle
➢ Good specific mechanical and tribological properties
➢ Natural image, design aspects
➢ Light weight structures with high modulus values
➢ Low coefficient of thermal expansion
➢ Good acoustic and vibration damping capacity
➢ Increased recycling possibilities → better energy recovery
➢ Less environmental impact due to material production.

94
 Natural Fibers
Some data on energy utilisation for fibre production:
• Lignocellulosic fibres 4-15 MJ/kg
• Natural fibre mat 9.7 MJ/kg
• Glass fibre 30-50 MJ/kg
• Glass fibre mat 55 MJ/kg
• Carbon fibre 130 MJ/kg

Fig: Application of natural fibers in the automotive industry

95
 Natural Fibers
Types of Natural Fibers
Natural fibers

Plant Animal Mineral

Seed Fruit Stem Leaf Wood Stalk Grass Hair Silk

(or bast) fibers

Lamb’s wool Tussah silk Asbestos

Cotton Coir Flax Pineapple Hard Wheat Bamboo
Goat hair Mulberry silk Fibrous brucite
Kapok Hemp Abaca Soft Maize Bagasse
Angoral wool Wollastonite
Milkweed Jute Henequen (flour) Barley Esparto
Ramie Sisal Rye Sabei Cashmere
Kenaf Oat Phragmites Yak
Rice Communis Horse hair

96
Ref: Akil, H., Omar, M.F., Mazuki, A.A.M., Safiee, S.Z.A.M., Ishak, Z.M. and Bakar, A.A., 2011. Kenaf fiber reinforced composites: A review. Materials & Design, 32(8), pp.4107-4121.
 Natural Fibers
Production of Natural Fibers

Fig: Schematic representation of natural fiber production

97
Ref: Akil, H., Omar, M.F., Mazuki, A.A.M., Safiee, S.Z.A.M., Ishak, Z.M. and Bakar, A.A., 2011. Kenaf fiber reinforced composites: A review. Materials & Design, 32(8), pp.4107-4121.
 Prepregs
Introduction
➢ A prepreg (pre-impregnated) is a resin-impregnated fiber, fabric, or mat in flat
form, which is stored for later use in hand lay-up or molding operations.
➢ Fibers laid at 0° orientation and preimpregnated with resin are called
unidirectional tape.
➢ Various types of prepregs available as unidirectional tape, woven fabric tape,
and roving.
➢ Unidirectional tape provides the ability to tailor the composite properties in the
desired direction. Woven fabric prepregs are used to make highly contoured
parts in which material flexibility is key.
➢ It is also used to make sandwich panels using honeycomb as a core material.
Preimpregnated roving are primarily used in filament winding applications

Matrix

Fiber mat
98
Fig: Carbon fiber-epoxy prepreg (Source: http://cdn.fibreglast.com/images/LC_Prepreg.jpg)
 Prepregs
Manufacturing

Heating is done only till stage B

Solution will contain solvent and

epoxy. Solvent will control the
Fig: Schematic of prepreg manufacturing. viscosity of the resin solution

99
 Prepregs
Properties of Prepregs

100
 Prepregs
Applications
➢ Prepregs are being increasingly used in high performance applications in the
composites industry and also in other sectors. Some key areas where prepregs
currently find use are listed below:
➢ Aircraft interiors, aerospace components, aircraft flooring, cargo liners
➢ Automotive parts and components, tooling, ballistic panels
➢ A/C ducting, electronic-transmission applications
➢ UV resistant parts, sporting goods, high temperature parts
➢ Honeycomb and foam panels, flame retardant laminates,
➢ Carbon-carbon composites, high-rise flooring, high impact surfaces,
➢ UAVs, seatbacks, doubles

101
 Preforms
Introduction
➢ Preforms are feedstock for the RTM and SRIM processes, where a
reinforcement in the form of a thick two- or three-dimensional fiber architecture
is put in the mold cavity and then resin is injected into the cavity to obtain the
composite part. Preforms are made in several ways.
➢ To make a preform by braiding and filament winding, dry fibers are laid over a
mandrel.
➢ Preforms can be of any shape, depending on the requirements and size of the
component.
➢ Preforms are stable and offer a good strength-to-weight ratio.

102
 Preforms
Manufacturing

Fig: Schematic of short fiber preform fabrication.

103
 Honeycomb Materials
Introduction
➢ These materials are generally used for sandwich structures as cores between
two thin high-strength facings.
➢ These materials are joined with facings using an adhesive strong enough to
transfer the loads from one face to another.
➢ The honeycomb material acts like a web of I-beams, taking the shear loads as
well as providing structural rigidity by keeping high-strength materials away from
the neutral axis where tensile and compressive stresses are high.
➢ The difference between sandwich structure and I-beam is that in sandwich
structure, the web is spread over the entire cross section, providing high
torsional rigidity; whereas in I-beam, the web is only in the middle, thus
providing less torsional rigidity.
➢ The sandwich construction provides the highest stiffness-to-weight ratio and
strength-to-weight ratio.

104
 Honeycomb Materials
Introduction

Fig: Honeycomb structures Fig: Honeycomb crash absorption structure

made of injection moulded thermoplastic
polymer on a BMW i3

105
 Honeycomb Materials
Manufacturing
➢ Honeycomb materials are made:
➢ Aluminum
➢ Nomex (Nylon with aromatic backbone)
➢ Polycarbonate
➢ Polypropylene
➢ Wood (Bast)
➢ Expansion
➢ Used for making aluminum and Nomex honeycombs.
➢ In the expansion process, sheets of material are stacked together in a block form.
➢ Before stacking adhesive node lines are printed on the sheets to obtain interrupted adhesive
bonding.
➢ The stack of sheets is then cured. Slices of appropriate thickness are cut from the block and then
expanded to obtain the desired cell size and shape.
➢ Corrugation.
➢ In the corrugation method, the sheet of material is transformed into corrugation form using
corrugating rolls.
➢ The corrugated sheets are stacked together, bonded, and cured.
➢ Honeycomb panels are cut from the block into the desired shape and size without any expansion.

106
 Honeycomb Materials
Applications
➢ Honeycomb materials are used in aircraft, transportation, marine,
communication, sporting goods, and many other industries.
➢ Honeycomb materials provide predictable crash behavior and are used for the
design of crash resistant parts.
➢ These materials are used for the design of computer and communications
rooms because of their radiation shielding characteristics.
➢ The repetitive cellular structure acts as a myriad of waveguides, attenuating
signals across a wide frequency range.

107
 Reinforcement forms
Introduction

➢ Filament is obtained by passing molten material through spinneret.

➢ Fiber is generally having long aspect ratio. Length greater than 0.5 cm is fiber
and below that is whisker.
➢ Short fibers, also known as, stapled fibers are useful for SMC/BMC. Length is
1.3 cm to 10.2 cm.
➢ Filament group is known as strand and is untwisted, if filament is twisted to keep
fibers in bundle its known as yarn.

108
 Reinforcement forms
Woven and kitted fabrics
➢ Various weave patterns are available to handle characteristics such as
openness, drape and strength
➢ Openness is the space between parallel fibers. It is inversely proportional to
wrap and fill count.
➢ Drape is the ability to hang without crease and ability of the fibric to confirm
shape of mold.
➢ Wrap count is the number of yarns or ends per inch (or cm)
➢ Unravelling edge ae known as selvage

109
 Reinforcement forms
Woven and kitted fabrics
➢ In the weaving process, fibers are arranged in a parallel array on a loom
between two supports.
➢ The fibers are aligned in the warp, longitudinal, or machine direction. The
machine direction is usually 0°.
➢ These interwoven, crossing fibers are called the weft, woof, fill, or transverse
direction fibers. These fibers are arranged at 90° to the machine direction

110
 Reinforcement forms
Types of knit

111
 Reinforcement forms
Types of weave

Weft knitting
Giver greater drape i.e. fabric can be
contoured. Useful with complex
geometry parts like aircraft conduits,
aircraft electrical wiring.

Triaxial knitting
Useful where loads are chiefly along
45degree axis, like drive shafts

112
 Reinforcement forms
Non-woven fabrics (Mats)

Popular in boats to be used in spray up

technique. Low cost composite
products.

Properties better than chopped strand

mat., handling can be rough.
Strength only 35% to 50% then woven
laminates as there more randomness
in fiber direction.

113
Manufacturing of thermoset composites

114
 Unsaturated polyesters
➢ Also known as thermoset polyester (its an condensation polymer)
➢ Most common used thermoset due 25% to 50% cheap than vinyl ester and
epoxy.
➢ Advantages: Ease of curing and molding
➢ Disadvantages: Poor durability, brittleness, sensitive to polar solvents like water
(but is still popular)
➢ Unsaturated polymers is mixed with fiberglass to form FRP in form of SMC
(sheet molding compounds)
➢ Monomers: Glycol and Diacids combine (ester group).
➢ Resulting molecule has two active ends, permitting additional reactions with
monomers.

115
 Unsaturated polyesters
Crosslinking in polyesters
➢ Curing or crosslinking has a major impact on economics of the molding process.
➢ During crosslinking, bonds are formed between polymer molecules enabling
them to form enormous interconnected network.
➢ As crosslinking happens, polyester becomes dramatically hard, stiff and exhibits
good strength
➢ The reinforcing fibers must be introduced before curing so that proper wetting
between fibers and resin can take place.
➢ Some initiator or catalysts may be added to start the crosslinking reaction.
➢ Crosslinking of UP is a complex process and critical to achieve good composite
part.
➢ Cure exotherm plot indicates increase in temperature during crosslinking.
➢ Cure exotherm temperature increases as thickness of the part increases
because heat retention and accompanying higher reactivity.
➢ Initiators and accelerators are added to start and speed up the curing process
therefore reducing the cycle time.

116
 Unsaturated polyesters
Crosslinking in polyesters

117
 Cure control additives
Additives
➢ Purpose is to increase the shelf life of unsaturated polyester UP so storage time
is longer
➢ Pot life is the time needed when all materials are mixed and placed in the mold.

➢ [A] Inhibitors
➢ These materials inhibit crosslinks (especially premature crosslinking) and
extend the shelf life. The work by deactivating the free-radicals. Ex.
Hydroquinone & catechol

➢ [B] Promotors
➢ Free radicals are activated by heating the materials. Organic peroxides split
apart into free radicals. Ex. Cobalt Napthlate.

118
 Molding compounds

➢ Mixing of resin, filler, additive, inhibitor and promotor in proper proportion is

done to prepare the molding compounds. Reinforcement may sometimes be
part of molding compounds.
➢ Economies of scale may apply
➢ Once prepared, molding compounds are ready for molding (ready to use).
➢ Entire ingredients commonly mixed, packaged and stored.
➢ Time and temperature during storage have to be carefully monitored.
➢ Molding compounds are available in form of
➢ BMC: Bulk molding compounds
➢ SMC: Sheet molding compounds

119
 BMC

➢ Also known as dough molding compounds (DMC).

➢ Reinforcement is form of short fibers and strands may be added to have dough
like consistency..
➢ Suitable for metered quantity/shot by shot/open molding Ex. Compression
molding
➢ Because of high viscosity, BMC cannot move over longer distance therefore part
length not too long

120
 SMC

➢ Useful for large size parts.

➢ Composition same as BMC but method pf mixing the compounds is different
➢ Resin, with filler additives etc., are doctored on a plastic sheet
➢ Chopped (shirt fiber) reinforced is sprinkled on the resin film
➢ Resin filler & chopped reinforcement is sandwiched between the plastic carrier
film.
➢ Longer fiber can be used & process does not impede their movement
➢ BMC & SMC are popular with automobile parts.

121
 Epoxies
➢ 50% use is as adhesives (like aldralite)
➢ In reinforced form, largest market in laminate sheets.
➢ Used in electrical circuit boards due low conductivity and high dielectric
strength.
➢ Advantages: good adhesives and mechanical properties so used with carbon
fiber in high performance composites like aerospace, sporting goods etc.
➢ Chemical structure of epoxy is characterized by three member ring epoxy
group. The ring structure is the active site on the epoxy molecule.

122
 Epoxies
➢ Unlike unsaturated double carbon bonds present in between the polymer chain,
epoxy groups are present at the end of the polymer chain.
➢ The main contribution of epoxy molecule is to addition of hydroxyl group which
is formed as part of epoxy curing process by some amine (curing agents). The
hydroxyl group adds adhesiveness to final cured polymer.

123
 Epoxies

➢ When the end of the amine hardener comes into close proximity with the epoxy ring,
the nitrogen on the hardener (which has a slight negative charge and is therefore
called a nucleophile) seeks the slightly positive carbon in the epoxy ring.
➢ The nitrogen forms a bond with the carbon and thus breaks open the epoxy ring.
The nitrogen loses a hydrogen molecule as it forms the bond with the carbon.
➢ The hydrogen, which is slightly positive, will then bond to the oxygen that was part of
the epoxy ring. 124
➢ The new carbon-nitrogen bond is the critical bond for crosslinking.
Epoxies

➢ Although epoxy polymerization are

condensation in nature, no by-
products are generated during the
process. This greatly simplifies the
process.

➢ Molecules that have reactive groups

used to cure epoxies are known as
hardeners or curing agents.

➢ For epoxy, several types of reactive

groups open the epoxy ring and start
the crosslinking.

➢ Common reactive groups include

amines, amides, acids, phenols,
analines.

125
 Epoxies

➢ Molecules containing these groups are known as hardeners or curing agents

➢ Through mixing of epoxy & hardeners may Most hardeners react fast with
application of heat which facilitates the movement of epoxy and hardener
molecules.
➢ Some combination of epoxy and hardeners don’t react at room temperature.
➢ Mixing ratios are specified by the epoxy manufacturer and is given to give excat
right number of active sites.

➢ Number of crosslinks per unit length is known as crosslink density.

126
Epoxies

127
Epoxies vs. Unsaturated Polyester

128
 Some High Performance Thermosets
➢ VINYL ESTERS
➢ Cost in between UP and epoxy
➢ Have similarities and fit between unsaturated polyesters and epoxies.
➢ Have superior toughness and corrosion resistance
➢ Easier to cure than epoxies
➢ Popular where chemical resistance better than polyesters is required (ex. Pipes
and tanks for chemical industries, air pollution control, marine applications)
➢ Chemical structure is intermediate between epoxies and thermoset polyesters

129
 Some High Performance Thermosets
➢ VINYL ESTERS
➢ Vinyl ester are formed by reacting acrylic acid and epoxy. The acrylic acid opens
the epoxy ring and forms new bonds between O and C near the epoxy ring site.

130
 Some High Performance Thermosets
➢ VINYL ESTERS
➢ The ester linkages at the end of the molecule make the resin more susceptible
to water and other solvent attack (but not as much as polyester)

131
 Some High Performance Thermosets
➢ PHENOLICS
➢ First synthesized thermoset under the name of Bakelite.
➢ Cost is 10-15% higher than polyesters
➢ Mostly used as non-reinforced thermosets for electrical switches, junction
boxes, automotive molded parts.
➢ Due their high crosslink densities they are quite brittle.
➢ Filler like saw dust, shells of nuts are added to improve toughness
➢ Major properties:
➢ Excellent flammability retardency
➢ Low heat transfer
➢ High thermal stability
➢ High electrical resistance
➢ Good adhesion

132
 Some High Performance Thermosets
➢ PHENOLICS
➢ Polymer structure

133
 Some High Performance Thermosets
➢ PHENOLICS
➢ Because of favorable flame retardancy,
phenolic composite are popular in walls,
celling, floors of aircraft interior, train interior
etc.
➢ Special application as CF/phenolic composite
in exit nozzle of rocket due for ability to form
char, which has good thermal insulation. Also
char ablates (erodes slowly)

134
 Some High Performance Thermosets
➢ CARBON MATRIX
➢ No supplier gives carbon matrix
➢ Instead some resin is converted into carbon matrix
➢ Popularly phenolic material can be converted into carbon.
➢ These have good thermal stability, strong bonds,
➢ These require high activation energy to break bonds
➢ Useful in high temperature applications, like rocket nose cones, exit throats
when used as CCC
➢ Also used in gas turbines combustors, brake pad linings for racing cars etc.

135
 Some High Performance Thermosets
➢ CARBON CARBON COMPOSITES (CCC)

➢ Starting materials is phenolic resin and CF. Fiber preform is placed into the mold
after which phenolic resin is introduced to impregnate the fibers.
➢ Next in pyrolysis (heating in absence of air) so resin chars does not burn.
During charing H, O are removed
➢ Holes are left behind which may lead to poor mechanical properties.
136
 Some High Performance Thermosets
➢ CARBON CARBON COMPOSITES (CCC)
➢ Holes are again created by pyrolysis step
➢ After impregnation is complete, the carbonization happen at 2500 deg C. By this
time, all non-carbon atoms is few and porosity is so low that it can be ignored.
➢ Entire process to make one prat may take week or days because of which CCC
are very expensive.

137
 Thermoplastics
➢ Engg Comp: can be used for automotive, boats. They strength traditional
plastics.
➢ Adv Comp:: Used as in aerospace, submarines,

138
Thermoplastics

139
 Some advanced Thermoplastics
➢ PEEK (poly ether etherketone)
➢ Only T/P qualified for aerospace applications

➢ Due to high aromatic content, PEEK has high Tg, which gives it good thermal
stability.
➢ PEEK has low flammability, low electrical conductivity, high solvent resistance,
high strength and excellent toughness.
➢ Crystallinity in PEEK is high leading to high strength and high modulus.

140
Manufacturing Process of Composites

141
 Manufacturing Techniques
Feedstock of Composites

Thermosets Thermoplastics

Fibers and Prepreg SMC/ BMC Fibers and Thermo Molding

resins resins plastic/ compound
Prepreg

• Filament • Filament • Compression

winding winding molding
• Pultrusion • Filament • Autoclave • Autoclave
• Pultrusion
• RTM winding • Hot Press • Hot Press
• RTM
• Spray-up • Pultrusion • Tape • Tape
• Spray-up
• Hand lay- • Hand lay-up • RTM winding winding
up • Spray-up
• Hand lay-
up

142
 Manufacturing Techniques
Fundamentals
➢ Transformation of uncured or partially cured fiber-reinforced thermoset polymers
into composite parts or structures involves curing the material at elevated
temperatures and pressures for a predetermined length of time.
➢ High cure temperatures are required to initiate and sustain the chemical
reaction that transforms the uncured or partially cured material into a fully cured
solid.
➢ High pressures are used to provide the force needed for the flow of the highly
viscous resin or fiber–resin mixture in the mold, as well as for the consolidation
of individual unbonded plies into a bonded laminate.
➢ The length of time required to properly cure a part is called the cure cycle. Since
the cure cycle determines the production rate for a part, it is desirable to
achieve the proper cure in the shortest amount of time.
➢ The cure cycle depends on an number of factors, including resin chemistry,
catalyst reactivity, cure temperature, and the presence of inhibitors or
accelerators.

143
 Manufacturing Techniques
Factors to be considered
➢ Degree of Cure
➢ Viscosity
➢ Resin Flow
➢ Consolidation
➢ Gel-time test
➢ Shrinkage
➢ Voids

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 Manufacturing Techniques
Degree of Cure

➢ The degree of cure (αc) at any time t is defined as:

➢ H is the amount of heat released in time t and (dQ/dt) is the rate of heat
generation in an isothermal experiment conducted at a constant temperature T
➢ HR heat of reaction in dynamic heating

Fig: Schematic representation of the rate of heat generation in (a) dynamic and
(b) isothermal heating of a thermoset polymer in a differential scanning calorimeter (DSC). 145
 Manufacturing Techniques
Degree of Cure
➢ Higher cure temperatures increase the rate of cure and produce the maximum
degree of cure in shorter periods of time.

Fig: Degree of cure for a vinyl ester resin at various cure temperatures. (After Han, C.D. and Lem, K.W.,
J. Appl. Polym. Sci., 29, 1878, 1984.) 146
 Manufacturing Techniques
Viscosity
➢ Viscosity of a fluid is a measure of its resistance to flow under shear stresses.
➢ Low-molecular-weight fluids, such as water and motor oil, have low viscosities
and flow readily. High-molecular-weight fluids, such as polymer melts, have high
viscosities and flow only under high stresses.
➢ The two most important factors determining the viscosity of a fluid are the
temperature and shear rate.
➢ For all fluids, the viscosity decreases with increasing temperature. Shear rate
does not have any influence on the viscosity of low molecular-weight fluids,
whereas it tends to either increase (shear thickening) or decrease (shear
thinning) the viscosity of a high-molecular-weight fluids
➢ Polymer melts, in general, are shear-thinning fluids since their viscosity
decreases with increasing intensity of shearing

147
 Manufacturing Techniques
Resin Flow
➢ Proper flow of resin through a dry fiber network (in liquid composite molding
[LCM]) or a prepreg layup (in bag molding) is critical in producing void-free parts
and good fiber wet-out.
➢ In thermoset resins, curing may take place simultaneously with resin flow, and if
the resin viscosity rises too rapidly due to curing, its flow may be inhibited,
causing voids and poor interlaminar adhesion.
➢ Resin flow through fiber network has been modeled using Darcy’s equation,
which was derived for flow of Newtonian fluids through a porous medium.
➢ This equation relates the volumetric resin-flow rate q per unit area to the
pressure gradient that causes the flow to occur. For one-dimensional flow in the
x direction

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 Manufacturing Techniques
Consolidation
➢ Consolidation of layers in a fiber network or a prepreg layup requires good resin
flow and compaction; otherwise, the resulting composite laminate may contain a
variety of defects, including voids, interply cracks, resin-rich areas, or resin-poor
areas.
➢ Good resin flow by itself is not sufficient to produce good consolidation.
➢ Both resin flow and compaction require the application of pressure during
processing in a direction normal to the dry fiber network or prepreg layup.
➢ The pressure is applied to squeeze out the trapped air or volatiles, as the liquid
resin flows through the fiber network or prepreg layup, suppresses voids, and
attains uniform fiber volume fraction

149
 Manufacturing Techniques
Gel-time test
➢ The curing characteristics of a resin–catalyst combination are frequently
determined by the gel-time test. In this test, a measured amount (10 g) of a
thoroughly mixed resin–catalyst combination is poured into a standard test tube.
➢ The temperature rise in the material is monitored as a function of time by means
of a thermocouple while the test tube is suspended in a 82 °C water bath.

150
 Manufacturing Techniques
Shrinkage
➢ Shrinkage is the reduction in volume or linear dimensions caused by curing as
well as thermal contraction.
➢ Curing shrinkage occurs because of the rearrangement of polymer molecules
into a more compact mass as the curing reaction proceeds.
➢ The thermal shrinkage occurs during the cooling period that follows the curing
reaction and may take place both inside and outside the mold.

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 Manufacturing Techniques
Voids
➢ Presence of voids is considered the most critical defect in influencing its
mechanical properties.
➢ The most common cause for void formation is the inability of the resin to
displace air from the fiber surface during the time fibers are coated with the
liquid resin.
➢ The rate at which the fibers are pulled through the liquid resin, the resin
viscosity, the relative values of fiber and resin surface energies, and the
mechanical manipulation of fibers in the liquid resin affect air entrapment at the
fiber–resin interface.
➢ Voids may also be caused by air bubbles and volatiles entrapped in the liquid
resin.
➢ Solvents used for resin viscosity control, moisture, and chemical contaminants
in the resin, as well as styrene monomer, may remain dissolved in the resin mix
and volatilize during elevated temperature curing.
➢ In addition, air is also entrapped between various layers during the lamination
process

152
 Basic Manufacturing Steps

Impregnation

Lay up

Consolidation

Solidification

153
 Basic Manufacturing Steps
Impregnation
➢ In this step, fibers and resins are mixed together to form a lamina.
➢ The purpose of this step is to make sure that the resin flows entirely around all
fibers.
➢ Viscosity, surface tension, and capillary action are the main parameters
affecting the impregnation process.

154
 Basic Manufacturing Steps
Layup
➢ In this step, composite laminates are formed by placing fiber resin mixtures or
prepregs at desired angles and at places where they are needed.
➢ The purpose of this step is to achieve the desired fiber architecture as dictated
by the design.
➢ Performance of a composite structure relies heavily on fiber orientation and lay-
up sequence.

155
 Basic Manufacturing Steps
Consolidation
➢ This step involves creating intimate contact between each layer of prepreg or
lamina.
➢ This step ensures that all the entrapped air is removed between layers during
processing.
➢ Fibers go through elastic deformation when the compressive pressure
increases and resins flow out toward the boundary.

156
 Basic Manufacturing Steps
Solidification
➢ Vacuum or pressure is maintained during this period.
➢ The lower the solidification time, the higher the production rate achievable by
the process.
➢ This step ensures that all the entrapped air is removed between layers during
processing.
➢ In thermoplastics, there is no chemical change during solidification and
therefore solidification requires the least amount of time.
➢ In thermoplastics processing, the rate of solidification depends on the cooling
rate of the process.

157
 Basic Manufacturing Steps
Solidification
➢ Vacuum or pressure is maintained during this period.
➢ The lower the solidification time, the higher the production rate achievable by
the process.
➢ This step ensures that all the entrapped air is removed between layers during
processing.
➢ In thermoplastics, there is no chemical change during solidification and
therefore solidification requires the least amount of time.
➢ In thermoplastics processing, the rate of solidification depends on the cooling
rate of the process.

158
Open Mold Manufacturing Processes

159
 Open Mold Manufacturing Processes
➢ Simplest technique to mold composite part.

➢ Mold is single sided

➢ Popular for Engineering Composites.

➢ Two processes are popular:
➢ Hand lay up
➢ Spray lay up
➢ These processes come in category of layup molding

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 Open Mold Manufacturing Processes
➢ Concept of Gel Coat: Used for better outer surface of part. Gel coat is applied
on the mold but it ends with being on the part. Gel coat is a thermoset resin. Gel
coat is generally sprayed on the mold. Mainly intended for protective and
decorative surface.
➢ Material of Gel coat: Based on polyester or vinyl ester. Sometimes pigments,
additives for fast curing may be added.
➢ Storage: Shipped in drums and need to be stored at temp of 22-22 deg C
➢ Equipment: Application of gel coat is done with spraying it on the mold.
➢ Thickness of gel coat: 0.40 to 0.50 mm

161
 Hand lay-up and Spray lay-up techniques
Introduction
➢ Hand layup and spray techniques are perhaps the simplest polymer processing
techniques.
➢ Fibers can be laid onto a mold by hand and the resin (unsaturated polyester is
one of the most common) is sprayed or brushed on.
➢ Frequently, resin and fibers (chopped) are sprayed together onto the mold
surface.
➢ In both cases, the deposited layers are densified with rollers.
➢ Accelerators and catalysts are frequently used. Curing may be done at room
temperature or at a moderately high temperature in an oven.

162
 Hand lay-up techniques
Equipment

Fibers are laid onto a mold by hand, and the

resin is sprayed or brushed on

Fig: Hand layup technique

163
 Hand lay-up techniques
➢ Popularly thermoset are used as matrix, especially polyester and vinyl esters.
➢ Fillers and additives are mostly added by the molder rather resin manufacturer.
➢ Mostly shipped neat (i.e. without fillers or reinforcements).

➢ Reinforcement in form of mats, woven fabric, knits, popularly fiberglass is used

as matrix.
➢ Reinforcement are simply laid into or onto the mold.
➢ During wet out, fiberglass changes its color aiding monitoring of wet-out process
➢ Due to exotherm considerations, part cannot be too thick

➢ After curing, part is removed from the mold, trimmed or finished

164
 Spray lay-up techniques
Introduction
➢ Used when part is of sufficient size (not small parts) and spray can lead to
uniformly spread resin and reinforcement
➢ Advantage over hand layup is the speed with which fiber and resin be applied
on the mold.
➢ Disadvantages are requirement of special equipment, limited choice of resins,
high skill required.
➢ Spraying equipment consists of chopping mechanism on the spray gun. The
fibers are brought in the gun as roving and then chopped before they fall in
stream of resin just after the nozzle.
➢ Fibers are entrained with resin and are sprayed together onto the mold.
➢ Length of the chopped fiber should be short for ease of spraying and coverage
in thigh areas.
➢ Fiber of length 2.5 cm to 7.6 cm is most suitable for spraying.
➢ To ensure wet-out of sprayed fiber, a roller is used to make sure resin fully wets
the fiber bundles.

165
Spray lay-up techniques

166
 Tooling (molds)
➢ Mold not only defines the shape of the part, but also provides the surface on
which materials are deployed prior to cure.

➢ Materials of molds should be able to handle:

➢ Expected wear
➢ Temperature of cure
➢ Pressure exerted
➢ Thermal expansion
➢ Cost
➢ Materials used are metals like Aluminum, Stainless steel, Nickle, Invar, Alumina,
Gypsum based, glass/epoxy( FRP), graphite etc.

➢ Molds are shaped using CNC machining

167
 Open Mold Manufacturing Processes
➢ Challenges for Open Molding for advanced composites
➢ Difficulty in aligning of fibers
➢ Difficulty in optimizing amount of fibers
➢ Difficulty in controlling fiber/resin ratio
➢ Ensuring full fiber wet out
➢ Reducing void content

➢ For advanced composites, prepregs are used.

➢ Prepregs are carefully oriented so that the fibers are in the
desired direction to achieve the desired thickness.

➢ Prepregs can be manually layed up after cut and trimmed the

prepregs rolls using special knifes (like pizza cutters/shears)

➢ Laser cutting, water jet cutting, Die cutting can also be used

168
 Open Mold Manufacturing Processes
➢ After cutting, the cutouts are layed properly to avoid any wastage. This process
is known as Nesting.

➢ The prepreg pieces should have sufficient tack and drape so that the resin in
place in mold and also conform to the shape of the mold.

169
 Open Mold Manufacturing Processes
➢ Automatic tape layup (ATL)
➢ The prepreg roll is mounted on a payout drive of tape layup material. The
prepreg tapes are narrow (width 2-4 in.) for better drape.
➢ ATL are expensive, but they can accurately and quicky lay down plies of a
prepreg
➢ ATL works best for flat parts with gentle curvature, e.g., tail or wing section of
aircraft
➢ The prepreg pieces should have sufficient tack and drape so that the reain in
place in mold and also conform to the shape of the mold.
➢ For thermoplastic prepregs, the head heats the prepreg, which softens the
matrix.

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 Open Mold Manufacturing Processes
➢ Automatic tape layup (ATL)

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 Open Mold Manufacturing Processes
➢ Vacuum bagging
➢ Vacuum bagging is done after layup of prepregs is done. Purpose of using
vacuum is to remove trapped air after the layup and before the part is cured.
The process of air evacuation is known as debulking.
➢ For up to four plies, debulking operations can be done after layup and assembly.
For more than four plies, debulking operations can continue during the curing
process.
➢ Vacuum also ensure, resin flows across prepreg boundaries, thereby eliminating
boundaries and avoiding any delamination.

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 Open Mold Manufacturing Processes
➢ Vacuum bagging

➢ Release film or peel ply: It is used to simply pull all bagging system once curing
is complete. It a porous fil to allow excess resin to flow thorough it. Made of
Teflon sheet.
➢ Bleeder mat: Applied on top of release film. Bleeder mat absorbs excess resin.
Made of polyester felt, cotton etc.
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 Open Mold Manufacturing Processes
➢ Vacuum bagging
➢ Breather material: Is a highly porous layer. Acts as air distributor and help
volatiles escape and also acts as buffer between bag wrinkles and part
surfaces.
➢ Bleeder mat: Applied on top of release film. Bleeder mat absorbs excess resin.
Made of polyester felt, cotton etc.

➢ Vacuum line is connected to vacuum pump. To avoid any possibility of sucking

resin by the vacuum pump, a resin trap is used.

➢ Sealants is used to form airtrap seal with vacuum bag. But these should
withstand the curing temperatures.

➢ Sometimes, thermocouple wires and pressure sensor may be inserted in

vacuum bagging to monitor temperature and pressure during cure cycle.

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 Open Mold Manufacturing Processes
➢ Curing
➢ On molecular level curing leads to development of crosslinks between polymer
molecules.
➢ On a macroscale, during curing, heating is done and debulking is done.
Debulking is important to reduce the void content. A reasonable goal is to have
void content of 0.5% or less.

➢ Autoclave curing: These are pressure vessels that allow simultaneous

imposition of pressure by vacuum and heat. Vacuum is directly lead to the part.
However, autoclaves have high capitalization cost.
➢ Insert gas is also filled in autoclave to avoid any tendency of oxidation.
➢ Using autoclave, assembles may also be bonded together while they are cured.
Use of pressure ensure intimate contact so that bonding and curing occur
properly, known as co-curing.

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 Open Mold Manufacturing Processes
➢ Autoclave curing:

Fig: Autoclave
(http://www.boeingimages.com/Docs/BOE/Media/TR3_WATERM
ARKED/2/b/b/a/BI216312.jpg)

176