Chapter 5.

Introduction to Polymer Composite Processing

Hatsuo Ishida
NSF Center for Molecular and Microstructure of Composites (CMMC)
Department of Mascromolecular Science
Case Western Reserve University
Cleveland, Ohio 44106-1712

51. Introduction

5.2. Advantages of Composite Materials

5.3. Brief Overview of Major Composite Processing Methods

5.3.1.Hand lay-up Molding

5.3.2.Spray-up Molding
5.3.3.Compression Molding, Transfer Molding, Resin Transfer Molding
5.3.4.Injection Molding, Plunger-type Injection Molding
5.3.5.Reaction Injection Molding
5.3.6.Pultrusion
5.3.7.Filament Winding

5.4. Classifications and Definitions of Composite Materials

5.5. Surface Treatment of Reinforcement Materials

5.5.1.Cost Factor
5.5.2.Chemistry of Surface Treatment and Interfacial Structure
A. Glass Fibers and Inorganic Fillers
B. Carbon Fibers
C. High Modulus Organic Fibers

5.6. Selection of Materials

5.7. Selection of Processing Methods

5.7.1.Aspect Ratio
5.7.2.Shape of the Final Product
5.7.3.Time Necessary to Form Hard Solid

5.8. References

1
Chapter 5. Introduction to Polymer and Composite Processing
5.1. Introduction

Polymers are generally produced as powders, pellets, and liquids. In order to produce
polymeric products with desired shapes, thermoplastics must be melted and cool to a final
product shape whereas thermosetts must undergo further polymerization to complete
crosslinking reactions to finally solidify into the designed shape. These operations are called
processing. Many factors influence the processing operations. Those include viscosity,
orientation of heterogeneous phases, rate of reactions, and volatile formation. Among these
factors, the viscosity consideration is by far the most dominant factors in processing.
Viscosity is strongly influenced by temperature, share rate, molecular weight and its
distribution, molecular structure of the polymeric chains and heterogeneity of materials. Thus,
the study of flow behavior of polymeric materials, which is called rheology, is very important
in understanding the proper conditions for processing.

A composite is a heterogeneous substance consisting of two or more materials which

does not lose the characteristics of each component. This combination of materials brings
about new desirable properties. Naturally occurring composites include tendon, bone,
bamboo, rock, and many other biological and geological materials. For composite engineering
applications, we restrict ourselves to synthetic polymer matrices which are used with naturally
occurring mineral fillers such as wollastonite, silica, mica, and calcium carbonate, and synthetic
fibers like glass fibers and carbon fibers.

In the subject of composite processing, we will learn how to make the best use of these
available materials through the understanding of chemical interaction of ingredients, structural
changes during processing, suitable processing methods for desired product shapes and the
resultant consequence on the mechanical and physical properties. Therefore, we will deal with
interdisciplinary subjects including rheology, chemistry, mechanics, machinery, and
sometimes, economy.

5.2. Advantages of Composite Materials

Composites have many engineering advantages over synthetic polymers and copolymers.
Some of these advantages are:

i. Reinforcement of the resin resulting in increased tensile strength, flexural strength,

compression strength, impact strength, rigidity and combination of these properties.

ii. Increased size stability.

iii. Improved fire retardancy.

iv. Corrosion protection.

v. Improved electrical properties; reduction of dielectric constant.

vi. Coloring.

v. Improved processibility; controlled viscosities, good mixing, controlled orientation of

fibers.

2
One of the most important properties composite materials offer is the strength per density or
modulus per density termed as specific strength and specific modulus, respectively. For
transportation applications including aerospace applications, the weight of the vehicle is a
critical importance for energy saving and payload increase. Those materials used for
polymer-matrix composites have usually much less density than metallic materials, thus
specific properties often far exceeds that of matellic parts. Figure 1.1 illustrates the specific
strength and specific modulus of typical materials.
300
Specific tensile modulus (GPa/g/cm3 )

Carbon (P120)
200

Carbon (T1000)
Boron
100 Carbon (T300)
Alumina
SiC
Aramid (Kevlar 49)
Aluminum
S-glass
Steel E-glass
0
0 1 2 3
Specific tensile strength (GPa/g/cm 3 )

Figure 1.1. Specific tensile modulus versus specific tensile strength of various materials.
Properties are those of fibers.

5.3. Various Processing Methods

In many cases, polymer composite processing utilizes the same technique as polymer pro-
cessing which include injection molding, compression molding and extrusion. There are other
techniques which are unique only to polymer composite processing. These include filament
winding, pultrusion, and hand lay-up. In spite of the fact that some techniques are used
commonly with polymer processing, the operational conditions can be very different; thus, it is
important not to directly transfer knowledge without careful consideration. In this section, a
brief explanation of various processing methods will be given.

5.3.1.Hand Lay-up Molding

Hand lay-up molding is the method of laying down fabrics made of reinforcement and
painting with the matrix resin layer by layer until the desired thickness is obtained. This is the
most time and labor consuming composite processing method, but majority of aerospace
composite products are made by this method in combination with the autoclave method. Due
to the hand assembry involved in the lay-up procedure, one can align long fibers with
controlled orientational quality. Another advantage of this method is the ability to

3
accommodate irregular-shaped products. Such advantages are utilized in low performance
composites including fiber-glass boat and bath tub manufacturing.

Brush
Reinforcement

Mold

Figure 1.2. Schematic diagram of hand lay-up operation.

5.3.2.Spray-up Molding

Spray-up booth

Spray-up gun

Resin Catalyst
Glass
Mold roving

Figure 1.3. Schematic diagram showing spray-up operation

Spray-up molding is much less labor intensive than the hand lay-up method by utilizing a
spray gun and a fiber cutter. However, only short fiber reinforced composites can be made. A

4
continuous fiber is fed into the cutter and chopped. The chopped fiber is sprayed upon a
mold with the stream of resin mist and catalyst delivered through separate nozzles. The
sprayed mixture of fiber and resin soon cures on the mold at room temperature and the
product is produced. Because of the spraying operation, large and complex-shaped objects
can be easily made.

5.3.3.Compression Molding, Transfer Molding and Resin Transfer Molding

Compression molding uses a press to compress either a dough of resin and fiber mixture,
or the layers placed by a hand lay-up method or mechanical means, typically at an elevated
cure temperature. With the compressive force, the void content is lower than the ordinary
atmospheric pressure processing method.

Matched metal die

Composite material

Platen

Hydraulic press

Figure 1.4. Schematic diagram of a compression molding press

A matched die mold allows shaping of the composite precursor into reproducible shapes.
Although a compression molding machine is used, it is still a labor intensive method as the
dough or layed-up materials must be weighed and hand-fed into the mold.

Transfer molding is the improved version of compression molding from the material
metering point of view as the fiber/resin mixture is transfered from the reservoir into the mold
cavity by the press. However, a long-fiber reinforced composite cannot be made. This
method is nearly identical to a plunger-type injection molding operation based on the material
flow. The term "transfer molding" is used for a compression press operation while plunger-
type injection molding is obviously carried out in an injection molding machine.

Resin transfer molding is the same as the ordinary transfer molding except that only the
resin is transfer molded into the mold cavity where fabrics are placed beforehand. Preforms
of glass fibers and other reinforcements can be made with short fibers and sometimes con-
tinuous fibers. Preforms must be made to withstand the pressure of resin injection in order to
avoid compression of the fibers during mold filling which would lead to inhomogeneous fiber
distributions in the final part. Curing proceeds typifcally after filling at an elevated
temperature.

5
5.3.4.Injection Molding

Injection molding is probably the most extensively used method for processing short-fiber
reinforced thermoplastics. The fiber/resin mixture, whether it is preblended or fed as a
physical mixture, is fed into the hopper and transfered into the heated barrel. The material
softens by the heat transfer from the barrel wall. At the same time, the screw rotates to apply
high-shear process to further heat the material and fill the barrel. The molten material is
collected in front of the screw by the rotation of the screw, and then injected with a high
pressure into the mold cavity through the runner and the gate. The mold is cooled below the
solidification temperature of the resin in case of thermoplastics composites. The level of
automation of this method is the highest among many processing methods. Due to the
intensive mixing with high-shear and passage through a narrow gate, extensive fiber damage
occurs, therefore, injection molding for composite materials is suitable only with short fiber
reinforced or particulate-filled polymers.

Hopper

Mold Composite Material

Screw

Barrel

Figure 1.5. Schematic diagram of an injection molding machine

There is a critical length of fibers below which the fiber length does not degrade. The critical
length is determined by the rheological properties of the composite mold, fiber properties and
instrument factors. Less fiber damage occurs when a plunger-type injection molding machine
is used rather than a screw-type injection molding machine. Because the plunger-type
injection molding machine does not achieve a high degree of mixing in the machine, the raw
materials must be thoroughly mixed prior to feeding.

5.3.5.Reaction Injection Molding

Reaction injection molding (RIM) is one of the newest processing methods. Instead of
using already polymerized materials as matrices, highly reactive monomeric or oligomeric in-
gredients are placed in two tanks which are then quickly mixed by impingement, and injected
into the mold cavity. As soon as the two materials are mixed, chemical reaction begins to form
a polymeric matrix, which completes typically within 5-30 seconds. Thus, the major portion
of the RIM machine is a high pressure pump and a metering system. Again, with high in-
tensive shear, only short fibers and fillers can be used as reinforcements. However, RIM
utilizes low viscosity chemicals and this allows the preplacement of continuous fiber-woven
fabrics in the mold in the same manner as resin transfer molding. Distinction is made
between these two methods based on the preparation of the resin precursor. When the resin
formulation is already made, the method is called resin transfer molding while if the resin is
prepared in-situ by an impingement or static mixer, the method is termed RIM.

6
 Chemical A Chemical B

Impingement
mixing head
Mold

Figure 1.6. Schematic diagram of a reaction injection molding machine.

5.3.6.Pultrusion

Pultrusion is used only for polymer composite processing. A bundle of fiber rovings is
passed through a wet resin bath, squeezed into a desired shape, passed through a heated die,
and cured into a final composite. The solidified composite, typically reinforced unidirec-
tionally with continuous fibers or sometimes bidirectionally, is pulled by a puller to continu-
ously feed the uncured portion of the wet fibers into the hot die, thus the name, "pultrusion".
This is one of very few continuous processing methods for continuous fiber reinforced com-
posites. Only constant cross-sectional products can be made; the shape of the cross-section
does not necessarily have to be the same, however.

Roving

Eyelet
Heated die Puller Cut-off saw

Resin bath

Figure 1.7. Schematic diagram of a pultrusion machine.

5.3.7.Filament Winding

Filament winding is also a unique processing method for polymer composite processing
with a continuous reinforcing fiber. Resin-wet rovings are wound with a certain pattern

7
around a mandrel. The wound mandrel is then placed into an oven and cured to a solid com-
posite. Due to the controlled tension, squeezing action and controlled winding pattern, the
fiber content can be very high to produce composites with one of the highest mechanical
properties. The winding process is time consuming and is the cause of low productivity.
However, due to its very high mechanical properties with automated operation, it is actively
evaluated by aerospace industries.

Motor Mandrel

Roving

Eyelet
Resin bath

Figure 1.8. Schematic diagram of a filament winding machine.

5.4. Classifications and Definitions of Composite Materials

The term reinforced polymer is often used for composites with fibrous materials while
filled polymer is the description used for polymers with particulate fillers. Examples of the
reinforced polymers are fiber-glass reinforced polyesters and carbon fiber reinforced poly-
imides. A vast number of filled polymers are used today, including calcium carbonate filled
poly(vinyl chloride), clay-filled polyethylene and carbon black-filled polybutadiene.

The role of fibers is relatively obvious and simple; reinforcing the strength of weak poly-
mers. The properties tend to be anisotropic. However, fillers have complex roles and many
of them are interactive. Some are added to homogeneously increase modulus and strength,
and others are for dimensional stability, viscosity control, increased hardness, pigmentation,
and even for cost reduction. Fillers do not necessarily lead to overall improvement of prop-
erties, and thus the role of added fillers must be carefully examined prior to use. For example,
calcium carbonate is often added to unsaturated polyester resin for cost reduction, rheology
control, and dimensional stability, but in sacrifice of the strength.

Reinforced composites can be further classified into high-performance composites like fil-
ament wound plastics with glass fibers, or carbon fiber reinforced high temperature polymers
made by hand lay-up method; and low-performance composites such as injection molded
bulk molding compound (BMC) or composites made by the spray-up method. Extremity of
the performance, whether it be the strength or use temperature, is the key factor for high
performance composite. In general, high-performance composites tend to use a high fiber
content as the mechanical and physical properties of reinforcing fibers are generally much
greater than the matrix resin.

Filler is a term used for materials other than continuous fibers and, in general, implies that
the reinforcement effect is rather low. Fillers may be particulate or fibrous but the size is
usually less than a millimeter. For the reinforcement effect of fillers, the aspect ratio, i.e. the

8
length-to-diameter ratio, is a critical importance. Extender is the word used for a filler which
has almost no reinforcement effect and is used simply to reduce the amount of a plastic re-
quired.

A hierarchy exists in the terminology of reinforcing fibers. The thinnest component is a

filament whose diameter is typically between several micrometers to several tens micrometers.
A few hundred to few thousand filaments are bundled together, which is assisted by a film
former, to form a strand. Finally, many tens of strands make up a roving.

When good mechanical properties are maintained in the temperature range around 150 oC,
the polymer is called an engineering plastic. Nylon, polycarbonate, poly(ethylene tereph-
thalate) and epoxy all belong to this category. Sometimes the term super engineering plastic
is used to indicate polymers with further elevated use-temperatures above 200 oC. These
include polyimide, poly(aryl ether ether ketone) and poly(phenylene sulfide).

5.5. Surface Treatment of Reinforcing Materials

5.5.1. Cost Factor

Surface treatment is done to improve the adhesion of fillers and fibers to matrix resin by
modifying the surface of the solid. Often, chemical structure and sometimes topology of the
surface change upon the treatment. Those techniques used include chemical, plasma, corona
discharge and flame treatments. When cost reduction is the major goal of a change in
fabrication, surface treatment of a filler is not a viable option. This point may be clarified by
the following example. As of 1981, a certain polyethylene was priced $ 0.30/lb while typical
untreated fillers were $ 0.05/lb. The cost of mixing the filler into the resin was about $
0.07/lb. Hence, the higher the filler content the lower the cost of the composite. However,
once the filler was surface treated, the unit cost went up to about $ 0.20 - 0.25/lb. When
combined with the mixing cost, there is essentially no economic advantage. The economic
factor is often ignored in the academic institution. However, it is one of the most essential
motivations for manufacturing composites in today's industries and without understanding
this point, a true grasp of composite processing cannot be achieved.

5.5.2. Chemistry of Surface Treatment and Interfacial Structure

A. Glass Fibers and Inorganic Fillers

Inorganic materials like glass fibers and many fillers have poor compatibility at the
fiber/matrix or filler/matrix interface. In order to improve adhesion at the interface, com-
pounds with dual property, i.e. molecules having chemical functionalities similar to the fiber
and the matrix resin, are used. Due to the coupling action of the fiber and the resin by the
compatibilizing compound, this type of compound is often referred to as a coupling agent,
such as a silane coupling agent. In addition to the adhesion promotion, coupling agents aid in
protecting fiber surfaces and prevent inhibition of polymerization by the solid surfaces. A
small amount of a coupling agent can often dramatically improve the mechanical and physical
properties of composites. A typical loading level of coupling agent ranges from a small
fraction of a percent to a few percent based on the weight of the fiber or filler. Other
treatments such as plasma and corona discharge changes the chemical structure of the surface
layers of fillers and fibers in an attempt to obtain similar compatibilization and adhesion
promotion effects through chemical reactions.

The coupling agent may be added to the filler as a neat liquid, an organic solution, or an
aqueous solution. If a coupling agent is mixed into the filler/resin mixture, the treatment is

9
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either termed as the dry blending method or the slurry treatment method. The dry blending
method utilizes typically a small amount of a concentrated silane/organic solvent solution
which is sprayed onto the tumbling fillers. Since the amount of the solution is small, and is
an organic solution, the tumbling filler has an appearance of dry powder, thus the name dry
blending method. The slurry method uses a large amount of a dilute silane solution, typically
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RSi (OR') 3 RSi (OH) 3 + 3 R'OH
Hydrolysis
Organosilanetriol

Adsorption

R
R R
HO Si OH

O - O - Si - O - Si - O -
H H Condensation
O Polymerization O O

Si Si Si
currentpoint 192837465
Figure 1.9. Chemical processes during surface treatment of silaceous materials by a
silane coupling agent.

Regardless of the treatment methods, the silane loses its alkoxy groups and chemically re-
acts with the hydroxyl groups of the mineral surfaces. The reaction proceeds as follows.

i. Dry Blending

The unreacted alkoxy groups will further react with the surface silanols or water on the
filler surface. When the alkoxy groups are hydrolyzed, siloxane bonds between the silane
molecules can be formed. Dry blending may be performed after prehydrolysis of the silane
with a small amount of water added in the organic solvent, which leads to the similar chemical
processes described in Figure 1.9.

10
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currentpoint
R
R
R'O - Si - OR'
H + R'O - Si - OR' + R'OH
O O

Si OR' Si
currentpoint 19283746
Figure 1.10. Chemical reactions possible on a dry filler surface.

ii. Prehydrolysis; Slurry Treatment

This method leads to the chemical reactions described in Figure 1.9. If the surface is flat on
the molecular level of the silane, thick multilayers can be easily formed.

Although dry blending is a preferred method for a powdery filler because of the ease of
drying, the alkoxy group of the coupling agent may not be completely hydrolyzed especially
when the surface coverage is more than a monolayer. This results in small silane oligomers
which are not chemically bound to the surface. This portion of the coupling agent, ph-
ysisorbed silanes, migrates into the matrix resin during processing and modifies the structure
of the matrix near the filler surface creating a region termed "matrix interphase" whose prop-
erties differ from the matrix bulk. The importance of this portion of the coupling agent has
only recently been recognized and its roles are not fully understood. The addition of a small
amount of water in the treating organic solution prior to the mixing helps the silane to hy-
drolyze more thoroughly.

A fine particulate tends to form a cake which can be later crushed to reobtain a fine powder
form. Therefore, the slurry treatment is usually avoided for this type of materials. Glass
beads, coarse fillers or fibrous fillers are exceptions since they do not form hard cakes upon
drying. Whenever permitted, wet treatment is preferred from the view point of environmental
consideration. The concentration of aqueous treating solutions generally range from 0.05 to 2
% by weight. A further advantage of the wet treatment is that a more uniform surface
treatment is achieved due to the abundance of the treating solution that can wet the entire
surface of the filler or fibers. Also, the silane is hydrolyzed to an organosilanetriol. After the
adsorption, the unstable silanetriols condense into the siloxane linkages forming large, cross-
linked networks. Thus, the structure of the adsorbed silane is relatively insensitive to moisture
compared to the dry blended silane.

After the surface treatment, the reinforcements are usually dried at room temperature
overnight followed by a heat treatment at an elevated temperature. A heat treatment at 110 oC
for 5 to 30 min is typical. Too much curing of the coupling agent can be harmful and may
lead to a loss of the organofunctionality. Industrially, the drying may be done immediately
after the surface treatment by passing through an oven.

In addition to the coupling agent, there are a number of ingredients in the so-called sizing
agent including a lubricant, a film former, and an antioxidant. Detailed compositions are not
disclosed other than in patent literatures.

Figure 1.11 shows how the silane treatment can improve the dry and wet strength of fiber-
glass reinforced unsaturated polyester compared with the untreated glass fibers. The figure
also shows the chronological progress of various coupling agents for polyester applications.

11
Another useful function of the coupling agent is to increase bond permanence under hy-
drothermal degradation, and healing of the surface flaws of the fiber.
Dry Strength
Wet strength

600
Flexural Strength (MPa)

400

200

0
A B C D E F
Category

Figure 1.11. Progress in fiber-glass reinforced polyesters (from ref. 1).

A: no surface treatment
B: BJY treatment
C: chrome complex
D: vinyl-functional silane
E: methacrylate-functional silane
F: vinylbenzyl cationic silane
Wet strength was measured after 2 h boil in water.

Understanding the surface chemistry of reinforcements is very important when the func-
tion of the coupling agent is considered. A typical thickness range of the silane layers on a
glass fiber surface is 1 to 10 nm as compared to the typical diameter of the glass fiber, 10,000
nm ( 10 µm). In spite of its very thin layer, the structure of the silane layers on glass and
metal surfaces has been under extensive investigation. Many monograms and review articles
on the subject are available (2-7). Some of the major findings are listed below.

i. Silanes adsorb onto a smooth surface such as a glass fiber as multilayers while a rough
surface shows essentially a monolayer adsorption. This is due to the topological rea-
sons influencing the orientation of the silane molecules (8).

ii. At the glass/silane interface as well as the silane/matrix interface, chemical bonds can be
formed (9-11).

iii. Within the silane multilayers, the molecules tend to form organized layers and the de-
gree of organization depends on the flexibility of the organofunctionality (8, 12).

12
 iv. Silanes tend to adsorb head-to-head configuration because silanetriols form strong hy-
drogen bonds (12).

v. Silanes preferentially adsorb onto the surface of fillers and change the surface energet-
ics. As a result, the viscosity of the filler/resin system decreases dramatically by im-
proved dispersion of the fillers (13, 14). Also, the catalytic effect of the fillers are in-
hibited by a thin film of silane (15), thus the inorganic fillers act as organic fillers.

vi. Silane interphase can intermix with resin matrix to form interpenetrating networks (16,
17).

B. Carbon Fibers

The surface treatment of carbon fibers is done quite differently from the aforementioned
silane treatment of glass fibers because of the dissimilarity in surface functionalities. Carbon
fibers are covered with the basal plane of graphite crystals, crystal edges of the graphite, and
nongraphitic carbon. At the edge of the crystal, non-aromatic structures can exist including
hydroxyl, carbonyl, and carboxylic acid groups (18-20). Typical example of the surface
composition after a mild surface oxidation is 73% hydroxyl groups, 17% carboxylic acid
groups, and 10% hydroxyl groups, while after an extensive oxidation it is 24% hydroxyl
groups, 54% carboxylic acid groups and 22% carbonyl groups (21).

Surface treatment of carbon fibers can be divided into two categories. Usually, the word
surface treatment refers to the oxidative treatments on the carbon fiber surface. Those treat-
ments include oxidation in a concentrated nitric acid, an electrochemical treatment, and a
plasma treatment (22). The structural modification is usually confined within the layers very
near the surface. The oxidative treatment increases the surface polarity and improves the ad-
hesion with polymeric matrices. However, due to the increased polarity, the hydrothermal
stability of carbon fiber reinforced composites is somewhat compromised.

Another kind of surface treatment is referred to as a surface finish or a primer where typi-
cally a polymer or an oligomeric precursor of a polymer is coated on the fiber surface. This
type of surface treatment is used for a protective coating as well as an interphase modifier
(23). Although there is no clear definition of terminology, the word finish is used for a very
thin surface coating while the word primer is used for a much thicker coating. In this context,
the coating usually applied on carbon fibers is a primer. The thickness of the primer is
usually in the range from 100 to 500 nm. Often used materials include epoxies and
polyimides.

C. High Modulus Organic Fibers

Little is known on the surface treatment of high modulus organic fibers such as poly(para
terephthalamide) (PPT) or gel processed polyethylene fibers. The typical method used is
plasma treatment or corona discharge treatments of the fiber surfaces.

Surface amination of PPT fibers has been studied (24): Improved mechanical strength of a
PPT reinforced epoxy composite has been obtained by treating the PPT fibers in ammonium
plasma at 50 W for 60 sec. This treatment introduced an amine functionality onto the
aromatic portion of the PPT molecules. Introduction of an epoxy functionality has also been
attempted (25, 26). Hydrolysis of the PPT surface was used to introduce the functional group
for epoxidation but the degree of the hydrolysis was found to strongly influence the
mechanical strength of the fibers (25).

13
 Very recently, the surface treatment studies of ultra-high modulus polyethylene fibers has
been reported. Chemical treatment by chromic acid (27, 28) or fuming nitric acid(29), corona
discharge(30) and plasma treatment(31) are some of the techniques used. In many cases, the
effectiveness of the surface treatment was reported to decrease as a function of time, probably
due to the molecular mobility of the surface species.

5.6. Selection of Materials

Selection of materials is based on the preference in properties that need to be achieved. Let
us suppose that one desires a composite with very high tensile strength. The first choice is
very high strength fibers such as carbon fibers, S-glass fibers, poly(para terephthalamide) or
ultra-high modulus polyethylene fibers. Then, a resin is chosen so that the compatibility and
processibility is appropriate with the fiber chosen. If further properties are desired, for
example, hydrothermal stability, then more severe selection will be imposed on the resin, the
reinforcing fiber, and the surface treatment method. Since composites are heterogeneous, the
selection of materials only is not sufficient. One must also consider the form or topology of
the reinforcement. Would it be fibrous or powdery? Or, would it be woven cloth or simple
roving ? Once the proper materials and their forms are selected and the compatibility is ad-
justed by a surface treatment, the materials are subjected to processing.

5.7. Selection of Processing Methods

No processing machine or method is universal and, therefore, a proper selection of a

processing method must be made for each reinforcement/resin system. When one selects a
processing method, the following factors play a major role.

A. Aspect Ratio of the Reinforcing Material

This is the length/diameter ratio of the reinforcing material. Usually, a reinforcing material
with a high aspect ratio is difficult to injection mold or extrude, thus a particulate-filled, milled
glass fiber-filled or chopped glass strand-filled resin is used for this type of process.
Continuous fibers are used for filament winding and pultrusion. Sometimes, preforms made
of continuous fibers are used with reaction injection molding and resin transfer molding.
Woven materials are suitable for compression molding, hand lay-up processing, and pultru-
sion.

B. Shape of the Final Product

Screw injection molding can make complicated shapes while compression molded parts are
relatively simple. Intermediate complexity can be achieved using transfer molding or plunger-
type injection molding. Filament winding can produce relatively complex shape with dull
curvatures while pultrusion produce complex shape only in the cross-sectional direction.
Among the pultrusion method, vertical pultrusion is suitable for more complex shapes than
horizontal pultrusion. However, the majority of pultrusion is now done using horizontal
pultrusion. Hand lay-up and spray-up methods are time and labor consuming but can be
used to produce large, complicated shapes.

C. The Time Necessary to Form Hard Solid

This concept applies mainly for thermosetting resins since most of them are either liquid or
soft solid. Thermosetting resins require chemical reactions during processing in order to
form usable, solidified composites while thermoplastics need only to experience a solid-
molten liquid-solid cycle without chemical reaction. Using thermal polymerization, chemical
reaction is relatively slow and requires somewhat a long hold-up time of the machine per part.

14
Filament winding is usually used for high performance composites and the time consideration
is more relaxed. Pultrusion, on the other hand, is a continuously flowing system and curing
time is very short on the order of a few minutes. Compression and injection molding
generally require 2 to 20 min for thermosetting matrices while the autoclave method utilizes
longer times. Stamping is a form of compression molding but it utilizes a preheated resin and
the time necessary to complete a part is much shorter than regular compression molding.

There are other factors to be considered such as the viscosity or the reinforcing mate-
rial/resin mixture, the effect of shear rate on the interfacial bonding, degradation of resin and
reinforcing material by the shear stress and the heat generated by both the shear, etc.
However, each method is unique in its own right and different processing methods are seldom
interchanged for the above reasons.

5.8. References

1. E.P. Plueddemann in "Molecular Characterization of Composite Interfaces", H. Ishida

and G. Kumar, Eds., Plenum, New York (1985) p.13.

2. "Interfaces in Polymer Matrix Composites", E.P. Plueddemann, Ed., Academic, New

York (1976).

3. "Silylated Surfaces", D.E. Leyden and W. Collins, Gordon and Breach, New York
(1980).

4. E.P. Plueddemann, "Silane Coupling Agents", Plenum, New York (1982).

5. "Molecular Characterization of Composite Interfaces", H. Ishida and G. Kumar, Eds.,

Plenum, New York (1985).

6. H. Ishida and J.L. Koenig, Polym. Eng. Sci., 18, 128 (1878).

7. H. Ishida, Polym. Composites, 5, 101 (1984).

8. H. Ishida and J.L. Koenig, J. Polym. Sci. -Phys., 17, 1807 (1979).

9. H. Ishida and J.L. Koenig, J. Colloid Interface Sci., 64, 555 (1978).

10. S. Naviroj, J.L. Koenig and H. Ishida in "Progress in Science and Engineering of
Composites", T. Hayashi, K. Kawata and S. Umekawa, Eds., ICCM-IV, Tokyo (1982)
p.227.

11. J.D. Miller and H. Ishida in "Silanes, Surfaces, and Interfaces," D.E. Leyden, Ed.,
Gordon and Breach, New York (1986) p.525.

12. H. Ishida, J.L. Koenig and K.H. Gardner, J. Chem. Phys., 77, 5748 (1982).

13. C.D. Han, C. Sanford and H.J. Yoo, Polym. Eng. Sci., 18, 849 (1978).

14. J.D. Miller, H. Ishida and F.H.J. Maurer, (submitted).

15. H. Ishida and J.L. Koenig, J. Polym. Sci. -Phys., 17, 615 (1979).

16. E.P. Plueddemann,"Silane Coupling Agents", Plenum, New York (1982) p.134.

15
17. H. Ishida and J.L. Koenig, J. Polym. Sci. -Phys., 18, 1931 (1980).

18. J.V. Hallum and H.V. Drushel, J. Phys. Chem., 62, 110 (1958).

19. H.P. Boehm, Angew. Chem., 6, 533 (1966).

20. J.B. Donnet, Carbon, 6, 161 (1968).

21. A. Ishitani in "Molecular Characterization of Composite Interfaces," H. Ishida and G.

Kumar, Eds., Plenum, New YOrk (1985) p.321.

22. J. Delmonte,"Technology of Carbon and Graphite Fiber Composites", Van Nostrand

Reinhold, New York (1981).

23. L.T. Drzal, M.J. Rich and M.F. Koenig, Proc. 38th Ann. Tech. Conf., Reinforced
Plastics/Composites Inst., SPI, Section 4-F (1983).

24. R.E. Allred, E.W. Merrill and D.K. Roylance in "Molecular Characterization of
Composite Interfaces," H. Ishida and G. Kumar, Eds., Plenum, New York (1985) p.
333.

25. T.S. Keller, A.S.Hoffman, B.D. Ratner and B.J. McElroy in "Physicochemical Aspects
of Polymer Surfaces," K.L. Mittal, Ed., Plenum, New York (1983) p.861.

26. H. Chatzi, H. Ishida and J.L. Koenig in "Composite Interfaces," H. Ishida and J.L.
Koenig, Eds., Elsevier Science, New York (1986) p. 285.

27. I.M. Ward and N.H. Ladizesky, Pure and Appl. Chem., 57, 1641 (1985).

28. I. Ward and N.H. Ladizesky in "Composite Interfaces," H. Ishida and J.L. Koenig, Ed-
s., Elsevier Science, New York (1986) p.37.

29. A. Taboudoucht and H. Ishida, Polym. Composites (submitted).

30. S.L. Kaplan, P.W. Rose, H.X. Nguyen and H.W. Chang, SAMPE Quaterly, 55 (1988).

31. N.H. Ladizesky and I.M. Ward, J. Mat. Sci., 18, 533 (1983).

16