39

CHAPTER 3

PROPERTIES OF GFRP MATERIALS

3.1 GENERAL

FRP composites are a state-of-the-art construction material, an

alternative to traditional materials such as concrete, steel and wood. Among
many applications of FRP in civil infrastructures, bridge decks have received
much attention because of their light weight, high strength-to-weight ratio,
and corrosion resistance. Other advantages of FRP bridge decks are the
reduction in bridge deck construction time and increase in service life. The
attractiveness of FRP composites as construction materials derives from a set
of advantages gleaned from the tailorability of this material class through the
synergistic combination of fibres in a polymeric resin matrix, wherein the
fibre reinforcements carry load in predesigned directions and the resin acts as
a medium to transfer stresses between adjoining fibres through adhesion and
also provides protection for the fibres. The selection of matrix and
reinforcement for fabrication of any composite product mainly depends on the
properties of matrix and reinforcement.

3.2 FIBRES

Fibres are the principal constituents in a fibre 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. The
effectiveness of fibre reinforcement depends on the type, length, volume
 40

fractions and orientation of fibres in the matrix. Proper selection of the fibre is
influenced by following characteristics.

Density

Tensile and Compressive strength

MOE

Fracture

Fatigue performance

Response to impact loads

Electrical and Thermal properties

Cost

Principal fibres in commercial use for production of civil

engineering applications are

i) Carbon

ii) Aramid

iii) Glass fibres

E-glass fibres have been employed in this study. A brief description

about its composition, advantages, and properties are presented below.

3.3 GLASS FIBRES

The most extensively used class of fibres in composites are those

manufactured from E-glass. E-glass is a low alkali borosilicate glass
originally developed for electrical insulation applications. It was first
produced commercially for composite manufacture in 1940’s, and its use now
approaches 2 MT per year worldwide. Many different countries manufacture
 41

E-glass and its exact composition varies according to the availability and
composition of the local raw materials. It is manufactured as continuous
filaments in bundles, or strands, each containing typically between 200 and
2000 individual filaments of 10-30 µm diameters. These strands may be
incorporated into larger bundles called roving and may be processed into a
wide variety of mats, clothes, and performs and cut into short-fibre formats.
Glass filaments have relatively low stiffness but very high tensile strength
(~3GPa). In spite of their initial very high strength, glass filaments are
relatively delicate and may become damaged by abrasion and by attack from
moist air. It is therefore always necessary to protect the newly drawn strands
with a coating or size (also referred to as a “finish”). This is usually applied as
a solution or emulsion containing a polymer that coats the fibres and binds the
fibres in the strand together (film former), a lubricant to reduce abrasion
damage and improve handling, additives to control static electric charges on
the filaments, and a coupling agent, usually a silane, that enhances the
adhesion of the filaments to the matrix resin and reduces property loss on
exposure to wet environments.

3.4 REINFORCEMENT FORMAT

The reinforcement fibres are generally available in the form of a

tow, or in a band. In some processing operations (e.g. filament winding),
tows, or rovings, of continuous fibres are converted directly into the
component. Following forms of GFRP are generally available:

CSM (Emulsion)
CSM (Powder)
WR
Spray - up Rovings
SMC Rovings
 42

Assembled Rovings
Direct Roving

Among these forms, the present study deals with CSM (Emulsion)
and WR.

3.4.1 Woven Rovings

Woven clothes and rovings are very widely used in the manufacture
of laminated structures. A simple plain weave WR allows a Vf of up to 0.6 to
be achieved in the laminate. In-plane strengths are much higher than for the
random materials. Stiffness, strength, and drape are also influenced by the
weave pattern. The plain weave leads to a high degree of crimp, which may
reduce stiffness by up to about 15% compared with a similar fraction of
straight fibres. Twill and satin weaves offer better drape, and the satin weaves
in particular have less crimp.

Five and eight-harness satin weaves are widely used in composite

laminates, especially in the lighter weights, which are more appropriate in
many highly stressed designs. The tighter fibre structure in cloths renders
them more difficult to infiltrate and consolidate than the random mats. WR
fabrics are specifically designed to meet most demanding performance,
processing and cost requirements. These fabrics deliver a unique combination
of properties. They offer one of the highest strength-to-weight ratios possible
for reinforced plastics and through careful selection and placement of fabrics,
designers can put the strength exactly where it is needed, making optimum
use of the fibre strength. WR fabrics provide the most economical solution for
raising glass content of laminates and increasing laminate stiffness and impact
resistance without adding thickness, weight or other non-reinforcing
materials. Figure 3.1 shows the typical WR mat.
 43

Figure 3.1 Woven rovings

3.4.2 Chopped Strand Mat (Emulsion)

Chopped strands are produced by cutting continuous strands into

short lengths. The ability of the individual filaments to hold together during or
after the chopping process depends largely on the type and amount of size
applied during the fibre manufacturing operation. Strands of high integrity are
called “hard” and those that separate more readily are called “soft”. Longer
strands are mixed with a resinous binder and spread in a two dimensional
random fashion to form CSMs. Thus a CSM is made up of random yet evenly
distributed strands chopped from continuous “E” Glass fibres into 50mm
length and bonded with “Emulsion binder”. It possesses excellent surface
bonding efficiency. These mats are suitable for hand lay - up mouldings and
provide nearly equal properties in all directions in the plane of the structure.
Figure 3.2 shows a typical CSM.
 44

Figure 3.2 CSM 450 E gsm MAT

3.5 FUNCTIONAL RELATIONSHIP OF POLYMER MATRIX

TO REINFORCING FIBRE

The matrix gives form and protection from the external

environment to the fibres. Chemical, thermal, and electrical performance can
be affected by the choice of matrix resin. But the matrix resin does much
more than this. It maintains the position of the fibres. Under loading, the
matrix resin deforms and distributes the stress to the higher modulus fibre
constituents. The matrix should have an elongation at break greater than that
of the fibre. It should not shrink excessively during curing to avoid placing
internal strains on the reinforcing fibres. If designers wish to have materials
with anisotropic properties, then they will use appropriate fibre orientation
and forms of uni-axial fibre placement. Deviations from this practice may be
required to accommodate variable cross section and can be made only within
narrow limits without resorting to the use of shorter axis fibres or by
alternative fibre re-alignment. Both of these design approaches inevitably
reduce the load-carrying capability of the molded part and will probably also
adversely affect its cost effectiveness. On the other hand, in the case of a
complex part, it may be necessary to resort to shorter fibres to reinforce the
molding effectively in three dimensions. In this way, quasi-isotropic
 45

properties can be achieved in the composite. Fibre orientation also influences

anisotropic behaviour.

3.6 MATRIX RESINS

There are mainly three different types of matrix materials- organic

polymers, ceramics and metals. Thermosetting polymer resins are the type of
matrix material commonly used for civil engineering applications. Polymers
are chain like molecules built up from a series of monomers. The molecular
size of the polymer helps to determine its mechanical properties. Polymeric
matrices have lowest density, hence, produce lightest composite materials. A
major consideration in the selection of matrices is the processing requirement
of the selected material. The most common thermosetting resins used in civil
engineering applications are polyesters, epoxies, and to a lesser degree,
phenolics. ISO and ER have been used in the study. Polyester resins are
relatively inexpensive, and provide adequate resistance to a variety of
environmental factors and chemicals. Epoxies are more expensive but also
have better properties than polyesters. Some of the advantages of epoxies over
polyesters are higher strength, slightly higher modulus, low shrinkage, good
resistance to chemicals, and good adhesion to most fibres.

The matrix resin must have significant levels of fibres within it at

all important load-bearing locations. In the absence of sufficient fibre
reinforcement, the resin matrix may shrink excessively, can crack, or may not
carry the load imposed upon it. Fillers, specifically those with a high aspect
ratio, can be added to the polymer matrix resin to obtain some measure of
reinforcement. However, it is difficult to selectively place fillers. Therefore,
use of fillers can reduce the volume fraction available for the load-bearing
fibres. Another controlling factor is the matrix polymer viscosity.
 46

3.6.1 Epoxy Resins

ERs are used in advanced applications including aircraft, aerospace,

and defense, as well as many of the first- generation composite reinforcing
concrete products currently available in the market. ERs are available in a
range of viscosities, and will work with a number of curing agents or
hardeners. The nature of epoxy allows it to be manipulated into a partially-
cured or advanced cure state commonly known as a “prepreg”. If the prepreg
also contains the reinforcing fibres the resulting tacky lamina can be
positioned on a mold (or wound if it is in the form of a tape) at room
temperature. ERs are more expensive than commercial polyesters and vinyl
esters.

Although some epoxies harden at temperatures as low as 80 oF

(30oC), all epoxies require some degree of heated post-cure to achieve
satisfactory high temperature performance. Large parts fabricated with ER
exhibit good fidelity to the mold shape and dimensions of the molded part.
ERs can be formulated to achieve very high mechanical properties. However,
certain hardeners (particularly amines), as well as the ERs themselves, can be
skin sensitizing, so appropriate personal protective procedures must always be
followed. Some epoxies are also more sensitive to moisture and alkali. This
behaviour must be taken into account in determining long term durability and
suitability for any given application. Curing time and increased temperature
required to complete cross-linking (polymerisation) depend on the type and
amount of hardener used. Some hardeners will work at room temperature.
However, most hardeners require elevated temperatures. Additives called
accelerators are sometimes added to the liquid ER to speed up reactions and
decrease curing cycle times. The heat resistance of an epoxy is improved if it
contains more aromatic rings in its basic molecular chain. If the curing
reaction of ERs is slowed by external means, (i.e., by lowering the reaction
temperature) before all the molecules are cross-linked, the resin would be in
 47

what is called a B-staged form. In this form, the resin has formed cross-links
at widely spaced positions in the reactive mass, but is essentially uncured.
Hardness, tackiness, and the solvent reactivity of these B-staged resins depend
on the degree of curing.

3.6.1.1 Hardeners for Epoxy

ERs can be cured at different temperatures ranging from room

temperature to elevated temperatures as high as 347oF (175oC). Post curing is
usually done. Epoxy polymer matrix resins are approximately twice as
expensive as polyester matrix materials. Compared to polyester resins, ERs
provide the following general performance characteristics:

A range of mechanical and physical properties can be obtained

due to the diversity of input materials
No volatile monomers are emitted during curing and processing
Low shrinkage during cure
Excellent resistance to chemicals and solvents
Good adhesion to a number of fillers, fibres, and sub-strates

3.6.2 Isophthalic Polyesters

Isophthalic polyesters, which use Isophthalic acid as a saturated

acid are premium resins. ISO is a medium viscosity, Unsaturated Polyester
Resin based on Isophthalic acid. It is specially designed for corrosion resistant
applications. It exhibits excellent mechanical properties along with good
chemical resistance. They cost about 20% more than orthos based on current
pricing but have improved corrosion resistance, superior mechanical
properties, and higher heat distortion temperatures. ISO rapidly wets the
surface of glass reinforcements resulting in fast curing and a tack free surface.
It is recommended for moderate chemical resistance applications. At
 48

moderate temperatures, the resin has good resistance to water, acids (dilute to
medium concentrations), weak bases and good resistance to petroleum
solvents. The FRP components manufactured using it exhibit excellent
hydrolytic stability and resistance to outdoor weather. There is no anhydrate
form of Isophthalic acid since the two acid groups are not on adjacent
carbons.

This requires that the isopolysters be made in two steps, by a so-

called double cook process, because the Isophthalic acid does not react as
quickly as the Maleic anhydride with the glycol. The double cook process has
two advantages that offset the higher lost: the oligomers are more consistent
batch-to-batch with the more uniform distribution of unsaturated
functionality, and they build higher molecular weight, are generally thought to
be responsible for the superior thermal, mechanical and chemical resistance of
isophthalic polyesters. The level of instaurations in the oligomer determines
the cross-link density of the cured resin, which in turn greatly affects the
properties of the resin. Decreasing the cross link density by increasing the
isophthalic acid: maleic anhydride ratio (IPA: MA) results in a reduction in
heat distortion temperature and Young’s modulus and an increase in failure
strain (elongation and break). Higher resin elongation enhances performance
in some application of polyester composites. A notable example is large
diameter pipe liner, which must resist cracking during installation to be
effective corrosion barriers. Also higher strain to failure resins are sometimes
used in structural application. Good co-relation exists between resin tensile
elongation and laminate mechanical properties in glass fibre reinforced
polyesters.

3.7 GEL COAT

Much is required of gel coats, and as a result, their formulation is

complicated. The basic problem is that a gel coat must cure in thin layers.
 49

This is made difficult by the low resin mass and high mould mass, both of
which minimize exothermic temperature, a situation aggravated by the effect
of air inhibition of the free radical cure mechanism in gel coat. In addition gel
coats must be durable, i.e. must be resistant to cracking and crazing, must not
blister, and must retain colour and gloss after long exposure to UV light
clearly. All these criteria cannot be met indefinitely but it should be realized
that gel coats are remarkable for how well they perform.

3.8 PARTICULATE FILLERS

Particulate fillers are not reinforcements in the sense that stiffness

and strength of the resin are greatly enhanced, but they are widely used in
composite formulations. Typical fillers are the various forms of chalk
(calcium carbonate), silica aerogels, glass ballotini, glass and polymer micro
balloons, and carbon black. Their main function is to modify the matrix resin
and especially to improve the surface finish. Since resins are very expensive,
it will not be cost effective to fill up the voids in a composite matrix purely
with resins. Fillers are added to the resin matrix for controlling material cost
and improving its mechanical and chemical properties. Fillers are added to a
polymer matrix for one or more of the following reasons:

Reduce cost (Since most filler are much less expensive than the
matrix resin)

Increase modulus

Reduce mould shrinkage

Control viscosity

Produce smoother surface

Particulate fillers are not reinforcements in the sense that stiffness

and strength of the resin are greatly enhanced, but they are widely used in
 50

composite formulations. The three major types of fillers used in the composite
industry are the calcium carbonate (Chalk), kaolin, and alumina trihydrate.
Other common fillers include mica, feldspar, wollastonite, silica, talc, and
glasses. When one or more fillers are added to a properly formulated
composite system, the improved performance includes fire and chemical
resistance, high mechanical strength, and low shrinkage. Other improvements
include toughness as well as high fatigue and creep resistance. Some fillers
cause composites to have lower thermal expansion and exotherm coefficients.
Wollastonite filler improves the composites' toughness for resistance to
impact loading. Aluminum trihydrate improves the fire resistance or
flammability ratings. Some high strength formulations may not contain any
filler because it increases the viscosity of the resin paste. High viscosity resins
may have a problem wetting out completely for composite with heavy fibre
reinforcement.

3.9 CATALYST

There are numerous initiators that can be used to cure polyesters

and when considered in combination with various amounts of promoters and
co-promoters, should be realized that cure behaviour can be adjusted over a
wide range. Resins can be catalyzed to gel in few minutes or few hours at
room temperature or at elevated temperature. Inhibitors are chemicals whose
main function are to increase storage life of resins, and as such are added by
the manufacturer. They apparently work by consuming free radicals, so cure
can only proceed after all the inhibitor is depleted. Methyl Ethyl Ketone
Peroxide (MEKP) 50% solutions in pithalate plasticizer selected as catalyst.

3.10 ACCELERATOR

MEKP and the other initiators cannot cure polyester (or) vinyl ester
resins without promoters at ambient temperature because they decompose into
 51

free radicals too slowly. The function of the promoter usually cobalt
napthenate (CoNaP) is to decompose the initiator rapidly at room
temperature. The promoter is true catalyst that is, it is not consumed in the
curing reactions, and so only a small amount of cobalt salt is needed to
decompose the initiator. It is usually added to the resin as a dioctyl phthalate
solution that is 6% by weight of cobalt. It imparts a slight purple hue to the
resin, which turns to brown when the transition state of the cobalt change
from Co2+ to Co3+ which occurs when the cobalt complex decompose the
initiator.

3.11 CHALK

It is used as filler in many systems, particularly sheet and bulk

moulding compounds. Its function is to replace part of the resin matrix,
reducing thermal and cure shrinkage and thus improving surface finish. These
fillers also reduce the cost as they are cheaper than either the resin or the
(glass fibre) reinforcement.

3.12 CALCULATION OF PROPERTIES OF THE COMPOSITE

Table 3.1 presents the various properties obtained for E - Glass

fibre, ER and ISO from the manufacturer. The properties include MOE,
Volume fraction and Poisson's ratio.

Table 3.1 Properties of E-Glass Fibre, ISO and ER

E - Glass
Properties ISO ER
Fibre
MOE, (in N/ mm²) 72400 3450 5000
Volume fraction, V 33.33 % 66.67 % 66.67 %
Poisson's ratio, 0.22 0.33 0.30
 52

The properties of GFRP composites depend on the properties of

material constituents (i.e., reinforcing fibre, matrix) and the corresponding
volume fractions. The following methods are available for the calculation of
material properties of the composite based on the properties of its
constituents.

i) Micromechanics

ii) Simplified composite micromechanics equations (Chamis)

iii) Carpet Plots

iv) Equations given by Tsai - Hahn

The methods (i), (ii) and (iii) can be adopted for E-Glass - ISO
composites and methods (i), (ii) and (iv) are suitable for E-Glass - ER
composites

3.12.1 Micromechanics

Transverse modulus, ET = (Ef Em)/[(Em Vf) + (Ef Vm)] (3.1)

Longitudinal modulus, EL = (Ef Vf) + (Em Vm) (3.2)

Longitudinal Poisson's ratio, LT = (Vf f) + (Vm m) (3.3)

Transverse Poisson's ratio, TL = LT x (E T / E L) (3.4)

Shear modulus, GLT = Gm {[(Gf / Gm) (1 + Vf) + Vm] /

[(Gf / Gm) Vm+ 1 + Vf]} (3.5)

where Gm = Em / [2 (1 + m)]

Gf = Ef / [2 (1 + f)]
 53

3.12.2 Simplified composite micromechanics

Transverse modulus, ET = (Ef Em)/[Ef - Vf(Ef - Em)] (3.6)

Longitudinal modulus, EL = (Ef Vf) + (Em Vm) (3.7)

Longitudinal Poisson's ratio, LT = (Vf f) + (Vm m) (3.8)

Transverse Poisson's ratio, TL = LT x (E T / E L) (3.9)

Shear modulus, GLT = (Gf Gm)/[Gf - Vf(Gf - Gm)] (3.10)

where, Gm = Em / [2 (1 + m)]

Gf = Ef / [2 (1 + f)]

3.12.3 Carpet Plots

Figure 3.3 Ratio plots for Ex Figure 3.4 Ratio plots for Ey
 54

Figure 3.5 Ratio plots for G Figure 3.6 Ratio plots for
xy xy

Figure 3.7 Carpet plots for Figure 3.8 Carpet plots for
laminate properties (Ex) laminate properties (Ey)

Figure 3.9 Carpet plots for Figure 3.10 Carpet plots for
laminate properties (Gxy) laminate properties ( xy
)
 55

Using Carpet plots given by Davalos et al (for WR + ISO resin)

From Figure 3.3 (Ex)33.33 % / (Ex) 50% = 0.7

From Figure 3.4, (Ey)33.33 % / (Ey) 50% = 0.7
From Figure 3.5, (Gxy)33.33 % / (Gxy) 50% = 0.7
From Figure 3.6, ( xy)33.33 % /( xy) 50% = 1.02
From carpet plot, Figure 3.7 (Ex) 50% = 5.55E+06 psi
= 38.28 GPa
From carpet plot, Figure 3.8 (Ey) 50% = 1.60E+06 psi
= 11.03 GPa
From carpet plot, Figure 3.9 (Gxy) 50% = 6.30E+05 psi
= 4.35 GPa
From carpet plot, Figure 3.10 ( xy) 50% = 0.29
(Ex)33.33 % = 0.7 × (Ex) 50% = 3885000 psi = 26.71 GPa
(Ey)33.33 % = 0.7 × (Ey) 50% = 1120000 psi = 7.70 GPa
(Gxy)33.33 % = 0.7 × (Gxy) 50% = 441000 psi = 3.03 GPa
xy)33.33 % = 1.02 × ( xy) 50% = 0.296

3.12.4 Tsai Hahn’s Equations

Transverse modulus, ET = (Vf + T1Vm) Ef Em/[Em Vf + T1Vm Ef ]

T1 = 0.516 for ER and E-Glass (3.11)

Longitudinal modulus, EL = (Ef Vf) + (Em Vm) (3.12)

Longitudinal Poisson's ratio, LT = (Vf f) + (Vm m) (3.13)

Transverse Poisson's ratio, TL = LT x (E T / E L) (3.14)

Shear modulus, GLT = (Vf + T2V m) Gf Gm/

[Gm Vf + T2Vm Gf ] (3.15)
 56

Where, Gm = Em / [2 (1 + m)]

Gf = Ef / [2 (1 + f)]
T2 = 0.316 for ER and E-Glass

Summary of the properties of the composite calculated by various

methods is given in Tables 3.2 and 3.3.

Table 3.2 Material Properties of the E-Glass - Isophthalic Polyester

Composite

Simplified Carpet Carpet

Property Micromechanics composite plots plots
micromechanics (WR) (CSM)

Ex (in
26.433 26.433 26.71 14.92
GPa)

Ey (in
5.055 7.664 7.70 14.82
GPa)

Gxy (in
2.44 2.90 3.03 5.29
GPa)
xy 0.293 0.293 0.296 0.41

yx 0.056 0.085 0.085 0.41

 57

Table 3.3 Material Properties of the E-Glass - Epoxy Composite

Property Micromechanics Simplified composite Tsai Hahn’s

Micromechanics Equation
Ex (in 27.467 27.467 27.467
GPa)
Ey (in 7.250 10.810 6.49
GPa)
Gxy (in 3.44 4.09 4.40
GPa)
xy 0.293 0.293 0.293
yx 0.077 0.115 0.050

3.13 CONCLUDING REMARKS

ER and ISO are chosen as resin WR and CSM are chosen as matrix
for the present study. The appropriate properties have been obtained by using
four popular methods, namely (i) Micromechanics, (ii) Simplified composite
micromechanics, (iii) Carpet plots and (iv) Equations given by Tsai - Hahn.
The properties are tabulated in 3.1, 3.2 and 3.3 are used for analytical
evaluation.