Chapter Three

Composite Classification

Introduction
Composites are made by combining two or more materials to give a unique combination of properties .As apposed to metal alloys, each material retains its spread chemical, physical and mechanical properties .The two constituents are normally the reinforcements (fibers , or particulates , or whisker's) and the matrix may be metal (MMC), polymer (PMC) and ceramics (CMC). There are modern classification of composite into (CCC) carbon carbon composite and (IMC) intermetalic matrix composite. They used instead of various materials in the fields in different applications in medicine, civil engineering and military due to their specific properties such as strength and stiffness.

1 Applications of Composite Materials,

Composite materials have found applications in a wide range of industries. In this chapter we attempt to give an overview of the applications of composite materials.

1 -1 Aerospace
Airplane structures as shown in Fig. (3-1) .

3 -1 -2 Automotive
- Body panels in passenger cars as well as race cars are commonly made out of

composite materials. Other applications include composite leaf springs for suspensions and composite drive shafts.

-Tyre has a complex internal structure with multiple reinforcing plies at various
orientations. Reinforcement can be steel wires, polyester or Kevlar cords and the matrix is a synthetic Elastomer with carbon black as a particulate reinforcement as in Fig.(3-2)

Figure (3-1) Use of composite materials in Airbus A320 commercial airplane

Fig.(3-2) Typical structure of a car tire

3.1 -3 Civil Engineering:

New bridges are being built using composite materials bridge. Retrofit of existing bridges, underground pressure vessels, sport equipment, tennis rackets, golf clubs, water skis, baseball bats, bicycle are made of composites Also there are many applications in medical material and sports and agriculture applications. We conclude from the above section that special type rubber of can be used as a matrix composite .

2 Rubber composite

High elastic polymer composites are very important in the applications of rubber industries, such as tyres transportation belts, pipes for fluids and oils transmission, damping and support parts in the mobiles as well as diaphragm. Rubber composite materials with different type of rubber are used in dampers and supports application. Therefore it is occupied a wide field studies ,because rubber has good characterization in the high elastic strain damping which is obtained from the suddenly impact loading because of different acceleration of the system ,therefore a different modification of new type of rubber composite for loading resistance in addition to the interference of the usages conditions with the mechanical loads such as environment effects at high temperatures in the presence of oils and friction result in creation of blended polymers such as (NBR, SBR , NR , CR , ..Etc). Also a new type of polymers which is supported by thermosetting polymers type is developed for heat resistance purposes ,also different types of blended rubbers are improved by supporting methods such as by using particles and fibers for dynamic properties improvement for high loads purposes.

3 Composites for Damping Application

The uses of rubber composite materials in the damping purposes under conditions of heat and oil (leaks from the motor) require good mechanical properties for these products under similar conditions as well as the fixation methods for these products with other parts of supporting .There are various methods for fixation such as adhesion ,compression and bolts ,etc. The usages of adhesion method requires the study of adhesion theory including the mechanical link ,electrical attraction, chemical bond, in which composition material are linked to the coated and uncoated carbon steel with copper .

4 Introduction to Composite Materials.

Since the early 1960s, there has been an ever-increasing demand for newer, stronger, stiffer, and yet lighter-weight materials in fields such as aerospace, transportation, and construction. High demands on materials for better overall performance has led to extensive research and development efforts in the composite fields. These materials have low specific gravity that make their properties particularly better in strength and models Composite materials are constructed from two or more elements to provide a material that has different properties from the individual elements Composite materials that exist today can be categorized into five major classes, which include ceramic matrix composites (CMCs), metal matrix composites (MMCs), intermetallic matrix composites (IMCs), carbon-carbon composites (CCCs) and polymer matrix composites (PMCs) In this discussion, considerable attention is paid to the latter class of materials (PMCs), which include rubber matrix composite (RMC) specially Acrylonitril Butadiene Rubber ( NBR). There are three important kinds of reinforcement system of polymer matrix, particularly, short-fiber and continuous-fiber composites as shown in Figure 3 3

4 1

Polymer Matrix Composites (PMCs)

Polymer Matrix Composites (PMCs) are the most common composites, and are also known as Fiber Reinforced Polymers (or Plastics) FRP. These materials use a polymer-based resin as the matrix, and a variety of fibers such as glass, carbon and aramid as the reinforcement. Matrix materials are thermosetting thermoplastic, elastomer, and rigid rod plastic, thermoelastic plastic polymers. Reinforcing fibers are either continuous or chopped. In general, polymer composites processing includes contracting of polymer and fibers, shaping, controlled heating and / or reactions, and

Polymer

PMC

Metals MMC

Vf

Ceramics CMC

Reinforcement

IMCs Inter metallic

CCCs

Carbon - Carbon

Fig. (3

3): the Classes of composites materials.

cooling. The technology of polymer composites has been driven to a large extent by aerospace arid military applications.

4 2

Metal Matrix Composites (MMCs)

Metal matrix composites can be obtained using either a primary liquid phase approach such as squeeze casting/infiltration or spray deposition, or a primary solid state processing such as powder techniques and foil diffusion. Common MMCs are aluminum based MMCs, fiber reinforced titanium alloys, and magnesium alloy-SiC particulate MMC. The aluminum-based materials are the most popular for reasons of cost and ease of fabrication.

4 3 Ceramic Matrix Composites (CMCs)

Ceramic Matrix Composites (CMCs) are used for very high temperature environments. The definition of the ceramic matrix can be rather broad. It includes inorganic silica-based glasses, crystalline ceramics, glass-ceramics, intermetallics and carbon. All of these have implicit unifying thread in that they are fairly hightemperature structural materials. In CMCs, the ceramic matrix covers a wide variety of inorganic materials, which are generally nonmetallic and are processed at high temperatures. Common ceramic matrix materials include various glasses, glassceramics and ceramics, such as carbon, silicon carbide, silicon nitride, aluminides and oxides. The reinforcements can include carbides, borides and oxides .

4 4 Carbon - Carbon Composite (CCC s)

The development of carbon-carbon materials began in 1958 and was nurtured under the US Air Force space plan program DynaSoar, and NASA 3 Apollo projects Carbon-carbon materials are a generic class of composites much like graphite /epoxy family of polymer matrix composites. They can be made in a wide variety of forms. From one dimensional to n-dimensional using unidirectional tow tapes or woven cloth. Because of their multiform, their mechanical properties can be readily tailored. Carbon materials have high strength and stiffness potential as well as high thermal and chemical stability in inert environment .They must however, be protected with coatings and /or surface sealants when used in an oxidizing environment.

4 5 Intermetallic Matrix Composites (IMC s).

Several major problems limit the development of inter-metallic-matrix composites (IMCs), including chemical incompatibility and CTE mismatch between potential reinforcing fibers and matrix materials, poor low- temperature ductility, and marginal high-temperature oxidation resistance of intermetallic materials. Composite fabrication and joining processes do not result in excessive fiber/matrix reaction or matrix contamination. The initial phase of the IMC program involves investigating available fiber compositions (SiC and Al203) in aluminides of iron, titanium, nickel, and niobium. These aluminides are Ti3 AI and Fe3C for applications to 1000C and NiAI and Nb- alloy/aluminides for higher temperature applications. Alloying studies of these materials are aimed at increasing toughness, ductility, and oxidation resistance, and promoting longtime stability with the candidate fiber materials. Candidate matrices will be evaluated using tensile, compression, fatigue, creep, and

oxidation tests. Measurement of appropriate thermal and physical properties is another planned task. Powder-cloth fabrication processes have been developed to produce IMC materials, and alternative processing procedures, such as thermal spraying, are being Ti3Al + Nb material, based on tensile, thermal-cycle, and strain-controlled fatigue studies for temperatures up to 815C . Studied Encouraging results have been obtained on SiC---reinforced.

Principle of Particles Reinforcement

Reinforcement by particle is divided into two categories depending on the size of the particles used for reinforcement in addition to the mean free path, the two categories are :-

5 1

Dispersion Strengthening

Reinforcement by particles causes increment in the resistances of the composite material against distortion and this depends on the way of the particles dispersion in the matrix material. In this type of reinforcement the size of the particle is less than 0.1 m and the mean free path ranges between 0.01 -0.3 m. For analysis of this kind of reinforcement suppose the particles size, and the volume fraction, Vf and the mean free path, mfp one can calculate it from the following relation: mf p = 2 / 3 V f .. (3-1 ) and to calculate the shear stress the following relation is used =Gmb/Dp (3-2) Where Gm the shear coefficient Dp the distance between particles b Burger s factor The relation (3-2) shows that composite resistance is inversely proportional to dispersed particles thus when distance between the particles decreases the movement of dislocations in the matrix decreases as in Fig.(3 4 ).

5 2 Particle Strengthening

The particle size in this type of reinforcement is higher than 1 m and the mean free path for the matrix material is higher than 1 m. The principle of its use is similar to that of dispersion strengthening because it prevents distortion of the matrix materials. In addition it bears the applied stresses on the composite due to its large volume Fig. (3 5 ) the yield resistance for particulate composite Rpc is inversely proportional to the square root of the distance between particles, Dp according to the relation.

Rpc

Dp

Normally fillers are used to change the thermal, electrical, and mechanical properties of the matrix. The coefficients of particulate composites near the minimum values of composites reinforced with fibers as shown in the fig. (3 6 ). When sand is mixed with polymer this will be much cheaper than in case of well arranged glass fiber in the same polymer. For this reason the slight increment in the hardness as a result of particles addition is economically important. Naturally the resulting particulate composite becomes isotropic instead of anisotropic as in case of fibring composites and this may be very beneficial in case of some applications which require isotropic characteristics. The filtered polymers may be formed and molded in normal ways, and for this reason they are manufacturing cheaply, they appear in the modern automobiles as dumpers, front windows bumpers, and shield external pieces. The following diagram in Fig.(3 7 ) shows the increment in rubber tensile, strength when reinforced with particles from different types of carbon black

Fig 3

4 The path of the crack for particulate composites under tensile strength .

Fig 3

5 The relation between the yield resistance cu Vs 1/(Dp)1/2 .

FIG 3

6 The change in the elasticity coefficient for particulate composites with

volume fraction change.

Fig 3

7 :The increment in rubber tensile strength when reinforced with particles from different types of carbon black .

3 6

Fibers

The potential of fibers for approaching the theoretical strength of the materials from which they are made, forms the basis of much of the research in the inorganic fiber industry. In many cases, the fiber strength may surpass the strength of the bulk solid material by a factor of the order of 10. The modulus of resilience (indicating energy absorption characteristics) of fibrous glass, for instance, can be increased a thousandfold over that of the bulk material, and the tensile strength a hundredfold. Also some of the crystalline substances that have the greatest theoretical strength are nonmetals such as graphite and alumina. These substances have the added virtue of a low specific gravity, so that their strength for a given weight can be four times that of the strongest steel.

10

Table (3
Material silicon carbide beryllia Type A boride iron whiskers E glass

1 ). Specific Tensile Strength of Fibers .

Tensile strength of fibers at equal weight N/mm2(Mpa) 7000 - 20 000 1000 - 4000 700-1 500 700-1 500 700-1 100 400-1 100 70-200 50-200 200-280 76-94

fused silica glass tungsten wire zirconia fibers steel Nylon 66

7 Principles of Fibers Reinforcement

The mechanical properties of composites depend on several factors including the specific properties of matrix material and the reinforcement phase especially the volume fraction, shape, the direction, and the linkage force between the two phases. When the analysis is for the stress and the strain behavior for a composite which contains cylindrical shape and continuous fiber exposed to stress parallel to axis No.1 as in Fig. (3 8 a) (suppose that matrix and fiber link are parallel) Fig.(3 8 b). Under the applied load an equal elongation in the stress direction (01) occurs, and the fiber and the matrix have equal strain . = m= f c = strain of the composite m = strain of the matrix f = strain of the fiber
c

(3-3)

11

The continuous fibers along a composite material in which volume of any part occupied by fibers and the matrix resemble the volume fraction for each of them, and the total stress of the composite is equal to the sum of the stresses in each according to its volume fraction (according to the mix base ) . Vf ) m1 .. (3- 4) 1 = Vf f1 + (1 where :1 = the stress applied in the axis (1) direction
f1

= the stress applied to the fibers by stress

= the stress applied to the matrix by stress 1 V f = the fiber volume fraction in which V f +V m = 1 Vm = the matrix volume fraction When strain becomes as elastic strain , under tensile stress parallel to the axis 1 , the
m1

12

relation between stress and strain for the fiber , matrix , and the composite obeys Hooke s law: =E f f1 m1 =E m m1 =E 1 1 1 E f, E m , E 1elasticity coefficient for fiber , matrix , and composite respectively by substitution for stress value in equation (3 4 ) , we obtain E 1 =V f E f +(1-V f )E m .. (3 5 ) because the strains for fiber, matrix, and composite are equal, note that the stress in the( 2-3) plane equals 0 (3 6 ) f2 = m2 f3 = m3 = 0
f1

it is noticed from equation (3 5 ) that with reinforcement by large volume fraction of the resins we get on elastic coefficient nearly equal to that of some metals such as aluminum (70 G Pa) as in Fig. 3 9

Fig. 3 9 Elastic coefficient for composite reinforced with continuous fiber. a) El in case of the stress parallel to the fiber b) E2 in case of the stress perpendicular to the fiber. When reinforcement is by large fiber volume fraction, the elastic coefficient of the composite will be E 1= E f .. (3 - 7)

13

always it is to be E m<< E f It is noticed in such kind of loading , the matrix in addition to its work as fixative material for the fiber shares the fibers in the resistance of the applied stress to the composite. When the stress has effect on the plane 2-3, in this case the tensile stress is parallel to the axis 2 (suppose that the matrix and the fibers link alternatively) as in Fig (3 10 ). Then the stress applied to the fibers is equal to the stress applied to the matrix which is equal to the stress applied to the composite. The total composite strain value is equal to the sum of the strains of each of the fiber and the matrix. .(3 - 8 ) 2 = V f + (1- V f) m After application of Hooke s law to the fiber and the matrix and substitution in equation (3 8 ) we get on E 2= E f E m / (1 V f)E f+ V f E m . (3 9 ) Notice that in such type of loading , the fibers play a second role in which it works to decrease the deformation quantity in the matrix. When equations (3 - 5) and (3 9 ) are applied to composite of epoxy reinforced with glass fiber, a large difference is noticed in the elastic coefficient due to the change in the loading direction .From that it is possible to say that composite can bear high force when the fiber is in the direction of the load and very low force when the force is perpendicular to the reinforcing fibers. In the light of use this material is considered anisotropic in mechanical properties To decrease this difference in order to get a strength in two directions, it is possible to use fibers woven by 0 - 90.

8 Structural composites

A structural composite is normally composed of both homogeneous and composite materials, the properties of which depend not only on the properties of the constituent materials but also on the geometrical design of the various structural elements Laminar composites and sandwich panels are two of the most common structural composites.

8 1 Laminar composites

Laminar composites are found in as many combinations as the number of materials. They can be described as materials comprising of layers of materials bonded together. These may be of several layers of two or more metal materials occurring alternately or in a determined order more than once, and in as many numbers as required for a specific purpose. It is not possible to achieve high strength materials unlike the fibre version. But sheets and foils can be made isotropic in two dimensions more easily than fibers. See figure (3 10 ).

14

Laminations may be also deconstructed using fabric material such as cotton, paper, or woven glass fibers embedded in a plastic matrix.

Figure (3 10 ) Laminar composite .

A hybrid composite comprises more than one type of fibre reinforcement or one or more matrices, or a combination of both. Foils or sheets or their combinations along with fibers are also accepted as hybrid composites or combinations of different particulate composites. Hybrid composites are cost effective. Hybrid composites have the following properties: 1. Enhancing the impact resistance, with the addition of ductile fibers, which helps in delay of the damage on impact. 2. Allow greater energy absorption. 3. Prevents breakage of structural materials.

8 2 Sandwich panels

Considered to be a class of structural composites, consist of two strong outer sheets, or faces, separated by a layer of less dense material, or core, which has lower stiffness and lower strength. The faces bear most of the in plane loading, and also any transverse bending stresses. Typically face materials include Al alloys, fibre reinforced plastics, titanium, steel, and plywood. Figure (3 11 ) shows honeycomb core sandwich panel. Core has two functions: 1. Separated the faces and resist deformations. 2. Provides a certain degree of shear rigidity along planes. A popular core consists of honeycomb structure. Sandwich panels are found in a wide variety of applications, they include roofs, floors, and walls of building and in aircraft for wings.

15

Figure (3 11 ) Honeycomb core sandwich panel

9 The Effective Factors on Composites Reinforced with fibers.

Properties of composite depend mainly on its composition and the way of mixture rule, it is found that the strength of the composite material against the stresses depends mainly on the elastic modulus and the strength of the reinforced fibers, thus it is possible to obtain preferred strength depending on the volume fraction of the reinforcing fiber. When increasing the volume fraction of the reinforcing fiber, the tensile strength of the composite increases, while in case of low volume fraction of the fibers , the composite will behave as the matrix behavior as shown in Fig.( 3 12 ) when V f <V f min the composite strength will be .. (3 - 10 ) c= muts (1- V f) where :resemble matrix ultimate tensile strength muts

16

Fig.(3

12 ) Effect of fiber volume fraction on the tensile strength

from the above equation we notice that the matrix behavior predominates the composite behavior, thus V f < V f min It is noticed that the composite properties start to decrease when fiber volume fraction exceeds the value 0.8 due to the weakness of the linkage between the fibers and the matrix and between fibers themselves and the excess of voids in high percent reinforcement .

9 1

Effective of Fiber Length

In the composite of discontinuous (short) fibers, may be these fibers are exposed to cracking during loading to any action, then the properties of the composite will not obey the mixing rule, and the reinforcement becomes ineffective unless the length of the fiber is taken in consideration in which it must be longer than certain length called critical length which is possible to calculate from the relation . lc =d f/2 where d fiber radius - shear stress parallel to the fiber f - the applied stress on fiber .. (3 - 11)

When we test the creating stresses at the two ends of the fiber which is immersed in the matrix as in Fig.[3 13 ] we notice a lowering in the tensile stress normal

17

value up to zero at the fiber end (cracking direction ), while shear stress of the interfacial surface increases from the normal value up to the its maximum value.

Fig.(3

13 ) Diagram for composite under stress in the fiber ends .

This fiber part in which this change occurs is Lc /2 which is considered as ineffective for bearing the applied tress on the composite , and the effective fiber length in the composite is that verifies the relation . l c/2rf = f max /2 max (3 - 12) where :maximum applied stress on the fiber f - the shear strength of the matrix In the cases in which deformation of the matrix is elastic , the percent l c/2rf decreases with increasing fiber volume fraction an shown in Fig.(3 14 )

18

Fig.(3 14 ) The effect of ratio L c/2r and v composite reinforcement with steel fiber .

on tensile strength aluminum

We notice the effect of the ratio l c/2rf and the volume fraction on the composite tensile strength in which the tensile strength increases as the volume fraction increases l c/2rf when the composite obeys the mixing rule.

3 9

2 Fiber Orientation

Alignment process in short fibers reinforced composite is considered as an important factor , in which unalignment of the fiber occurs during manufacturing due to the fine short fibers which are difficult to align. The fiber direction elative to the applied load has effect on the composite tensile strength as shown in Fig. (3 15 ). It is noticed that the composite strength becomes maximum when loading form an angle between 0-8? with the fiber axis while it starts severe lowering at larger than 8? which resembles the critical angle.

Fig.(3

15) Effect of fiber orientation on composite tensile strength .

Fig.( 3 - 16 ) shows the fibers different arrangement and Fig.( 3 17 ) shows the toughness change according to these arrangement . It is possible to obtain maximum toughness when the fibers are arranged in the same direction of the applied load, and

19

such orientation is used in the bars, and it is possible to obtain equal toughness in two perpendicular directions when the fibers are arranged in angel (0- 90?) with the applied load direction , this kind of reinforcement is used in the building structure , while if the fibers are randomly arranged , then the toughness are equal in all directions and this arrangement is used in making caps and bags .

Fig.( 3 - 16 ) The fibers in different arrangement.

Fig.( 3

17 ) The toughness change according to these arrangement.

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10 Fiber Composite Hybrids

The advantages offered by hybrid composite materials are often considered in terms of the improvement in a particular mechanical property resulting from the addition of a second reinforcement type. The existence of a positive or negative hybrid effect is determined by three factors : i) the relative volume fractions of the two fibers, ii) the arrangement of the fibers in the hybrid, and iii) the loading configuration.

10 1 Types of hybrids

One of the advantages of hybrids is flexibility in the choice and disposition of reinforcements and, if used, core materials. There are many types of structure; it is proposed to split up these structures into four general types, A, B, C and D .

10 1

1 Type A- Dispersed Fiber

In the limit, this consists of an intimate mixture of two or more types of continuous fiber aligned, but randomly dispersed throughout a common resin matrix.

10 1

2 Type B- Dispersed Fiber Ply

Basically this consists of a random or alternating mixture of two or more types of fiber ply. The fiber plies may be unidirectional, angled, or built up from dispersed fiber material, type A hybrids. The thickness of successive layers of the same material is not necessarily the same, nor does equal thicknesses of the different fiber types have to be used.

10 1

3 Type C-Fiber Skin and Core

This type consists of outer skins of one or more sorts of fiber laminate applied to a core made of another fiber laminate. Both skins and core may be made of unidirectional or angle ply materials of type A or B hybrids. It is usual, though not necessary, to have the stiffer fiber in the skins (e.g. carbon fibers applied to either side of a GRP core), and to have a structure which is symmetrical about a centre plane. However, hybrids have been produced in forms in which the core is reinforced on one side only, e.g. carbon fibers applied to the compressive side of an aramid reinforced plastic (ARP) core, or dissimilar skins applied to both sides of the core. Another variant uses thin strips of reinforcement let into the upper and / or lower surfaces of the fiber core.

21

10 1

4 Type D-Fiber Skin, Non Fiber Core

This type of hybrid, which consists of fiber skins applied to a core of foam, filled resin, some type of honeycomb, solid metal or wood, is often referred to as a sandwich structure. Materials of this type, though without high performance FRP skins, have been employed extensively for some years. The skins may again consist of one or more types of fiber arranged in a unidirectional or angle ply form or hybrids of types A or B. The structures are usually symmetrical about a centre plane, but need not necessarily be so. With some core materials, such as filled resin, solid metal, and wood, strips of reinforcement can be employed instead of skins. In many cases an adhesive layer, other than the resin matrix, is used to bond the skins and the core. Examples of type D hybrids are antennae dishes (CFRP and aluminium honeycomb), outhouses (CFRP and solid aluminium), and storage tanks (GRP and end grain balsa wood). There are additional structures as other types of hybrid. Payen describes a construction for the aircraft industry in which CFRP was sandwiched between aluminum skins. The different hybrids are illustrated schematically in Fig.(3 18 )

Fig. (3

18 ) Schematic diagrams of hybrid types

all end view.

It is helpful to consider a simple example of a practical hybrid which demonstrates some of the advantages to be gained from the construction. The system is a symmetrical fiber skin and core, type C hybrid, and the results are based on the work of Wells and Hancox . A sketch of the specimen, stressed in 3 point flexural loading, is shown in Fig. (3 19 ) together with a load deflection characteristic for a sample containing 50 v/O CFRP and 50 v/O GRP. It should be remembered that the carbon and glass fibers are continuous and aligned along the long axis of the bar.

22

Fig. (3

19 ): Load deflection curve for a hybrid beam .

10 2 Advantages of Hybridisation

Hybridisation offers several additional advantages in design and manufacture, which bring more demanding applications within reach. (1) Stiffness: Lager and thinner unsupported areas are feasible. (2) Thermal expansion: The coefficient of thermal expansion can be controlled to match design requirements. This is especially important in metal / FRP combinations where clearances and close tolerances must be maintained, and in design with metal inserts, where differential stresses must be minimized. The addition of as little as 5% carbon fibers to a chopped strand GRP reduces the thermal expansion coefficient to that of aluminium, and higher concentrations reduce the value to that of steel. (3) Dimensional stability: Relatively low additions of carbon fibers improve shape retention characteristics both in manufacture and service, facilitating accurate reproduction of precision components without shrinkage or warpage. (4) Corrosion resistance: The incorporation of surface layers of carbon fibers on FRP mouldings greatly enhances resistance to environmental attack. (5) Conductivity (thermal and electrical): Hybrids can be formulated with accurate control of in-plane and through thickness conductivity. Electro-magnetic shielding, heat transfer characteristics and thermal transient effects can therefore be modified. Hybridisation must necessarily play a key role in the synthesis of composites with predetermined sets of physical, chemical and mechanical properties. The significance of hybrid systems is that they provide the practical means of access to intermediate property/cost levels

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3 11 Resins
A material, generally polymer, which has an indefinite and often high molecular weight and a softening or melting range and exhibits a tendency to flow when it is subjected to stress. Resins are used as the matrices to bind together the reinforcement material in composites. The two classes of resins are the Thermoplastics and thermosets. A thermoplastic resin remains a solid at room temperature. It melts when heated and solidifies when cooled. The long chain polymers do not chemically cross link. Because they do not cure permanently, they are undesirable for structural application. Conversely, a thermosetting resin will cure permanently by irreversible cross-linking at elevated temperatures. This characteristic makes the thermoset resin composites very desirable for structural applications. The most common resins used in composites are the unsaturated polyesters, epoxies, and vinyl esters; the least common ones are the polyurethanes and phenolics .

11 1 Epoxy Resins

Epoxy resins are a range of compounds. They are long-chain compounds, which can be cross-linked with various other chemicals to give thermosetting compounds, crosslinking takes place without the liberation of water. One of the constituents of epoxy resin is epichlorhydrin. Most epoxy resins are based on the reaction between epichlorhydrin and a chemical, which is usually referred to as bisphenol . The epoxies used in composites are mainly the diglycidyl ethers and amines. The material properties and cure rates can be formulated to meet the required performance. Epoxies are generally found in marine, automotive, electrical and appliance applications. The high viscosity in epoxy resins limits it use to certain processes such as molding, filament winding, and hand lay-up. The right curing agent should be carefully selected because it will affect the type of chemical reaction, pot life and final material properties. Although epoxies can be expensive, they may be worth the cost when high performance is required. The chemical structure of an epoxy is :

Fig.3 20 : The chemical structure of an epoxy (diglycidyl ether of bisphenol A, DGEPA)

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12 Phenol-Formaldehyde (PF)

The 1940 s to 1960 s brought about much development in the chemistry of phenolic resole and novolac resins. However, it was not until the 1970 s to 1980 s that much effort was made in the reinforced composites industry to use these resins. The phenolic resins are made from phenols and formaldehyde, and they are divided into resole and novolac resins. The resoles are prepared under alkaline conditions with formaldehyde/phenol (F/P) ratios greater than one. On the contrary, novolacs are prepared under acidic conditions with F/P ratios less than one. Resoles are cured by applying heat and/or by adding acids. Novolacs are cured when reacting chemically with methylene groups in the hardener, the common procedure for curing phenolic novolac resins uses hexamethylenetetramine (HMTA) and releases volatiles during the cure, which produce networks with numerous voids. This results in materials that lack the toughness necessary for structural application. Phenolics are particularly suitable for electrical applications because of their good. dielectric properties, dimensional stability and resistance to moisture.The phenolics are also rated for good resistance to high temperature, good thermal stability, and low smoke generation. Finaly Polymeric phenolic compounds have a wide range of applications, including fields such as aerospace, construction, and electronics. There are three core reasons for the broad application range of these materials. First, the synthesis of phenolic prepolymers by electrophilic aromatic substitution is relatively simple and inexpensive. Second, methods for their conversion into thermoset networks are well established. Third, these networks are highly aromatic and thus, they are resistant to thermal oxidation. Phenolic resins are well known for their excellent fire, smoke, and fast smoke toxicity properties (FST); retention of properties after long-term exposure to high temperatures; excellent electrical resistance; and excellent chemical resistance, especially in chlorinated solvents. However, they are also known to be quite difficult to pultrude due to their high viscosities, slow cure rates leading to slow pull speeds, and high porosity content. Therefore, the efforts lead to development of a new series of low viscosity phenolic novolac resin systems processable at high speeds with excellent mechanical properties and outstanding fast strength tensile characteristics, For more details see reference.

12 1

Resoles

Resols are prepared under alkaline conditions with an excess of formaldehyde. The ratio of phenol to formaldehyde ranges from 1:1 to 1:3.The mechanism of the phenol formaldehyde reaction is a base catalyzed electrophilic aromatic substitution to form a combination of the mono, di and trihydroxymethylphenols . These hydroxymethylphenols are then reacted to form the prepolymers. The prepolymers are heated to promote cross linking of the resin by further reaction of hydroxymethylphenols. The approximate tures of resols is shown in Fig. (3 21 ) below.

25

Fig (3 - 21): Approximate tures of resoles .

12 2

Novolac

Novolacs are prepared under acidic conditions with an excess of phenol. Novolac oligomers, once formed, are stable and require an external cross linking reagent to produce networks. The most common cross linking reagent for novolacs is hexamethylenetetramine (HMTA). Typically between 5 and 15 wt % HMTA is used to produce the nitrogen containing cross linked network. With this process a significant amount of gas is produced during the cross linking reaction which contains at least 95 % ammonia, and the cured resin may contain up to about 6 % bound nitrogen. Therefore, about 75 % of the nitrogen from HMTA becomes chemically bound in the network. The volatiles released during the cure can create voids in the network, just as with the resols. An alternative to the HMTA, to avoid the production of volatiles during the cure reaction, is to convert the novolac to an alternative type of epoxy resin that can be cured with and amine . Novolacs are one of the most widely used engineering thermosets utilized in automobile, electrical, electronic, packaging, textiles and consumer applications because of their excellent mechanical properties. The approximate tures of novolacs are shown in Fig (3 - 22) below. Fig (3 - 23) shows the formation of the phenolic novolac epoxy net work .

26

Fig (3 - 22): Approximate tures of novolacs .

Fig (3

23 ): Network formation of Novolac - Epoxy .

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13 Fibers

Fibers are the most important class of reinforcements, as they satisfy the desired conditions and transfer strength to the matrix constituent. Influencing and enhancing their properties as desired. Glass fibers are the earliest known fibers used to reinforce materials. Ceramic and metal fibers were subsequently found out and put to extensive use, to render composites stiffer and more resistant to heat.

14 Types of fibers

Natural fibers (cellulosic and ligno cellulosic) have been used as structural materials since prehistoric times. Since several years, for economic and environmental reasons, there has been an increasing interest in using plant fibers in composite systems. Plant fibers have the following properties: 1. Cost effective. 2. Renewable. 1. Available in high quantity. 2. Have low fossil fuel energy requirements. 3. Can offer good mechanical properties. Organic and inorganic fibers are used to reinforce composite materials. Properties of organic fibers are: 1. Low density. 2. Low flexibility. 3. Low elasticity. While the properties of inorganic fibers are: 1. High modulus. 2. High thermal stability. 3. Posses greater rigidity than organic fibers. The use of fiber as high important characteristics: performance engineering materials are based on three

1. A small diameter with respect to its grain size or other microstructural unit. The strength of carbon fibre decreases as its diameter increase, figure (3 24 ). 2. A high aspect ratio (length / diameter, l / d) that allows a very large fraction of the applied load to be transferred via the matrix to the stiff and strong fibre.

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3. A very high degree of flexibility that is really a characteristic of a material having a high modulus and small diameter.

Figure (3 24 ) Decrease in strength( f) of a carbon fibre with increase of diameter (d)

15 Fibre factors

What factors contribute to the engineering performance of a fibre matrix composite? Among the most important are: a. Orientation b. Length c. Shape d. Composition of the fibers.

15 1 Orientation

Fibre orientation (how the individual strands are positioned) determines the mechanical strength of the composite and the direction in which that strength will be the greatest. There are three types of fibre orientation: One dimensional reinforcement, planar (two dimensional) reinforcement, and three dimensional reinforcement. As fiber orientation becomes more random, the mechanical properties in any one direction become lower. Figure (3 25 ) shows three types of orientation reinforcement.

Figure (3 25 ) Three types of orientation reinforcement

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15 2 Length

The orientation of fibers in the matrix can be accomplished with either continuous or short fibers. Although continuous fibers are more efficiently oriented than short fibers, they are not necessarily better. Composites made from shorter fibers, if they could be properly oriented, could have substantially greater strengths than those made from continuous fibers. This is particularly true of whiskers, which have uniform tensile strength as high as (10.3) Gpa. Because the shorter fibers can be produced with few surface flaws, they come extremely close to achieving their theoretical strength. In general, continuous fibers are easier to handle but more limited in design possibilities than short fibers. Short fibre composite materials are used to make many flat and irregular shapes. See figure (3 26 ). The matrix serves two very important functions: 1. It holds the fibrous phase in place. 2. Under an applied force it deforms and distributes the stress to the high modulus fibrous constituent. Critical length of fibre c dependent on fibre diameter (d) and * f (U.T.S) and fibre matrix bond strength ( c) as follow :2 c 2l= . (3 13 ) * fd

Figure (3 26 ) Schematic representation of: - (a) Continuous and aligned (b) Discontinuous and aligned (c) Discontinuous and randomly oriented fibre reinforced composites

15 3 Shape

Fibre shape can have an effect on the maximum fibre packing fraction. When relatively large fibers (diameters of 5 mils or greater) are utilized, the fibre shape can be used to advantage, since the fibers can aligned according to both their length and

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cross sectional geometry. In a given volume, circular filaments can theoretically be packed to a bout 91%, where as filaments having polyhedral cross section (if properly aligned) can be theoretically packed to 99%. See figure (3 27 ). (Note that a whisker is any material that fits the definition of a fibre and is a single crystal. While a filament is any fibre whose length to (effective) diameter ratio, or aspect ratio, is for all practical purposes infinity; namely a continuous fibre). Fibre shape can also affect composite properties.

Figure (3 27 ) Strength of carefully selected alumina whiskers as a function of size

15 4 Composition

Both organic and inorganic fibers are available for fibre composite materials. The organic such as polypropylene fibers can be characterized in general as lightweight, flexible, elastic, and heat sensitive. Inorganic fibers, such as glass fibers, can be generally described as very high in strength, heat resistant, rigid, and low in energy absorption and fatigue resistance. Figure (3 28 ) shows an application of fibrous composite. While many organic fibers satisfy both the strength and elasticity requirements for structural composites, graphite in recent years has become the most popular. The inorganics, notably glass, dominate the field.

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Figure (3 28 ) Application of composites: - UH-60A. Black Hawk helicopter

Note that for unidirectional continuous fibre composites the rule of mixtures assumes the following form:cu = fu Vf + m ( 1- Vf ) .. (3 14 ) where cu, fu are the U.T.S (ultimate tensile strength) of the composite and fibre, m is the matrix stress at the ultimate tensile strain of the fibers and Vf denotes fibre volume fraction. In the case of short fibre composites, the above equation is modified as: cu = fu Vf F (lC/l) + m ( 1- Vf ) (3 15 ) where lC and l denote critical and actual fibre length, respectively. The factor F(1c/1) which takes into account the effect of fibre length, is less than unity and: F (lC/l) = 1 ( lC/2l) (3 16 ) For the case of constant interfacial shear stress. While composite strength for discontinuous fibre composite is:-

c =

6/7 1 + (5lC/7l)

f Vf + m ( 1- Vf)

(3

17 )

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Figure (3 29 ) Fibre composite technology

16 Potential advantages of fibrous composite materials

to density ratio.

1. High strength and strength 3. Low density. 4. High stiffness to

2. High strength at elevated temperatures. density ratio.

5. Toughness (impact and thermal shock resistance). 6. Improved fatigue strength. 7. Improved stress rupture life. 8. Improved oxidation and corrosion resistance. 9. Controlled thermal expansion and conductivity. 10. Greater hardness and erosion resistance. See figures (3 29 )

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17 Fibrous Composite Properties

The behavior of a composite material is more than the linear sum of the behaviors of constituent materials. This fact provides engineers with a remarkable opportunity to create new composite materials for various engineering applications Many composite properties are strongly dependent on the arrangement and distribution of fibers: the fiber architecture. This expression encompasses intrinsic features of the fibers, such as their diameter and length, as well as the volume fraction of fibers and their alignment and packing arrangement. The mechanical behavior of polymer composites depends strongly on the adhesion between the polymeric matrix and the filler. Although most calculations on composite materials are based on the volume fractions of the constituents, it is sometimes important, particularly when calculating the density of the composite, to use weight fractions. The appropriate conversion equations are: w f f = ----------------------------(3 18 ) w f + wm m f f w = -------------------------f f + fm m (3 19 )

where f , fm are the volume fractions, w , wm are the weight fractions and the densities of the fiber and matrix respectively.

f,

are

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Fiber composites combine lightweight with high strength and stiffness, and have the highest structural efficiency of any material made by man:

17 1 Glass Fibers

It is the most popular fiber, because it's really cheap, strong and flexible. They are light and corrosion resistant. Most glass fibers are based on silica (SiO2), with additions of oxides of calcium, boron, sodium, iron and aluminium. These glasses are usually amorphous, although some crystallization may occur after prolonged heating at high temperatures, leading to a reduction in strength. Typical compositions of three types of glass popular for composites are given in Table (3 2). The most commonly used, E-glass (E for electrical), draws well and has good strength, stiffness, electrical and weathering properties. In some cases, C- glass (C for corrosion) is preferred, having better resistance to corrosion than E-glass, but a lower strength. Finally, S-glass (S for strength) is more expensive than E glass, but has a higher strength, Young's modulus and temperature resistance. Glass fibers are produced by melting the raw materials in a reservoir and feeding into a series of platinum bushings, each of which has several hundred holes in its base. The glass flows under gravity and fine filaments are drawn mechanically downwards as the glass extrudes from the holes. The fibers are wound onto a drum at speeds of several thousands meters per minute. Control of the fiber diameter is achieved by adjusting the head of the glass in the tank, the viscosity of the glass (dependent on composition and temperature), the diameter of the holes and the winding speed. The diameter of (E glass) is usually between (8 and 15) m . Three characteristics of glass fiber are advantageous in certain application: resistance to high temperatures the softening point is about 850 oC; transparency to visible light a composite therefore takes the colour of its matrix; and isotropy for example thermal expansion is identical in axial and radial directions. A disadvantage is that glass is very susceptible to surface damage. This can be caused by rubbing the surface or by the action of moisture, which seeks out and gradually dissolves certain of the oxides present at the fiber surface. As a result, the strength of the fibers in use is always lower than that of a freshly drawn fiber (by a factor of 2 or more). One function of the coating size is to protect the fibers from surface damage, both during processing and after incorporation in the matrix. Textile glass fiber may be supplied in the form of thread, twine, roving, mat, textile fabric, cut textile glass (approximately 6mm long) and milled short fibers(approximately 140 to 210 m long) .

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The reinforcing effect of the glass fibers is influenced by several factors: * the proportion of glass fiber. * the length/diameter ratio(long fibers are more effective than short). * the nature of the adhesive. * the position of the fibers relative to the direction of the strain (orientation). * the degree of fiber degradation occurring, especially in injection moulding. The strength and stiffness of glass fibers composite increase more or less proportionally to the fiber content. Glass fiber reinforced plastics (GRP) are used extensively in commercial and aerospace components such as canoes, automotive parts and helicopter rotor blades.

Table (3

2 ) Glass fiber compositions and properties E-glass 52.4 14.4 17.2 4.6 0.8 10.6 C-glass 64.4 4.1 13.4 3.3 9.6 4.7 0.9 10.3 0.3 S-glass 64.4 25.0

Composition (%) SiO2 Al2O3+Fe2O3 CaO MgO Na2O+K2O B2O3 BaO Properties (Mgm-3 K ) (Wm-1k-1 (10-6k-1) * (GPa) (GPa ) Tmax ( C)
o

2.60 13 4.9 3.45 76.0 550

2.49 13 7.2 3.30 69.0 600

2.48 13 5.6 4.60 85.5 650

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17 2 Kevlar Fibers

The chemical structure of Kevlar is

One of the most popular examples of modern body armor is Kevlar, the first organic fiber with enough tensile strength and modulus to be used in advanced composites. Because it is five times stronger than steel on a same weight basis while still combining lightweight with comfort and protection, Kevlar is the most well known material used for soft body armor. Kevlar is one of many synthetic polymers. Its official chemical name is poly ( - phenyleneterephtalamide). Its basic configuration is a series of aromatic amides. The aromatic components of the polymers have a radial orientation. This gives it a high degree of symmetry and regularity. This crystalline like regularity is the largest contributing factor in the strength of Kevlar. The aromatic groups are the carbon atoms attached in ring. The amides are the connecters between the aromatic groups. Kevlar long fibers are bundled together and interwoven to create a dense net. This keeps a projectile from penetrating the body as well as spreading the force of impact over the whole vest. The Kevlar fibers are woven in to a tight weave to reduce blunt trauma. Typically, the individual fibers are twisted to increase density and thickness at each point. To increase the rigidity, the Kevlar net is then coated with a resin substance and sandwiched between two layers of plastic filament. Kevlar 49 fibers have high modulus anisotropic, high tensile strength, high stability, premium organic fibers with the low density, low conductivity and textile processability normally associated with conventional organic fibers. The properties of Kevlar fibers show two drawbacks: (1) weakness in axial shear; and (2) yellow coloration (it imparts this colour to its composites). Fig.(3 30 )shows the stress-strain curve under compression load of three types of Kevlar fibers, the modulus of kevlar29 is somewhat smaller than 49 and 149. The compression curve of kevlar29 has a little up-swing shape. Comparison between Kevlar 29, 49 and 149 shows the first has the highest yielding stress of these fibers. On contrary, Kevlar 149 is the lowest. Table ( ) shows some the properties of Kevlar fibers.

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Strain Fig.(3 30 ): Stress-Strain curve of three types of Kevlar under compression load

Kevlar 29 is used in the manufacture of bullet-proof jackets and off-shore equipment whilst Kevlar 49 is the fiber being considered increasingly for sports goods and sports vehicles, for aircraft construction and space technology as well as for general engineering purposes. Laminates made with aramid fibers are lightweight and stiff. They are resistant to impact and vibration and strongly resistant to abrasion. Table ( Type K29 K49 K149 ): Elastic constants for Kevlar fibers

Comp.Ec(GPa) Tensile,EL (GPa)

( y,MPa)

(%)

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17 3 (Glass, Kevlar) Fiber Fracture

In tension, most fibers tend to fracture in a brittle manner. Glass, carbon and ceramic fibers are almost completely brittle and fracture without any reduction in cross sectional area. This can be seen in Fig. (3 31a). In contrast, aramid (Kevlar) fibers fracture in a ductile manner, although the overall strain to failure is still small. Pronounced necking precedes fracture and final separation occurs after a large amount of local drawing as shown in Fig. (3 31b), the fracture usually involves fibrillation of the fibers. The axial compressive strength of a unidirectional lamina made from Kevlar fibers is only 20% of its tensile strength, whereas for glass (which have similar diameters), the strengths are approximately equal in tension and compression. This arises because of the structure of the aramid fiber, which is shown in Fig. (3 32 ). In compression, elastic deformation (of the strong covalent bonds) only occurs to a limited degree before the weak vanderwaals forces between adjacent molecules are overcome and local fibrillation and damage occur. This leads to buckling and kink formation at low applied loads, as shown by the micrograph in Fig. (3 - 33).

(a)

(b)

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Fig.(3 - 31) SEM micrograph of fibers fractured in tension: (a) E-glass,(b) aramid

Fig.(3 - 32): Planner array of poly- p-phenylene terephthalaminde molecules showing inter-chain hydrogen bonding. (b) Supramolecular structure of Kevlar 49, depicting the radially arranged pleated system

Fig.(3 - 33): Scanning electron (SEM) micrograph of Kevlar 49 (aramid) fiber showing deformation bands on the compression side of a sharp bend

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17 4

Carbon Fibers

The graphite or carbon fiber is made from three types of polymer precursors polyacrylonitrile (PAN) fiber, rayon fiber, and pitch. The tensile stress-strain curve is linear to the point of rupture. Although there are many carbon fibers available on the open market, they can be arbitrarily divided into three grades as shown in Table (3 4 ). They have lower thermal expansion coefficients than both the glass and aramid fibers. The carbon fiber is an anisotropic material, and its transverse modulus is an order of magnitude less than its longitudinal modulus. The material has a very high fatigue and creep resistance. Since its tensile strength decreases with increasing modulus of elasticity , its strain at rupture will also be much lower . Table (3 4 ): Typical properties for different types of carbon fibers.

17 5

Asbestos

Asbestos is the name for a group of naturally occurring silicate minerals that can be separated into fibers. The fibers are strong, durable, and resistant to heat and fire. Asbestos is the name for a group of naturally occurring mineral fibers found in certain types of rocks. These silicate minerals are fibrous and have excellent heatresistant properties and tensile strength. Because of their unusual physical and chemical properties, asbestos fibers have been used in products before the Industrial Revolution. During the 20th century, asbestos was heavily used as a strengthener, insulator and binding agent in products such as thermal insulation, cements, textiles, floor tiles, wallboard, gaskets, ropes, fireproof clothing, brakes and other products. Types of Asbestos, There are two main types of asbestos: serpentine and amphibole. 1- Serpentine Asbestos Known for its snake-like, curly appearance, this soft, flexible serpentine type of asbestos can be mixed and woven into products that require high-tensile strength and flexibility. 2- Amphibole Asbestos

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A second form of commercial asbestos, amphiboles has a needle-like shape and a harder composition. Common Asbestos Fibers: There are several types of asbestos fibers, of which three have been used for commercial applications: The most common types of asbestos fibers are Chrysotile known as white asbestos; Amosite known as brown asbestos; and Crocidolite known as blue asbestos. The colors refer to the minerals in their raw state.

17 6

Alumina

Alumina (Al2O3) is among the strongest and hardest of all ceramic materials and is useful at high temperature. They also have a high dielectric strength and at elevated temperatures such as those encountered in many applications. Their electrical resistance is excellent. Alumina ceramics also feature very high mechanical strength, high thermal conductivity, and high resistance to chemical and corrosion attack at room and elevated temperatures. Table.(3 5 ) Some mechanical, thermal and electrical properties of pure alumina.

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