A perspective view of composite materials development

B Harris* Abstract

Athough ancient in concept, the realistic exploitation of composite materials is relatively new. The logical principle of improving engineering materials by combining them to produce new materials with novel properties has engendered new developments in materials research and has demanded increasingly sophisticated attitudes to design and materials production, attitudes which, in passing, have also improved the designer's approach to materials as a whole. Recent history has involved the establishment of basic theories of composite materials, first with metal-matrix composites, and subsequently (and predominantly) with resin-based composites. The latter have so far dominated our thinking in relation to design and practical application, but, freed of some of the earlier constraints, current R&D programmes are already making exciting progress in the manufacture and use of improved metal and ceramic matrix composites. The important question is: "Are we ready for them?"

In most branches of engineering there has been a certain commonality of development in the use of engineering materials. In structural and building engineering, the great traditions of construction with wood and stone and masonry substantially gave way to cast iron and steel during the 19th and 20th centuries. The same period saw the simultaneous growth of the industrial society, with mechanical engineering largely dominated by metallic materials and, in particular, by steel. The aircraft industry, a late starter by comparison, moved rapidly from wood and textiles to metallic construction for aircraft structures, although in this case, and for obvious reasons, it was aluminium that dominated the industry. Chemical engineering plant, in the scaling up process from laboratory glass-ware to manufacturing plant scale, was inevitably built first with cast iron and then with steel, even though lining reaction vessels with glass may have been necessary in some cases. Steels, then, were regarded by engineers of all persuasions as the appropriate structural and general engineering material. The steel.makers responded to the challenge by offering a vast range of compositions and microstructures to meet most requirements. And for those special purposes for which steel was not appropriate, there were plenty of other alloys with corrosion resistance, high temperature oxidation resistance, fatigue resistance, creep resistance, wear resistance, and so forth. The whole ethos of manufacturing in the first half of this century was centred on the ability to produce and form metals. And as late as the fifties, in Europe as in the USA, materials education was exclusively metallurgical. It was thus, in this metallurgically-dominated industrial society, with an associated science base that was becoming increasingly sophisticated, that people like Griffith, Orowan, Taylor and Polanyi began asking questions about the strengths of engineering materials in general. Why were the practical strengths of glass and metal crystals so much lower (ie by several orders of
*School of Materials Science, University of Bath, Claverton Down, Bath BA2 7AY, UK. Tel: +44 (0)225 826826. Fax: +44 (0)225 826098
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magnitude) than might have been expected from a knowledge of the atomic and molecular bond strengths? Thermodynamic arguments and the developing theory of crystal dislocations were able to explain away the discrepancies, although in the twenties and thirties it required an act of faith to accept those theories since the techniques did not yet exist to render Griffith's cracks and Taylor's dislocations visible. Nonetheless, it was readily apparent that glass could be made strong by making it into fine fibres, and the strongest metals of the day were patented carbon steel wires and heavily drawn tungsten lamp filaments the structures of which had been deliberately contrived so as to inhibit motion of dislocations. The concept that filamentary materials were almost always stronger than the same solids in bulk form, together with appreciation of the reasons for this state of affairs and of the fact that fine filaments by themselves were of relatively little use as engineering materials, effectively established what was to become the composite materials industry. The first practical composites, the earliest glass fibre reinforced thermoset plastics, or GRP, were introduced in the 1940s, but made little or no impact in the metalsdominated industrial scene. The reasons for this are not hard to fathom. The potential advantages to the designer of those early, imperfect products were simply too insignificant to provide a driving force for the replacement of metal components by GRP. Research on strong materials in fibre form and composites in general continued in a somewhat desultory manner for nearly 20 years. By the early 1960s, glass reinforced plastics were commonplace but not very seriously regarded as engineering materials. There was, nevertheless, an undercurrent of interest in the possibilities of using GRP even in relatively severe environments. By the end of the 50s, for example, Rolls Royce in the UK were experimenting with GRP for the large fan of a vertical lift gas turbine engine, although the project did not come to fruition, and a number of demonstrations had been made of helicopter rotor blades fabricated from GRP. It was generally accepted that GRP were insufficiently rigid for load-bearing components and structures and were therefore useful only for cladding
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0261-3069/91/050259-14 1991 Butterworth-Heinemann Ltd

independently rigid structures for protection or decorative purposes. Structural engineers were beginning to use them in folded-plate structures so as to build in the necessary structural rigidity, and boat builders were utilising double curvature to the same end, but progress was slow. In the USA, Texaco and the United Aircraft Research Laboratories were producing a new species of fibre boron filaments vapour-deposited onto fine tungsten wires. These fibres were relatively thick, of the order of 100/~m in diameter, and, being brittle, were very difficult to handle, unlike glass fibres which, although also brittle, were very much finer, about lO/~m. At that time, their properties were a significant advance on other available fibres, principally cold-drawn tungsten and tungsten alloys and the so-called "Taylor wires", and of course they were of very much lower density. There was nevertheless scepticism about their potential stability when embedded in alloy matrices for use at high temperature. By the mid-sixties, too, whiskers were a familiar form of potential reinforcing fibre, although extremely expensive. Thermokinetic Fibres Inc in the USA, for example, were offering sapphire whiskers in gram quantities at some $ 50/g. Gordon and his collaborators at the Waltham Abbey establishment of the Ministry of Defence were committed to large scale production of Si3N4 whiskers and were developing techniques for incorporating them into metal matrices. In both the USA and the UK the continuing development of interest in composites remained substantially in the hands of the metallurgists who, seeing the inevitable limitations on the thermal stability of metallic alloys, especially for use in gas turbines, were anxious to develop composites reinforced with metallic reinforcements. The early development of both practical and theoretical aspects of the subject was indeed dominated by considerations of metal-matrix composites. At NASA and other aerospace organisations in the USA efforts were largely concentrated at the high temperature end of the application range, with studies of the stability and high-temperature mechanical response of nickel and titanium alloys reinforced with refractory metal wires. A considerable part of that effort was simultaneously being e x p e n d e d on the development of diffusion barriers to overcome the inevitable fibre/matrix compatibility problem. Much research was also being carried out on directionallysolidified eutectic alloys, starting with simple model systems like AI/CuAI 2 and progressing to more complex and more refractory systems. Rolls Royce were one of the few industrial organisations in the UK which continued to appreciate the potential importance of fibre composite materials, and in their Old Hall Research Laboratories Morley, Baker and their collaborators laid down some of the important foundations of the science and technology of metal matrix composites. By the early sixties, however, interest in metal.matrix composites rapidly waned, partly because of the concurrent rise in interest in reinforced plastics, and partly because of what seemed at the time to be the intractable problem of incompatibility and long-term high-temperature instability inherent in non-equilibrium metal-matrix composites (MCC). This waning interest is manifested in the fact that the technical literature of the 1970s contains almost no reference to MMC. Indeed, in 1972
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a paper was published by Calow and Moore of the AWRE in the UK (J Mat Sci vol 7, pp 543-558) with the memorable title: "No hope for ceramic whiskers and fibres as reinforcement of metal matrices at high temperature". The authors considered that the future of MMC turned on two factors: the question of economics for low-temperature applications, and the matter of interfacial stability during thermal cycling for high-temperature applications, and on both counts they ruled out large-scale utilisation of MMC. For almost 10 years, nothing happened to change that situation, but, as we shall see later, current attitudes are very different. In the gas turbine business, the high-temperature materials problem was temporarily postponed by the concurrent developments of unidirectional solidification of single crystal blades of nickel-based superalloys, and incorporation of blade cooling. Interest in metal fibre reinforced glass and ceramics also flared briefly during this period, but the thermal expansion mismatch problem was again pronounced intractable, and the work was dropped. It was undoubtedly the invention and early exploitation of high-performance carbon fibres at the Royal Aircraft Establishment that caused an acceleration of engineering interest in fibre composites. The British patent, 1,110, 791 of Johnson, Phillips and Watt, filed in 1964 and granted in 1968, led to widespread reappraisal of the potential for fibre composites, and a reassessment of the likely advantages of reinforced plastics over conventional metallic materials. These fibres had properties that far more nearly approached the theoretical strengths of solids than bulk materials, were significantly stiffer than glass fibres and less susceptible to damage by handling. They could be produced in large quantities by sensible commercial processes; and they could be converted into practical composite materials with relatively little difficulty. Few engineering materials have ever gone from laboratory preparation to attempted commercial exploitation in so short a time and without adequate long-term testing or proper understanding of the basic structure/properties relationships. By the end of the 60s, Rolls Royce planned to manufacture a large by-pass engine, the RB211, with a fan manufactured from carbon fibre reinforced plastics (CFRP). For a variety of reasons this project met with difficulties, and in the end plans to use CFRP were delayed when Rolls failed financially and the engine was manufactured with titanium fan blades. Although there is no question of the financial failure being directly attributable to the proposal to use carbon fibres, the two inevitably became linked in the minds of press and public alike, and this association proved to be a set-back to the more general utilisation of composites in stressed applications. There followed a period of consolidation when attention was not constantly being drawn to the "marvellous new carbon fibres", and a measure of rational work was possible in the course of which new materials were develeped and better understanding of the nature and properties of composite materials in general was obtained, it is against this background that we shall now take a more detailed look at developments in composites and some of the prospects for the future. Scope for reinforcement of conventional materials The science of composites represents in several ways
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an epitomisation of the broader subject of materials science. Practitioners must understand the nature and behaviour of the gamut of substances - metallic, ceramic and polymeric - and the interactions between these characteristics. With this knowledge they may manipulate them in combinations whose properties, being determined by their microstructure, ought to be predictable if that microstructure can be adequately characterised. Ideally, the properties of engineering materials should be reproducible and accurately known. And since satisfactory exploitation of the composite principle depends on the design flexibility that results from tailoring the properties of a combination of materials to suit a particular requirement, we also need to be able to predict those properties successfully. At the present time some of the more important engineering properties of composites can be well predicted on the basis of mathematical models, but many cannot. Elastic behaviour of fibre composites, for example, is successfully treated by existing composite mechanics theories, but toughness, fatigue response and time.dependent behaviour are not. For such properties as these, therefore, the designer must consult available experimental evidence and design with caution. As a result, the potential for economic use of composites is often lost in the safety factors that are needed to accommodate this state of uncertainty.

moderately easily shaped and joined. It is largely a consequence of their ductility and resistance to catastrophic crack propagation that metals, as a class, are the preferred engineering materials. On the basis of such a superficial comparison it is apparent that each class has certain intrinsic advantages and disadvantages, although metals pose fewer problems for the designer than plastics or ceramics.

Scope for reinforcement

A composite matrix is required to fulfil several functions, most of which are vital to the satisfactory performance of the composite. Bundles of fibres are, in themselves, of relatively little use to an engineer, no matter how strong or rigid the individuals in the population may be, and it is only the presence of a matrix or binder that enables us to make use of them. The matrix in a fibre composite performs a variety of functions the appreciation of which is vital to an understanding of the true composite action which characterises the mechanical behaviour of a high-performance composite. These functions include binding the fibres together and holding them aligned in required directions; separating the individual filaments so as to prevent catastrophic crack propagation; protecting the filaments from damage by abrasion and from the environment; providing the composite with some measure of intrinsic compression strength; and helping to improve the toughness, among others. The potential for reinforcing any given material will depend to some extent on its ability to carry out some or all of these functions. We now consider the likely qualities of the various classes of matrix materials.

Limitations of conventional materials Over the past 30 years or so the strongest incentive for technological advance in the composites field has been in the development of reinforced plastics. This is a comprehensive term which describes a multitude of materials of diverse character, it is profitless to try to draw up a detailed table of comparative materials characteristics in order to assess their relative strengths and weaknesses. The reason for this is that the generic terms - metals, plastics, ceramics - each cover whole families of materials within which the range of available properties is sometimes just as broad as that which we associate with differences between the three classes. A comparison in general terms, however, can reveal some of the more obvious advantages and disadvantages of the different types of engineering materials, even though such generalisations can rarely be sustained in the face of more detailed examination. Such comparisons as may be made are as follows:
P l a s t i c s are of low density, they lack thermal stability, and they have good chemical resistance but only m o d e r a t e resistance to environmental degradation. They possess relatively poor mechanical properties, but they are easily fabricated and joined. Ceramics may be of low density (although some, like TaC, are very dense), they possess great thermal stability and they are resistant to most ordinary forms of attack. Although intrinsically very rigid and strong, they are all extremely brittle, and they can be formed and shaped only with difficulty. M e t a l s are mostly of medium to high density; only magnesium, aluminium and beryllium can compete with plastics in this respect. Many have good thermal stability and may be made corrosion resistant by alloying. They have generally useful mechanical properties and high toughness, and they are
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Metals
Metals are (arguably) the most versatile of engineering materials and they owe this versatility to the fact that they can be plastically deformed and can be strengthened by a variety of methods which, by and large, act by inhibiting the motion of dislocations. Ironically, as a consequence of the non-directional nature of the metallic bond, dislocations are highly mobile in pure metals which are therefore very soft. But by controlling the number and distribution of these defects the materials scientist can adjust the properties of a metal or alloy system to suit his requirements. There are limitations, however. Increases in strength can usually be achieved only at the expense of the capacity to deform plastically, with the consequence that the strongest alloys often lack the vital quality of toughness and are less tolerant of the presence of defects or stressconcentrating design features. Since brittleness is a drawback no designer can afford to underestimate, this leads to the use of large safety factors which, in turn, means that the full potential of high-strength alloys can often not be realised in practice. Many solid-state hardening methods used in alloys involve producing a material in a metastable state which may subsequently tend to revert to the more stable but unstrengthened condition if sufficient driving force is provided. Thus, alloys strengthened by precipitation hardening, such as the strong aluminium alloys, those depending on phase transformations of the martensitic type, such as steels, and those depending simply on the
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presence of a high dislocation density, as in heavily coldworked materials, will all tend to soften at elevated temperatures. The strongest aluminium alloys begin to lose their strengths at temperatures little over 150C, for example. Furthermore, in such metastable alloys the problem of fatigue is intensified because the cyclic deformation generates large quantities of point defects which enhance diffusion and can cause reversion of the metastable alloy structure even at room temperature. Many conventional metallic systems have the disadvantage of being relatively heavy. For many landbased engineering projects this will be of no consequence, but economic arguments relating to payloads (in civil aircraft) and tactical arguments relating to manoeuvrability (in military aircraft) have always been a powerful driving force for the use of low-density materials in aerospace engineering. In the energyconscious 1980s the economic incentive for lightening automobiles has already considerably influenced the motor car designer. For structural applications involving compression or flexural design loads, as opposed to those which are predominantly tensile, the relevant structural stiffness index is not simply Young's modulus, E, or the modulus/density ratio, E/d, but may instead be either of the ratios E / d 2 or E / d ~. For aerospace applications it has been shown that modifications to materials that result in lowered density may be more profitable than attempts simply to improve their strength or stiffness. The foregoing arguments show why it is worthwhile to attempt to use strong, stable fibres of low density to reinforce (without inducing brittleness) some of the lighter engineering metals and alloys. Ironically, at a time when many aircraft manufacturers have already made great strides in incorporating substantial quantities of carbon, glass and Kevlar-49 fibre reinforced plastics in both fixed wing aircraft and helicopters, for both structural and non-structural applications, the advanced state of development of the high-strength, low-density aluminium/lithium alloys for aerospace use has some engineers believing that these alloys offer almost all of the advantages of carbon fibre composites, and without the need for the large-scale retooling that is necessary for economic composite production. The argument continues: the outcome may be of considerable significance to the industry.
Polymeric materials

Some applications of composites

The panels contain a brief listing of some current and proposed applications of composite materials in various branches of industry. It is not intended to be comprehensive or all-embracing, but merely to give an indication of the range of possibilities for designers.

Aerospace
A wide range of load-bearing and non-loadbearing components are already in use in both fixed-wing and rotary wing aircraft. At the present time the dominant design philosophy is one of substitution where appropriate, with conventional metallic components and high-performance composites being used in combination. Many military and civil aircraft now contain substantial quantities of light-weight, high-strength carbon, Kevlar and glass fibre composites, as laminated panels and mouldings, and as composite honeycomb structures with metallic or resinimpregnated paper honeycomb core materials. They are used in air frames, wing spars, spoilers, tail-plane structures, fuel tanks, drop tanks, bulkheads, flooring, helicopter rotor blades and structural components, pressurised gas containers, radomes, nose and landing gear doors, fairings, engine nacelles (particularly where containment capability is required for jet engines), air distribution ducts, seat components, access panels, and so forth. A particularly interesting (and important) application of boron/epoxy composites - one of the few - is in its development as a means of repairing battle damage (patching) in metal aircraft structures. Many modern light aircraft are being increasingly designed to contain as much lightweight composite material as possible. The Boeing Chinook helicopter contains some 23% by weight of composites: the Slingsby sailplane is constructed almost entirely of GRP. For elevated temperature applications carbon-fibrereinforced carbon is in use or is under consideration. Concorde's disk brakes are made from this material, rocket nozzles and re-entry shields have been fashioned from it, and there are other possibilities for its use as static components in jet engines. Rocket motor casings and rocket launches are also frequently made of reinforced plastics. (see also: Technical Report, August 1991 issue)

Few polymers are thermally stable by comparison with metals or ceramics and even the most stable, like the polyimides, or poly(ether ether ketone) (PEEK) are degraded by exposure to temperatures above about 300C. There is nothing that reinforcement can do to combat chemical degradation, but the associated fall in strength and increase in time-dependent (creep or viscoelastic) deformation, a feature common to all polymers, though less serious in cross-linked resin systems than in thermoplastics, can be delayed by fibre reinforcement. A more serious problem in polymers is their very low mechanical strength and stiffness in bulk form: and like metals, the weakest plastics tend to be ductile (or even tough) but the strongest tend to be brittle, although there are exceptions. Polymers are traditionally insulators and in their application as such strength is usually a secondary
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consideration. It is increasingly likely, however, that the electrical and thermal conductivity of plastics reinforced with carbon fibres will be of considerable importance in many aeronautical applications. Most polymers are already low-density materials, and the addition of fibres does not confer significant advantages in this respect. In such materials as these, then, there is perhaps the greatest scope for improvement, and it is in the field of fibre-reinforced plastics that the greatest successes have already been achieved. There is a thriving, international reinforced plastics industry, for which both the science
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Table 1
Type and polymer

Thermal stability of some matrix polymers

Symbol Crystallinity T~* (oC) Max use temp (C)

Thermosets:
Polyester Epoxy Phenolic Bismaleimide Polyimide PE Ep Ph BMI PI no no no no no 80-100 120 - 180 130 - 180 180 - 200 300 - 330 50 150 200 220 280

Thermoplasts:
Polyamide (Nylon) Polycarbonate Polysulphone Poly(ether sulphone) Poly(phenylene sulphide) Poly(ether ether ketone) Poly(ether imide) Thermoplastic PI PA PC PS PES PPS PEEK PEI TPI yes no no no yes yes no no 80 145 190 230 100 143 210 270 125 125 150 180 260 250 170 240

*Cure temperature for thermosets: glass transition for thermoplasts

and technology are highly advanced, although it appears that the level of awareness of the merits of reinforced plastics on the part of designers in general engineering is very low. The same is not true, however, of the aerospace industry for which the potential benefits of very high strength and stiffness, combined with low density, are easily recognised. An indication of the thermal stability of some typical polymer matrix materials, including some of the new thermoplasts, is given in Table 1.

Ceramics and glasses Glasses have high chemical stability, but many lose their mechanical strength at relatively low temperatures as they pass through the glass transition (T~). Special glasses have been developed with high Tg, however, and many are at least as resistant as some of the less stable steels. The principal problem with glassy materials is that they are always brittle. The difficulty is not that glasses are not strong, for with careful preparation very high strengths can be achieved. The drawback is that they are highly notch.sensitive, and their measured strengths are in consequence subject to wide variation at ordinary temperatures. They are not able to relieve stress concentrations at crack tips by plastic deformation, and they are not, therefore, fail-safe. A constant disadvantage, aggravated by low thermal conductivity, is that glass usually has poor thermal shock resistance unless it also has a low thermal expansion coefficient. Many of these difficulties can be overcome by reinforcement with fibres like carbon or silicon carbide, and with the added bonus of a saving in weight. Most ceramics, whether the conventional whitewares and porcelains, or pure ceramics like AI203, suffer from the same defects as glasses in the sense that though they are potentially high-strength solids, they are also brittle and highly notch-sensitive. Most ceramics retain their strength to very high temperatures, however, unlike glasses, and several have good thermal shock resistance. Improving toughness and reducing notch sensitivity are perhaps the only reasons for attempting to reinforce such materials since the modulus of many ceramics is not very different from that of carbon fibre. For high-temperature stability it could be supposed that
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the best possiblity for reinforced ceramics is perhaps an equilibrium system in which whisker-like crystals of a reinforcing phase are grown within a polycrystalline matrix of a chemically-related ceramic. Concrete is a ceramic material in which crystalline aggregate particles are embedded in a glassy or microcrystalline silicate matrix. It is therefore a composite, but like most ceramics and glasses it is brittle and exhibits a very low tensile failure strain. Engineers cope with this by using it exclusively in compression or with macroscopic reinforcing bars to carry tensile loads. In design, the tensile load-bearing ability of concrete is ignored. Reinforcement of concrete in the composite sense has been widely studied, with attempts to produce stronger, stiffer and tougher structural materials by adding fibres of asbestos, glass, steel, polymeric materials, and even carbon. Improved properties can be obtained, although usually only at the expense of a severe economic penalty, given the fact that concrete is the cheapest structural material available. The addition of even a few percent of the cheaper reinforcing fibres may raise the price sufficiently to cause the engineer to accept a thicker section of unreinforced material in preference to the more expensive thinner section of reinforced concrete. Such small additions do very little, in fact, to increase the cracking stress or elastic modulus of cement, but by introducing complex cracking and failure modes they can substantially improve the overall work to fracture. The scope for improvement of bulk poured concrete is therefore probably negligible. It is much more likely that the present trend towards changes in design philosophy and the use of speciality products in fibre-reinforced concrete will continue. High fibre volume fractions of well-aligned fibres can be obtained by vacuum dewatering and filament-winding and the products of these processes can be used in much thinner sections than is conventional with concrete. Traditional attitudes and design procedures are of course no longer applicable for such materials. Carbon Carbon is a unique material with many attractive engineering qualities. It can be prepared in a variety of forms - conventional hot-pressed carbons and
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graphites, densified (impermeable) graphite, pyrolytic graphite, and vitreous carbon - with a wide range of engineering properties. It is valuable for its lubricating properties, its electrical properties, its nuclear characteristics and, in the pyrolytic and vitreous forms, for high strength and resistance to oxidative and chemical attack. The opportunity to improve the mechanical properties of such an important material and reduce its brittleness somewhat has been the driving force for the development of an invaluable material, carbon fibre reinforced carbon, that has been used for rocket nozzles, aerospace components, and surgical implants, to mention only three areas of application.

Reinforcing filaments
A search for materials that should theoretically have high strength and stiffness leads directly to elements or compounds possessing a high density of either pure covalent or mixed covalent/ionic bonds. Elements having these characteristics are carbon, boron and silicon, while compounds that suggest themselves are ceramics like SiO2, SiC, A1203, BN and Si3N4. It is of course not coincidental that these are all very brittle solids of low density. Such materials are unpromising in the bulk form, and it is only when we convert them into fine fibres, eliminating as far as possible the strength-limiting defects normally present in brittle solids, that we obtain strong, rigid materials capable of being used in engineering structures. The most important fibres that are at all widely used in modern man-made composites are glass (SiO2), carbon, boron, SiC, and highly-drawn polymers like polypropylene, poly(ethylene terephtha. late) (PET), and aromatic polyamides (sometimes known as Aramids) such as poly(paraphenylene terephthalamide) (Kevlar 49). We now consider some aspects of the major reinforcing fibres in a little more detail.
Glasses Glass fibres are as strong as any of the newer inorganic fibres but they lack rigidity on account of their molecular structure. The properties of glasses can be modified to a limited extent, but it is rarely worthwhile to use any other than ordinary borosilicate E-glass in composites despite the availability of slightly stronger and stiffer glasses like S (or R) glass. Attempts to produce crystallisable glasses with a view to making glassceramic fibres have not apparently been profitable since, although the rigidity is thus improved, the high degree of surface perfection to which vitreous glass owes its high strength is harder to achieve in a polycrystalline glass-ceramic. Ordinary glass fibres cannot be used to reinforce ordinary Portland cement because the alkaline environment is highly corrosive towards normal silicate glasses. Glass reinforced cements (GRC) other than the infamous high alumina variety (HAC) lose strength rapidly and exhibit none of the toughness of cements reinforced with steel wire or organic fibres. Pilkington in the UK developed alkali-resistant glasses, marketed as Cemfil, which are derived from soda-silica glasses containing zirconia, although these are by no means immune to attack by the alkaline environment. Further research appears to be required in this area, and it may perhaps always be necessary to use protective polymer
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coatings on glasses to be used for GRC if long-term structural requirements are involved. As a result of rapid cooling from the molten state, certain metallic alloys may be produced in a glassy state with unusual characteristics. Typical alloys that can be treated in this way include various combinations of Fe, Ni, Cr, P, B, Si and C. When cooled at rates of up to 106 degrees per second, such as may be obtained by 'splat' quenching or melt spinning, dense homogeneous tapes or filaments are obtained with an amorphous, or perhaps a micro-crystalline, structure. The elastic modulus of a glassy alloy is only 70 to 80% of that of the crystallised form, values of 100 to 150 GPa being common, and the best of such glasses are thus about twice as stiff as ordinary glass. The strengths of glassy alloys are usually of the order of E / 5 0 - exceptionally high among structural materials - the alloy FesoB2o having a yield strength of 3.6 GPa. Being capable of plastic deformation by highly Iocalised shear flow, these glasses are not brittle like ordinary glasses, and they are very corrosion resistant. With such a combination of properties, metallic glasses appear to be ideally suited for polymer or metal reinforcement, although they have not yet been used commercially for this purpose. Continuous tapes can be produced with width-tothickness ratios of 20 or more, and the use of such materials for reinforcement has significant advantages, particularly in respect of transverse strength and toughness. Rapidly.cooled alloys are also being studied in combination with resins for their special magnetic or magnetostrictive qualities.
Carbon fibres

By oxidising and pyrolysing a highly drawn textile fibre such as polyacrylonitrile (PAN), preventing it from shrinking in the early stages of the degradation process, and subsequently hot-stretching it, it is possible to convert it to a carbon filament with near theoretical modulus, although the final strength is usually well below the theoretical strength of the carbon-carbon chain. The influence of strength-limiting defects is considerable, and clean.room methods of production can result in substantial increases in tensile strength of commercial materials. Fibres are usually surface treated prior to sale by chemical or electrolytic oxidation methods in order to improve the quality of the fibre/matrix bond. In the early days of fibre production, two varieties were available, a high modulus (or HM) fibre with a modest strength, and a high strength (HS) variety with a modest modulus. The user was often therefore faced with a compromise. The first attempt to move away from the two extremes was by the introduction of a high-strength fibre with a slightly improved stiffness, the XA8 fibre which has for many years been the first choice of aerospace users. In recent years, however, improvements in processing methods and control of microstructure have led to the introduction of a new generation of fibres known as the IM, or intermediate modulus fibres which have significantly higher strength and stiffness than other types of carbon filament, and it is these that are now the preferred reinforcements for most high performance CFRP on account of their high strains to failure. Thus, depending upon processing conditions, a wide range of mechanical properties (controlled by structural variation) can be obtained, and
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Automotive engineering
There is increasing interest in weight reduction to permit both energy conservation and increased motoring economy. Reduction in the weight of an automobile structure achieves primary weight saving and if carried to sufficiently great lengths enables the designer to use smaller power plants, thus achieving substantial secondary improvements in fuel economy. The majority of automotive applications involve glass-reinforced plastics because the extra cost of carbon or Aramid fibre is rarely considered to be acceptable in this market. Even so, the cost of using GRP is usually being weighed against the much lower cost of pressed steel components, and the substitution is often rejected on purely economic grounds, leaving aside the question of energy saving. A wide range of car and truck body mouldings, panels and doors is currently in service, including complete front-end mouldings, fascias, bumper mouldings, and various kinds of trim. There is considerable interest in the use of controlled-crush components based on the high energy absorbing qualitites of materials like GRP. Leaf and coil springs and truck drive shafts are also in service, and GRP wheel rims and inlet manifolds have been described in the literature. Selective reinforcement of aluminium alloy components, such as pistons and connecting rods, with alumina fibres is much discussed with reference to increased temperature capability.

Boron and BorSiC Commercial boron fibres are thick filaments of the order of 0.1ram in diameter produced by pyrolytic deposition onto fine tungsten filaments. The basic properties of the boron fibres are similar to those of the early carbon fibres, but the larger filaments are more difficult to handle in manufacturing processes than the much finer carbon or glass fibres. Modifications to the basic boron fibres have been made by the introduction of fibres coated with boron nitride or silicon carbide, the latter being referred to as BorSiC fibres. These are diffusion barrier coatings that have been developed to inhibit the rate of degradation of the filaments when used as reinforcement for MMCfor high temperature use. Although a good deal of work was carried out at one time on the possibility of using boron as a reinforcement for plastic matrices, such materials could not compete with GRP and CFRP, and current interest in BorSiC remains limited to its use in MMC as a competitor for SiC itself.

Silicon carbide Continuous SiC monofilaments were first produced by pyrolytic decomposition of gaseous silanes onto fine filaments of carbon or tungsten. Like boron, these are thick fibres which continue to be of major interest to manufacturers of metal-matrix composites. The alternative production method, analogous to that for carbon described earlier, is based on the controlled thermal degradation of an organic precursor. This process, based on the work of Yajima, typically takes a precursor such as some mixture of dimethyl dichlorosilane and diphenyl dichlorosilane and converts it in an autoclave to a polycarbosilane from which a continuous fibre is made by melt-spinning. The fibre is then converted by pyrolysis at 1300C into a/3-SIC fibre of about 15/~m diameter. The characteristic commercial fibres can therefore be chosen from this range so as to fibre of this type is that known as 'Nicaion' which is give the desired composite properties. Although the marketed by the Nippon Carbon Co. It has a rough fibre is highly organised and graphite-like, the structure surface, making for good stress transfer, but is is not identical with that of graphite and the fibres should somewhat reactive towards oxygen, it is well wetted by not strictly speaking be referred to by that name, as is molten metals, yet is reasonably stable as a reinforcement for MMCbased on aluminium and copper. common in the USA. Carbon fibres are inherently expensive, since they are By comparison with the monofilamentary form of SiC, produced from precursor textile fibre of high quality. this kind of fibre suffers from the fact that it contains Since 1967 the price has fallen from several hundred a proportion of silica, which renders it unusable as a /kg to tens of /kg, depending upon quality. Carbon reinforcement for alumina in ceramic matrix composites is, nevertheless, still an expensive reinforcement: the on account of the mullite reaction that takes place current cost to a manufacturer of commercial quality during processing. It is also somewhat lacking in creep preimpregnated sheet (prepreg) for an IM fibre in a resistance, and structural modifications to improve this modern flexibilised epoxide resin, for example, is of the are being undertaken. order of 40/m 2. The search for a cheaper precursor In the context of SiC and boron-based fibres, it fibre that began in the sixties still continues, therefore. should be noted that despite their extra handling Experiments on the production of glassy carbon difficulties, the large diameter monofilamentary filaments from non-graphitising resins such as phenolics, materials have an important advantage over the finer and on filaments made from petroleum or coal-based fibres. The compression strengths of conventional CFRP pitches were unsatisfactory because of their low and GRP are notably lower than their tensile strengths. stiffness. More recently, however, improvements have It is interesting to note that although significant been made in techniques for producing fibres from improvements have been achieved in the tensile mesophase pitch by the elimination of defects in strengths of carbon fibres and composites made from precursor yarns and carbonised filaments, and moduli them, there has been far less improvement in the of the order of 400 GPa with reported strengths of 2.5 compressive strengths of the same materials. This is to GPa or more have been discussed. Mesophase pitch is a considerable extent due to the fact that fine filaments a cheap precursor that produces a graphite fibre with are unstable against buckling under compression forces, a high yield - 80%, compared with 50% for PAN- and on a simple Euler basis, a filament ten times as thick based production. is bound to be far more stable.
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Bioengineering
Carbon-fibre-reinforced plastic and carbon components are coming into use for prosthetic purposes, such as in orthopaedic fracture fixation plates, mandibular and maxillary prostheses (jaw remodelling, for example), and for external orthotic supports in cases of limb deformity etc. The femoral component of some light-weight hip prostheses are made from a composite stem surmounted by a ceramic ball. Pyrolytic carbon is used to manufacture heart valve components, and the substitution of a carbon/carbon composite is not unlikely. Some recent developments in the use of particulate hydroxyapatite as filler in a thermoplastic composite for bone remodelling or replacement also look promising.

Aluminium oxide
Following early enthusiasm for and disillusion with sapphire whiskers for the reinforcement of metals, the Du Pont Company developed an improved oxide fibre in the form of a polycrystalline yarn known as FP fibre. Said to be essentially ~> 99% ol-AI203, the filaments have a modulus comparable with those of boron and carbon, and a strength of the order of 1.8 GPa. This fibre too has a rough surface and is well-suited for the reinforcement of metals such as aluminium and magnesium on account of its chemical inertness, hightemperature stability, and its ability to form a good bond with these metals although it may be necessary to use alloying additives to promote good bonding. It is claimed that the strength and modulus of these fibres, unlike those of Nicalon, remain unchanged at temperatures up to 1000C. An alternative form of alumina reinforcement is that marketed by ICI under the name Saffil. This was introduced first in 1979 in response to a need for a lower priced reinforcing filament for advanced composites than those currently available, and was followed in 1982 by an improved grade (Rr). The fibre is manufactured in the form of a continuous mat which can be used as layers, or preforms, or as shredded material, with controlled fibre aspect ratios ranging from 50:1 to 500:1. It is a ~-A1203 crystal phase with added silica which improved wetting by a wide variety of aluminium alloys without the need for additional lithium or other wetting aids. The material combines ease of handling with low cost (up to one tenth the cost of continuous reinforcing fibres), and unlike competing fibres is produced on a large scale commercial plant. Its intrinsic properties are as good as or better than those of many competing fibres, although the fact that it is produced as a random mat means that the potential strength of composites containing it is more limited.

molecular 'chain structure can be achieved by superdrawing in the solid state, in this process, developed by Ward at Leeds University, both the crystalline and non-crystalline phase of the initially isotropic polymer are stretched out and aligned and there is an increase in crystal continuity. Such fibres have high strengths and elastic moduli similar to those of glass and aluminium. Apart from their excellent mechanical properties such fibres have the important advantage over inorganic fibres that they are not brittle. The other major development in organic fibres over the last two decades has been the production by the Du Pont Company of aromatic polyamide fibres, collectively known as Aramids, and of which the best known in the composites industry is Kevlar.49. These polymers are based on p-oriented diamine and dibasic acid intermediates which yield liquid crystalline solutions in amide and acid solvents. These solutions contain highly-ordered extended-chain domains which are randomly-oriented in the absence of force, but which may be oriented by inducing shear forces in the liquid. Highly-oriented fibres can therefore be produced by wetspinning these solutions, and poly(paraphenylene terephthalamide) (PPT) fibres such as Kevlar have strengths of the order of 2.6 GPa and moduli of up to 130 GPa, depending on the degree of alignment of the polymer chains. Having properties intermediate between those of carbon and glass, Aramids offer an extra degree of flexibility in composite design, and, again, they are inherently tough. Two disadvantages of the current grade of Kevlar-49 are that it is hydrophilic and lacking in resistance to shear and bending forces on account of its internal structure. New developments at Du Pont are said to have overcome these problems.

Whiskers
Potentially the strongest of all reinforcements, these fine, short, monocrystalline fibres were regarded in the seventies as being of no serious interest as reinforcing fibre, partly because of their high cost, partly because of the difficulties of manufacturing high.peformance composites containing them, and partly because of their instability in contact with metal matrix alloys (see the paper by Calow and Moore referred to earlier). This view was unchallenged until the end of the decade when Exxon announced that advances in processing had led to the development of high performance SiC whiskers "at a potential cost of no more than a few dollars per pound". Other recent developments include the manufacture of cheap, whisker-like fibres from rice-hulls which are considered to be an important possibility for use in ceramic matric composites. Developments in this direction are still awaited. A comparison of the physical characteristics of a range of common and less common reinforcing fibres is presented in Table 2.

Developments In composite systems

Polymer composites
It is this class of materials, of all composites, that has developed most rapidly ~o the stage of practical application in a wide range of engineering products during the last d e c a d e . But apart from the improvements in matrix and fibre properties already
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Organic fibres
Bulk polymers have Young's moduli no greater than 0.1 GPa, but if the polymer is spun into fibres and cold drawn so as to develop a high degree of molecular orientation, substantial improvements in both strength and rigidity can be achieved. In particular, polyolefin fibres with an exceptionally highly-orientated, extended
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Table 2

Typical mechanical properties of reinforcing fibres

Fibre
Relative density 1~ 1,7 1.9 1.8 2.0 2.6 2.7 4.0 3.3 3.2 2.6 2.4 3.0 2.5 2.6 2.2 1.5 1.0 7.8 diameter ~rn) 7-10 7-10 7-10 7-10 10 130 142 20 3 1-50 10 10 120 10 10 3-15 12 12 250 Young's modulus (G Pa) 400 200 220 300 380 440 400 350 300 480 200 210 430 70 90 80 100-150 130 117 210 Tensile strength (G Pa) 2.0-2.8* 3.0-3.5* 3.2* 5.6* 2.0- 2.4 3.5 3.1 1.8 2.0 up to 7.0 2,5-3.0 2.9 4.0 1.5- 2,0 4.6 3.5 3.6 (yield) 3.6 2.6 2.8

Material
Carbon(PAN) HM HT XA IM Carbon(mesophase) Boron BorSiC e-AI=O3(FP) ~AI20 s (Seffil) SiC (whisker) SiC (Nicalon) SiC ('l'ymnno) SiC (monofilament) E glass S (or R) glass Quartz (99.95% pure) Fe=B=o (metallic glass) Aromatic polyamide Polyethylene (UHM)

High carbon steel *Tested at 5 cm gauge length

Chemical engineering
A substantial amount of GRP is currently in use in chemical plant for containers, pressure vessels, pipe.work, valves, centrifuges etc. These may be filament-wound or moulded components for containment of process fluids.

Civil/structural engineering
Again the bulk of composites used in this field are glass-reinforced plastics. The low inherent elastic modulus of GRP is easily overcome in buildings by the use of double curvature and folded plate structures: thin GRP panels also offer the advantage of translucency. Glass reinforced cement (GRC) products are gradually being introduced as structural cement-based composites, but these GRC are still regarded with some suspicion by architects who prefer to consider only non-load-bearing applications for glass-reinforced cement. Development of suitable highly.drawn polymer fibres and net-like polymeric reinforcement has made it possible to produce stable polymer-reinforced cement for a variety of purposes. But concrete is the cheapest engineering material available, and it requires very little in the way of expensive reinforcing filaments to be added to it to make it uncompetitive. The answer is usually to use more concrete! But GRC is perhaps likely to attract the more adventurous designer with light.weight concrete structures in mind (thin shell structures for example). A good deal of GRP is used in this industry for folded-plate structures, cladding panels, decorative "sculptured" panels, services mouldings and ducting, racking, pipework, rainwater mouldings, domestic and industrial water tanks, form-work for concrete, and complete small structures like footbridges. Light-weight composite panelling for partitioning and similar applications has also been tried.

referred to, the major expenditure of effort and growth in reinforced plastics has been in the areas of manufacture and design, rather than in materials as such. A wide range of practical manufacturing processes has been developed, from hot press moulding of relatively crude moulding compounds containing mixtures of resin, particulate filler, and chopped fibres, to the use of computer-controlled equipment for the accurate construction and consolidation of high. performance laminates designed with the aid of software based on elaborate micromechanics and laminate theory models. Recognition that composites offer the possibility of made-to-measure materials and completely new solutions to engineering problems has been followed in many (but not all) industries by acceptance of the philosophy that integrated functional design must replace piecemeal substitution if the advantages of composites are to be properly realised with appropriate cost savings. The re.design of a complex system which follows naturally from a learning period of step-wise substitution (the inevitable first stage in the introduction of new materials and concepts) usually manifests itself as a simplification of the system as a whole. In most cases this simplification is achieved by integration of several parts into a single component permitting, as a consequence, a rationalisation of the processes and methods of fabrication. It is true that this integration brings with it the attendant problems of inspection and reliability during service, and of recycling at the end of service. There are already many examples in the aerospace and transport industries of redesign by integration. A notable development in the industrialisation of composite materials that has come about in the last decade, due in no small measure to the process of intregration at the design and manufacturing levels, is that there has grown up an industry in which, increasingly, all necessary skills and facilities are being encompassed within a single enterprise. The primary producer of the raw materials (fibres and resins), the converter (producer of fabricated products), the design

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engineers reponsible for the manufacturing processes and the design of the finished products, and the scientists responsible for Rr_,Dfunctions, are all being brought together, either as loosely associated networks, or as divisions of a single company. In the UK, for example, BP, originally a chemical company with interests in manufacturing plastics raw materials, now also owns a fibre p r o d u c e r and c o m p o s i t e s manufacturing plants, in addition to having a large corporate RE,D facility. The current developments relating to the composites activities of large corporations like ICI and BP perhaps ruin the value of this philosophy as far as the UK is concerned. The state of development of the scientific base of the polymer composites field is uneven. The elastic analysis of anisotropic materials has occupied many academic and industrial groups for two decades, to such an extent that our current ability to predict the elastic properties of a given composite, or to design a composite to meet a given set of conditions (within the elastic response region) is sufficiently accurate for most practical purposes, although theoreticians are hard people to satisfy in this respect and there is always a continuous process of refinement. A good deal of CAD software is nevertheless available that permits rapid calculation of the behaviour of highly complex laminates, and is able to take into account the additional problems introduced as a result of thermal stresses and the effects of moisture. Accurate prediction of strength is more difficult than prediction of elastic properties because it depends not only on the properties of the constituents but also on the mechanism of failure. The failure modes of composites vary widely because they depend on the way damage accumulates in the material under load. This damage, which is an inherent characteristic of the composite (and includes resin cracking, fibre breakage, debonding, transverse ply cracking, delamination, etc) is determined by both the microstructural and macrostructural nature of the material. Calculation of the strength of a laminate may be done as an extension of the classical thin laminate theory, but it requires the postulation of an appropriate failure criterion, such as those of Tsai and Wu based on a generalised von Mises approach. The method is usually one of "ply discounting', ie removing from the composite the first ply that fails as the load is raised and then recalculating the stress distribution for those remaining until the failure of one more ply results in destruction of the whole laminate. This method will usually underestimate the true strength of a laminate. Fracture mechanics methods have frequently been applied to designing with composites, but caution is necessary. Under some circumstances linear elastic fracture mechanics (LEFM)appears to be capable of being used. For example, in brittle composites with high fibre/resin bond strength or with brittle matrices, crack paths may be planar and the process (damage) zone small. The intrinsic heterogenity of the composite may not be apparent in such composites. Also, in random composites anisotropy is not a problem, and in cases of the growth of delaminating cracks LEFMand the Paris Law for fatigue appear to be capable of predicting life. In tough composites, however, damage is widespread and complex and single crack failure may not occur. Also in composites of low fibre content the uniformity
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Electrical engineering
Typical applications are radomes, structural components for switch gear, power generator coolant containment and large-diameter butterfly valves, high-strength insulators (eg for overhead conductor systems), and printed circuit boards. The majority of applications in this field again use GRP although the use of composites which are more thermally stable and more moisture-resistant is increasingly predicted for sensitive small-scale electronic components. Many prototype and practical wind-generator designs incorporate GRP or hybrid blading.

Marine Engineering
A vast range of pleasure craft has long been produced in GRP, but much serious use is also made of the same material for hull and superstructure construction of minecountermeasures vessels and various kinds of submersibles, including casings for towed transducer arrays for sea-bed sonar mapping. Also in composites of low fibre content the uniformity assumption is no longer valid. There is still a great deal of uncertainty over the question of the validity of LEFM, and generalisations should not be made. Composites suffer from fatigue as a result of the gradual accumulation of damage during repeated loading. There is a great deal of experimental information about fatigue behaviour of most kinds of composites and a wealth of data, but at present we have no generally useful guiding principles to help us design against fatigue. S/IogN data have been produced, but because of the complexity of fatigue damage and the fact that it is highly sensitive to materials and geometric variables, no single model appears to be capable of predicting fatigue response. It appears generally to be true that the stiffer a given laminate is the higher will be its fatigue resistance (ie the lower the slope of the S/IogN curve) at least within the normal laboratory test framework, which is limited by the time it takes to reach say 10 7 cycles with a material that exhibits hysteretic heating (and consequent thermal degradation). We have little idea, however, of the very long-term behaviour of composites at normal design stress levels. Apart from the general continuing development of new matrix resins with better thermal stability or with increased strain to failure (assumed to improve the overall toughness and fatigue resistance of the composite) and improvements in fibre performance (also with a view to obtaining increased failure strain), most of the progress made in the field of polymer composites over the last two decades has been in relation to improving our understanding of the behaviour of composites, increasing the range of manufacturing processes and products, providing better predictive models and design codes based upon them, all of these being necessary to improve the level of exploitation of these materials.

Metal matrix composites

Following the lull in activity in the MMC field previously referred to, there has been an extremely rapid growth
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of R&D activity since the early 80s. It was apparent at the end of the seventies that in the USA, particularly, a great deal of work was in progress, but a US government embargo on the transmission of strategic information outside the country prevented general knowledge of the details of this work. Even at International conferences in the USA it became common to hold closed sessions, to which non-nationals could not gain access, at which MMC work was discussed. Of the renewed activity in MMC, not all is associated with fibre reinforced materials. Several organisations on both sides of the Atlantic are developing particulate MMC, a class of materials that was formerly familiar to metallurgists as "cermets", although the classical cermet, the cemented carbides and other metal-bonded ceramic materials mostly used for cutting tools, contained a very low proportion of the metallic phase by comparison with modern MMC.The most familiar of the modern MMCare made by the incorporation of SiC particles (after treatment to improve particle/matrix adhesion) at volume fractions of 0.1 to 0.3 into aluminium alloys by various routes, including co-spraying, powder metallurgy, and liquid infiltration. These materials are claimed to show significant increases in specific stiffness and strength, although at the expense of ductility and toughness, with the advantage (eg over reinforced plastics) that they can be processed by conventional forming methods. For a 25% loading of SiC in 7090(T6) alloy, for example, a modulus of about 120 GPa, a tensile strength of 800 MPa, and a failure strain of 2% are typical. Short-fibre reinforced MMC are commonly made by liquid metal infiltration or squeeze casting into preforms of fibres such as Saffii, a net-shape forming technique that has much to recommend it for localised or general reinforcement of components such as automotive pistons, connecting rods, etc. among others. Powder processing is less satisfactory because of the possibility of fibre damage. There is now a wide range of continuous fibres available that are ideally suited for reinforcement of MMC, as Table 2 shows, and a wide variety of production techniques has been developed to make use of them. Liquid metal infiltration, squeeze casting, electroplating, diffusion bonding of plasma-sprayed tapes, and explosive welding have all been used, in addition to conventional roll-bonding and hot-pressing. For lowtemperature applications, carbon fibre reinforced aluminium alloys still hold possibilities, provided the problems of wetting (during manufacture) and galvanic corrosion (during service) can be overcome. But Nicalon SiC would still appear to be a better solution for most purposes, although even in this case there are still problems of interfacial reactions and instability during processing to be solved. For high-temperature service, different solutions are called for. In the next generation of gas-turbines, for example, it is still unclear whether MMCor ceramic matrix composites (CMC) may take the place of current metallic alloys in certain critical applications. As the temperature rises, we return to the problem of stability in service, and the need for diffusion barriers, the same problem that was faced in the 60s and for which no acceptable solution was found. The thermodynamically stable solution to the highMATERIALS & DESIGN Vol. 12 No. 5 OCTOBER 1991

temperature service problem may still rest with MMC produced by directional solidification from eutectic and other two.phased alloys - the so.called in situ composites. Very early in the history of composites such materials were already developed to a very high level, complex refractory alloy systems being used to obtain relatively high volume fractions of stable, fibrous carbide phases in superalloy or refractory metal matrices. Such alloys were frequently stronger and stiffer than conventional high-temperature alloys, even at temperatures in excess of 1000C, although some were insufficiently resistant to thermal fatigue to be of use. The French COTACalloys, consisting of TaC reinforced cobalt, already available in the mid 70s, were claimed to possess creep properties equivalent to those of conventional superalloys up to 900C and to be superior to them above that temperature, and were also resistant to thermal fatigue. They appeared then, and still appear, attractive for blades and vanes in low temperature turbine stages of advanced turbofan engines operating at temperatures in excess of 1000C, but we appear to hear less of these materials than might have been expected. In general one of the key problems for MMC users is likely to be the need to develop satisfactory joining techniques: this is clearly likely to be more of a problem for continuous fibre composite than for the other forms that we have discussed.

Sport
Perhaps the most visible development in the use of composites has been in the sports goods industry. Manufacturers have been quick to seize on the potential advantages of new materials like carbon and boron fibre composites over conventional wood and metal for sports equipment of all kinds, but whether the average sportsman (and perhaps even some of the above average ones) who have been inveigled into buying this more expensive composite equipment in the hope that it would improve their game have been able to demonstrate genuine improvement remains uncertain. GRP vaulting poles were perhaps the earliest of the composite sports gear, but one can now obtain tennis rackets, cricket bats, golf clubs, fishing rods, boats, oars, archery equipment, canoes and canoeing gear, surf boards, windsurfers, skateboards, skis, ski-poles, bicycles, and protective equipment of many sorts in composite materials of one kind or another.

Domestic
Injection-moulded reinforced thermoplastics and polyester moulding compounds are perhaps the most common composites used in consumer items for the domestic market, and the range is vast. Mouldings of all kinds, from kitchen equipment of all kinds to casings for the whole gamut of domestic and professional electrical equipment, motor cycle crash helmets, televison and computer casings, and furniture.

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Ceramic and glass matrix composites Early work in this area was not particularly fruitful, partly because in the 60s and early 70s there was no real incentive. But, again, interest has been rekindled in the past decade in the possibilities of overcoming some of the early difficulties, principally by resorting to the use of ceramic/ceramic or ceramic/glass.ceramic systems instead of metal fibre reinforced ceramics. It is interesting to reiterate some of the arguments for developing an intensive programme in this area. With appropriate fibres and fibre/matrix combinations, good increases in strength and, particularly, toughness are obtainable over unreinforced ceramics (even 'tough' ceramics like PSZ). This potential increase in toughness is in fact the main driving force for such RZ,D in this field as is now being carried out. Both ambient and high-temperature toughening are required, and ct,tc may provide both. The theoretical base of the subject offers the prospect of substantial improvements in high-temperature strength and toughness, based on a combination of mechanisms, including crack deflexion by rod-shaped reinforcements, dispersion and transformation effects in fine-grained mixtures, and debonding and fibre pull.out processes. Fabrication processes are likely to be complex and need to be carefully optimised because of the inevitable sensitivity of materials properties to microstructures controlled by processing conditions and interactions. There is an urgent need for a detailed correlation between the microstructure and chemistry of CMC materials and their properties. Work in this direction is moving apace in the USA, rather less rapidly in the UK. Although many engine and similar applications may be satisfied by existing materials, either with monolithic metallic components or MMCwith refractory coatings or metallic components with ceramic inserts, hightemperature applications will certainly depend on improved materials of a more refractory nature. There is therefore a large potential market for improved ceramics for engine components, for high-temperature plant, for heat-exchangers, etc., with appropriate strength and toughness and with adequate resistance to thermal shock, thermal fatigue, and high-temperature corrosion resistance. It is perhaps also worth remarking that although the driving force for developments in the CMCfield has most frequently been the needs of high-temperature applications in the aerospace industry, there are many other branches of engineering - automotive, chemical, marine, and general engineering, for example - where there is a need for reliable economic components possessing good strength and stiffness, together with wear/abrasion resistance and/or corrosion resistance, in combination with adequate impact and thermal shock resistance at ordinary or only slightly raised temperatures. For many such applications there is no need for resistance to elevated temperatures, and the problems relating to fibre/matrix interactions at high temperatures are not as serious as in gas turbine applications, for example, provided processing methods can be developed which do not require too high firing temperatures normally associated with ceramics manufacture. Recent work on cMc has so far largely followed relatively familiar routes in attempting to reinforce
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glasses (like borosilicate) and glass ceramics (like LAS, CAS and BMAS)with fibres such as Nicalon and Tyranno SiC. Substantial improvements in mechanical properties have been achieved, by comparison with early carbonfibre/glass composites, for example, the fibres being impregnated with a slurry of fine glass powder and subsequently hot-pressed (and ceramed where appropriate). Companies like Coming in the USA offer such materials for commercial sale. Critical control of manufacturing conditions is needed to produce appropriate interracial conditions for the optimum combination of strength and toughness. The advantage of the glass-ceramic route is that relatively modest processing temperatures are involved, although even so a typical residual thermal stress of the order of only 200 MPa may still be sufficient to cause cracking of the matrix in as-manufactured composites. However, for all work involving the production of a ceramic fibre reinforced ceramic composite by conventional pressing methods, there remains the problem of compatibility. Nicalon fibre with a starting strength as high as 3 GPa, for example, may lose half of its strength when pressed into composites with a (:AS or similar glass ceramic matrix, and following high-temperature exposure in service this load-bearing ability may be further impaired. Further development in the field will therefore require attention to the possible need for diffusion barrier coatings. Plus ca change... ! Recent ideas on the manufacture of fibres, the surface treatment of fibres, and the manufacture of the whole composite involve the use of sol-gel processing methods. Carbon fibre reinforced carbon composites have always been of considerable interest, and have been for many years in continuous service in the brakes of Concorde, to give only one example. Carbon is almost the only engineering material whose strength increases as the temperature is raised. C/C composites offer considerable potential in all manner of areas of application, but production is extremely slow and the materials themselves tend to be very expensive. For elevated temperature purposes in oxidising atmospheres there is still the need for protective coatings and/or oxidation inhibitors.

Hybrid composites The concept of mixed fibre composites is an extension of the composites principle of combining materials to optimise their value to the engineer, exploiting their better qualities while mitigating the effects of their less desirable properties. Mixing two or more types of fibre in one matrix allows even closer tailoring of composite properties to suit specific requirements than can be achieved with a single fibre species. Many hybrids of current interest represent attempts to reduce the cost of expensive composites with reinforcements like carbon by incorporating a proportion of cheaper, lower-quality fibres such as glass without too seriously reducing the mechanical properties of the original composite. Of equal importance is the reverse principle, that of stiffening a glass reinforced plastic (GRP) structure with a small quantity of judiciously placed carbon or Kevlar-49 fibre, without inflicting too great a cost penalty, in high technology fields the question of cost may be insignificant by comparison with the advantages of optimising properties. In demanding
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aerospace applications, one of the most important purposes of using hybrids is to utilise the natural toughness of Kevlar or glass reinforced plastics to offset the relative brittleness of typical carbon fibre composites. A widely-debated issue is whether or not it is possible to obtain greater improvements in some properties than might be predicted from calculations based upon properties of the separate components. This something-for-nothing synergism principle, which has been dubbed 'the hybrid effect' has obscured the interpretation of much experimental work. Hybrid properties higher than a mixture.rule prediction have often been hailed as evidence of synergism, regardless of the validity or otherwise of parallel-connected element models for the composite properties in question. The elastic properties of hybrid composites can be calculated to within limits acceptable for most design purposes by application of well-established principles of composite mechanics and classical thin laminate theory. Although elasticity calculations are largely independent of the nature of fibre distributions, predictions of properties such as strength, toughness, and fatigue behaviour are far more difficult because they depend on micromechanisms of damage accumulation which, in turn, are determined by the construction of the laminate and the scale of dispersion of the mixed fibres. At the grossest level of bybridisation, strips of GRP incorporated into a CFRPlaminate act as efficient crack arresters, provided the width of the strips is sufficient to dissipate the energy of a crack moving rapidly in the CFRP by localised debonding and splitting. The commonest type of hybrid, however, and that which is most easily achieved in practice, is made by laminating some balanced sequence of plies within each of which there is only a single species of fibre. In such laminates the failure strain of the higher elongation component is usually reduced by the presence of the other while that of the lower elongation component is often increased. This behaviour results from the state of elastic constraint in the fabricated laminate, the effect being greater the thinner the plies, and has been explained on the basis of energy arguments. An approximate statistical analysis shows that the failure process is affected by the statistical spread of failure strains of the two fibre species and predicts that the addition of high elongation fibres to a low failure strain composite raises the strain level needed to propagate fibre breaks because the higher elongation fibres behave like crack arresters on a micromechanical level. The strength of such a composite does not follow a mixture rule. For many of the applications that have been cited for the use of hybrids in aircraft, the service conditions are relatively easy to predict and design requirements correspondingly easy to satisfy. Typical examples are nose.wheel doors of combined CFRP and KFRP in the Fokker F28, main landing gear doors of co.cured GRP and CFRP in the Boeing YC14, engine cowlings of CFRP with knitted glass fibre ribbon in the SAAB MFI 15117, fairings of carbon and woven glass hybrids with boron/epoxy end caps in the Grumman F14, and a wide variety of doors, cowlings, and wing-to-body fairings of various composites, including carbon/Kevlar hybrids, in the Boeing 767, to name but a few. The principal virtue quoted for many of these applications lies in their
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potential for weight saving for a given strength or stiffness level. Savings of 20% or more over designs in conventional aluminium alloys have been quoted, especially when the hybrids are used in connection with honeycomb core materials. Mention is often made, however, of simultaneous cost reductions, perhaps partly as a result of higher cost efficiency (eg. strength per unit cost) of the composite materials, and partly because of the easier (and therefore cheaper) manufacturing methods employed. The electrical conductivity of hybrids containing carbon fibres may also be of vital importance in some applications. In more demanding applications, such as in helicopter rotor blades, fan blades, propeller blades, wing sections or other control structures, the conditions are less precisely definable, and longer term environmental problems relating to fatigue, creep, and effects of moisture must be considered.
Conclusion In conclusion, it seems worthwhile to offer a brief list of potential problem areas for the consideration of intending users of composite materials. This list is not exhaustive, and is arranged alphabetically rather than in order of importance.

Availability: particularly in relation to ceramic fibres for

high-temperature MMC and CMC, there is a serious lack of choice in the UK. Competition: the designer must be aware of the advantages and disadvantages of competing materials; not only, for example, the competition between conventional metallic alloys and reinforced plastics, but also between different classes of composite materials. Costs: it may often appear that the costs of the constituents of composites - ie the reinforcing filaments and the matrices - are very high by comparison with conventional materials, but overall reductions in costs may be possible because of cheaper processing/assembly methods. Damage tolerance: many composites are damage tolerant, but as a result of mechanisms that are quite different from those which operate in metallic materials. It is important to understand these mechanisms and to appreciate the effects of the damage on residual composite properties. Data: data relating to specific composites under particular service conditions may simply not be available. Data.bases are being constructed, but usually within companies and therefore not generally available. Design methods: composites offer new solutions to engineering problems, and encourage re.design of existing solutions. But it is important that conventional apmaches to designing with monolithic metallic or other materials are avoided. Piece-meal substitution of composites for metallic components is almost always unsafe and non-cost-effective. Environmental effects: composites react in different ways to service environments. Water damages many polymer composites, for example. Interface: the fibre/matrix interface is a vital element which controls many of the properties of a composite. "Interface engineering" is therefore an important part of design practice.
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Joining~machining: even re-design and near-net-shape

manufacturing may not completely eliminate the need for assembly, and the effects of joining methods (adhesive bonding, rivetting, etc) and machining methods must be understood when applied to fibre reinforced materials. Manufacturing: many sophisticated and flexible methods are now available for use with various kinds of composites, and fast, automatically controlled processes may be used. it is vital to appreciate the effects of manufacturing processes on product quality (eg in relation to distributions of fibres and matrix, uniformity of structure, presence or absence of defects (and their effects on properties). A major area of concern in rapid, automatic operation is that we have not yet fully developed the necessary pre-form technology - ie methods for the separate (and fast) construction of appropriate reinforcement architecture prior to infiltration by a matrix. NDT: non-destructive evaluation technology is largely adapted from the metallurgical field, but understanding must accompany the technology transfer. Recycling: There are serious problems as yet untacided,

relating to the disposal and/or recycling of composite materials. Standards: standards and codes of practice exist in some areas, but not in others. The next few years will be decisive in deciding which European country achieves dominance in this field. UK firms appear not to be very interested in developing standards for composite materials. Understanding: safe and economic use of composites requires a high level of understanding on the part of the designer of why these materials behave as they do.

Acknowledgement
Professor Harris has kindly permitted M&D to publish the text of his keynote address to the composites session of the Eurotech Direct conference, held in Birmingham, UK, 2-4 July 1991. We are grateful to The Institution of Mechanical Engineers, the conference organisers, for also giving approval. Proceedings of the materialsrelated sessions are available from MEP, Northgate Avenue, Bury St. Edmunds, Suffolk, IP32 6BW, UK (75.00, ISBN 0 85298 774 9).

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