Carbon and graphite bers

Carbon and graphite have a substantial capability as reinforcing bers, with great exibility in the proparties that can be provided. Primary characteristics for reinforcing bers in polymermatrix composites are high stiffness and strange. The bers must maintain these characteristics in hostile environments such as elevated temperatures, exposure to common solvents and uids, and environmental moisture. To be used as part of a primary structure material it should also be available as continuous ber . These characteristics and requirements have substantial implications for the physical, chemical and mechanical properties of the ber, which in tum implies processing and acceptance parameters. Interest in carbon bers for structural materials was initiated in the late 1Q5Us when synthesized rayons in textile form were carbonized to produce carbon bers for high temperature missile applications .One of the rst distinctions to be made is the difference between carbon and graphite bers, although the terms are frequently used interchangeably. Background information for these differences s contained in the following sections. The primary purpose of making this distinction here s to alert the reader those users may mean different things when referring to graphite versus carbon bers. Carbon and graphite bers are both based on grapheme (hexagonal) layer networks present in carbon. lf the grapheme layers or planes slack with three dimensional order the malenal is dened as graphite Usually extended time and temperature processing is required lo fom1 this order, making graphite bers more expensive. Because the bonding planes is weak, disorder frequently occurs such only the dimensional ordering within he layers is present. This material is three different precursor materials are commonly used at present to produce carbon hers: rayon, polyacrylonitile (PAN), and isotropic and liquid crystalline pitches {Reference 24.1.11}. Carbon bers are made predominately from carbonization of PAN. The fibers consist of intermingled brils of turbostratic graphite with basal planes tending to align along the ber axis. This forms an internal structure remains cent of an onion skin. Pitch bers may have a different internal structure, more like sheafs or spokes . The highly anisotropic morphology gives rise to moduli in the range. Fiber long axis. , single crystal {whisker} of graphite is about 1060 and 3 GPA, respectively, but these properties are not aainable in ber form. Ultra high modulus fibers can be prepared from liquid-crystalline mesosphere pitch; the higher degree of onantalion in the precursor translates through to he nal carbonized ber leading to larger and more oriented graphite crystallites. Processing High stiffness and strength implies strong interatomic and intermolecular bonds and few strength limiting was. Carbon ber properties are dependent on the ber microstructure, which is extremely process dependent, such that properties of hers with the same precursor but different processing can be dramaticallydifferent. The precursor itself can also change these properties. The processing may be optimized for high modulus or streng, or traded off with economics. Manufacture The manufacturing process for carbon ber descended below is for the PAN, which is one of The most common. Some differences beehives PAN processing and the pitch and rayon precursors are then descended aerwards. The manufacture of PAN based carbon ber can he broken down into the white ber and black ber stages. Most manufacturers consider the details of these processes.

White ber Production of PAN precursor, or white ber, is a technology in itself. Fairly conventional ber processes are perfomed: polymerization, spinning, drawing, and washing. Additional drawing stages may be added in the process. of the white ber inuence the processing and results for the black ber processing. Black ber The black ber process consists of several steps: oxidation (or thermosetting), pyrolysis (or carbonizing), surface treatment, and sizing. In the oxidation process the PAN ber is convened to a thermoset from a thermoplastic. For this oxidation process the ber diameter is limited by waste gas diffusion. In the pyrolysis process, which is performed under an inert atmosphere, most of the non-carbon material is expelled, forming ribbons of carbon aligned with the ber axis. In the surface treatment step the ber may be etched in either gas or liquid phase by oxidizing agents such as chlorine, bromine, nitric acid or chlorates. This improves the wettability for the resin and encourages of a strong, durable bond. Some additional improvement through removal of surface flaws may also be realized. This process can be electrolytic. The carbon fibers are often treated with solution of unmodied epoxy resin and for other products as a size. The sizing prevents ber abrasion, improves handling, and can provide an epoxy matrix compatible surface. As a rule PAN precursor can provide higher strength carbon bers, while pitch can provide higher moduli. Rayon based bers tend to be less expensive but lower performance. Pitch ber composites have been prepared with elastic moduli superior to steel and electrical conductivity higher than copper conductor. The shear strengths and impact resistance are degraded, however. Yield for PAN is approximately 50%, but for pitch can be as high as 90%.

Processing to microstructure Carbon ber properties are driven by the type and extent of defects, orientation of the ber, and the degree of crystallinity. The precursor makeup and heat treatment can affect the crystallinity and orientation. The defect content can be driven by contaminants and processing. Orientation is

also greatly affected by the drawing process which may be repeated many times in the processing of the bers. Typically limitations on the end use for carbon bers in composite structure depend more on the resin matrix than the ber. Some exceptions to this are present, however, in which case the oxidative stability, thermal conductivity, coefcient of thermal expansion, or other properties of the ber must be talren into account. Some lrey properties for carbon ber, including cost. Typical values for glass, aramid, and boron are shown for comparison. While some carbon ber properties are fairly universal, different products from different manufacturers can have substantially different properties. Three of the major manufacturers for the US are Amoco, Hercules and Toray. It should be noted that translation of fiber properties to composite properties is dependent on many factors in addition to rule of mixtures.

Aramid fibers
Aramid fibers are a class of heat-resistant and strong synthetic fibers. They are used in aerospace and military applications, for ballistic rated body armor fabric and ballistic composites, in bicycle tires, and as an asbestos substitute. The name is a portmanteau of "aromatic polyamide". They are fibers in which the chain molecules are highly oriented along the fiber axis, so the strength of the chemical bond can be exploited. Aromatic polyamides were first introduced in commercial applications in the early 1960s, with a meta-aramid fiber produced by DuPont as HT-1 and then under the trade name Nomex.[2] This fiber, which handles similarly to normal textile apparel fibers, is characterized by its excellent resistance to heat, as it neither melts nor ignites in normal levels of oxygen. It is used extensively in the production of protective apparel, air filtration, thermal and electrical insulation as well as a substitute for asbestos. Meta-aramid is also produced in the Netherlands and Japan by Teijin under the trade name Conex,[2] in China by Yantai Tayho under the trade name New Star, by SRO Group (China) under the trade name X-Fiper, and a variant of meta-aramid in France by Kermel under the trade name Kermel. Based on earlier research by Monsanto Company and Bayer, a fiber para-aramid with much higher tenacity and elastic modulus was also developed in the 1960s1970s by DuPont and Akzo Nobel, both profiting from their knowledge of rayon, polyester and nylon processing. Much work was done by Stephanie Kwolek in 1961 while working at DuPont, and that company was the first to introduce a para-aramid called Kevlar in 1973. A similar fiber called Twaron with roughly the same chemical structure was introduced by Akzo in 1978. Due to earlier patents on the production process, Akzo and DuPont engaged in a patent dispute in the 1980s. Twaron is currently owned by the Teijin company (see Production).

Para-aramids are used in many high-tech applications, such as aerospace and military applications, for "bullet-proof" body armor fabric. The Federal Trade Commission definition for aramid fiber is: A manufactured fiber in which the fiber-forming substance is a long-chain synthetic polyamide in which at least 85% of the amide linkages, (-CO-NH-) are attached directly to two aromatic rings. Aramids are generally prepared by the reaction between an amine group and a carboxylic acid halide group. Simple AB homopolymers may look like: nNH2-Ar-COCl -(NH-Ar-CO)n- + nHCl The most well-known aramids (Kevlar, Twaron, Nomex, New Star and Teijinconex) are AABB polymers. Nomex, Teijinconex and New Star contain predominantly the meta-linkage and are polymetaphenylene isophthalamides (MPIA). Kevlar and Twaron are both p-phenylene terephthalamides (PPTA), the simplest form of the AABB para-polyaramide. PPTA is a product of pphenylene diamine (PPD) and terephthaloyl dichloride (TDC or TCl). Production of PPTA relies on a co-solvent with an ionic component (calcium chloride (CaCl2)) to occupy the hydrogen bonds of the amide groups, and an organic component (N-methyl pyrrolidone (NMP)) to dissolve the aromatic polymer. Prior to the invention of this process by Leo Vollbracht, who worked at the Dutch chemical firm Akzo, no practical means of dissolving the polymer was known. The use of this system led to an extended patent dispute between Akzo and DuPont. Aramids share a high degree of orientation with other fibers such as ultra high molecular weight polyethylene, a characteristic that dominates their properties.

Kevlar
Kevlar is the registered trademark for a para-aramid synthetic fiber, related to other aramids such as Nomex and Technora. Developed at DuPont in 1965, this high strength material was first commercially used in the early 1970s as a replacement for steel in racing tires. Typically it is spun into ropes or fabric sheets that can be used as such or as an ingredient in composite material components. Currently, Kevlar has many applications, ranging from bicycle tires and racing sails to body armor because of its high tensile strength-to-weight ratio; by this measure it is 5 times stronger than steel on an equal weight basis. It is also used to make modern drumheads that withstand high impact. When used as a woven material, it is suitable for mooring lines and other underwater applications. A similar fiber called Twaron with roughly the same chemical structure was developed by Akzo in the 1970s; commercial production started in 1986, and Twaron is now manufactured by Teijin. Poly-paraphenylene terephthalamide branded Kevlar was invented by Polish-American chemist Stephanie Kwolek while working for DuPont , in anticipation of a gasoline shortage. In 1964, her group began searching for a new lightweight strong fiber to use for light but strong tires. The polymers she had been working with at the time, poly-p-Phenylene-terephthalate and polybenzamide,[7] formed liquid crystal while in solution, something unique to those polymers at the time. The solution was "cloudy, opalescent upon being stirred, and of low viscosity" and usually was thrown away. However, Kwolek persuaded the technician, Charles Smullen, who ran the "spinneret", to test her solution, and was amazed to find that the fiber did not break, unlike nylon. Her supervisor and her laboratory director understood the significance of her accidental discovery and a new field of polymer chemistry quickly arose. By 1971, modern Kevlar was introduced. However, Kwolek was not very involved in developing the applications of Kevlar.

Kevlar

is synthesized in solution from the monomers 1,4-phenylene-diamine (paraphenylenediamine) and terephthaloyl chloride in a condensation reaction yielding hydrochloric acid as a byproduct. The result has liquid-crystalline behavior, and mechanical drawing orients the polymer chains in the fiber's direction. Hexamethylphosphoramide (HMPA) was the solvent initially used for the polymerization, but for safety reasons, DuPont replaced it by a solution of N-methylpyrrolidone and calcium chloride. As this process was patented by Akzo (see above) in the production of Twaron, a patent war ensued. Kevlar (poly paraphenylene terephthalamide) production is expensive because of the difficulties arising from using concentrated sulfuric acid, needed to keep the water-insoluble polymer in solution during its synthesis and spinning.[citation needed] Several grades of Kevlar are available: Kevlar K-29 in industrial applications, such as cables, asbestos replacement, brake linings, and body/vehicle armor. Kevlar K49 high modulus used in cable and rope products. Kevlar K100 colored version of Kevlar Kevlar K119 higher-elongation, flexible and more fatigue resistant. Kevlar K129 higher tenacity for ballistic applications. Kevlar AP has 15% higher tensile strength than K-29.[10] Kevlar XP lighter weight resin and KM2 plus fiber combination.[11] Kevlar KM2 enhanced ballistic resistance for armor applications[12] The ultraviolet component of sunlight degrades and decomposes Kevlar, a problem known as UV degradation, and so it is rarely used outdoors without protection against sunlight.

Fiberglass
Fiberglass (or fibreglass) (also called glass-reinforced plastic, GRP glass-fiber reinforced plastic, or GFRP) is a fiber reinforced polymer made of a plastic matrix reinforced by finefibers of glass. It is also known as GFK (for German: Glasfaserverstrkter Kunststoff). Fiberglass is a lightweight, extremely strong, and robust material. Although strength properties are somewhat lower than carbon fiber and it is less stiff, the material is typically far less brittle, and the raw materials are much less expensive. Its bulk strength and weight properties are also very favorable when compared to metals, and it can be easily formed using molding processes. The plastic matrix may be epoxy, a thermosetting plastic (most often polyester or vinylester) or thermoplastic. Common uses of fiberglass include high performance aircraft (gliders), boats, automobiles, baths, hot tubs, water tanks, roofing, pipes, cladding, casts, surfboards and external door skins. Unlike glass fibers used for insulation, for the final structure to be strong, the fiber's surfaces must be almost entirely free of defects, as this permits the fibers to reach gigapascal tensile strengths. If a bulk piece of glass were to be defect free, then it would be equally as strong as glass fibers; however, it is generally impractical to produce bulk material in a defect-free state outside of laboratory conditions. The manufacturing process for glass fibers suitable for reinforcement uses large furnaces to gradually melt the silica sand, limestone, kaolin clay,fluorspar, colemanite, dolomite and other minerals to liquid form. Then it is extruded through bushings, which are bundles of very small orifices (typically 525 micrometres in diameter for E-Glass, 9 micrometres for S-Glass). These

filaments are then sized (coated) with a chemical solution. The individual filaments are now bundled together in large numbers to provide a roving. The diameter of the filaments, as well as the number of filaments in the roving determine its weight. This is typically expressed in yield-yards per pound (how many yards of fiber in one pound of material, thus a smaller number means a heavier roving, example of standard yields are 225yield, 450yield, 675yield) or in tex-grams per km (how many grams 1 km of roving weighs, this is inverted from yield, thus a smaller number means a lighter roving, examples of standard tex are 750tex, 1100tex, 2200tex). These rovings are then either used directly in a composite application such as pultrusion, filament winding (pipe), gun roving (automated gun chops the glass into short lengths and drops it into a jet of resin, projected onto the surface of a mold), or used in an intermediary step, to manufacture fabrics such as chopped strand mat (CSM) (made of randomly oriented small cut lengths of fiber all bonded together), woven fabrics, knit fabrics or uni-directional fabrics. An individual structural glass fiber is both stiff and strong in tension and compressionthat is, along its axis. Although it might be assumed that the fiber is weak in compression, it is actually only the long aspect ratio of the fiber which makes it seem so; i.e., because a typical fiber is long and [3] narrow, it buckles easily. On the other hand, the glass fiber is weak in shear that is, across its axis. Therefore if a collection of fibers can be arranged permanently in a preferred direction within a material, and if the fibers can be prevented from buckling in compression, then that material will become preferentially strong in that direction. Furthermore, by laying multiple layers of fiber on top of one another, with each layer oriented in various preferred directions, the stiffness and strength properties of the overall material can be controlled in an efficient manner. In the case of fiberglass, it is the plastic matrix which permanently constrains the structural glass fibers to directions chosen by the designer. With chopped strand mat, this directionality is essentially an entire two dimensional plane; with woven fabrics or unidirectional layers, directionality of stiffness and strength can be more precisely controlled within the plane. A fiberglass component is typically of a thin "shell" construction, sometimes filled on the inside with structural foam, as in the case of surfboards. The component may be of nearly arbitrary shape, limited only by the complexity and tolerances of the mold used for manufacturing the shell.

Organic Fibers
Under this name are included others such as chain polyethylene fibers or elongated fibers of thermotropic liquid crystalline polymers , but we will focus on aramid fibers , due to its use and its exceptional characteristics majority . Aramid types : - Fibers of low modulus ( E = 70 GPa ) - High modulus fibers ( E = 130 GPa ) Perhaps the most striking feature of the aramid is its high impact resistance , its high tenacity and high energy absorption capacity , grounds on which it is used even in bulletproof vests. However, we can highlight these other features : - High specific tensile strength (5 times stronger than steel ) . - Good mechanical stability in the range (-30 C/200 C) - High modulus and low elongation at break . - High chemical stability , except for strong acids and bases against highly concentrated . Are also flame resistant and self-extinguishing .

As for disadvantages we highlight a low compressive strength and flexural strength losses in the presence of moisture and low adherence to certain matrices , such as thermoplastics , in addition, the price is high compared to other fibers. Aramid fiber is made by an extrusion process and yarn.

ceramic fibers
These fibers arise from the necessity of reinforcements for aerospace high temperatures. In addition to this resistance , have very high performance in terms of tensile strength and chemical stability. However, their manufacture and handling is extremely complicated and expensive , so I use is limited to this sector and the metalworking industry, carburizing furnaces for thermochemical treatments , which can reach temperatures up to 950 C. Ceramic fibers within the whiskers include : short inorganic fibers perfectly crystalline structure with tensile strengths between 3 and 14 GPa and modulus of elasticity between 400 and 700 GPa , and a high temperature resistance .

Boron fiber
Fibers are obtained from the deposition substrate tungsten or carbon , the former being the most used , but only in the field of space or military aircraft because of its high cost. These include the following properties: - Density : 2570 kg / m - High strength : 3600 MPa - High modulus of elasticity 400 GPa - Can be combined with epoxy , aluminum and titanium matrices .

Silicon carbide fiber

This fiber has been successfully used to reinforce organic and ceramic matrices . Has a cost lower than that of boron , so that in use it further reinforcement. The manufacturing process is somewhat similar to boron fiber . These are the most important properties : - Density : 2800 kg / m - Tensile strength : 2.5 to 3 GPa - Modulus : 200 GPa - High maximum service temperature : 1250 C

Quartz fiber
From natural quartz crystals are formed filaments. About 200 filaments combined result in a fiber with high strength and flexibility . Can be used with most of the resins. Here are some of its properties: - Density : 2200 kg / m - Tensile strength : 3.45 GPa - Modulus of elasticity: 71 GPa - Deformation at break of 1%, are perfectly elastic fibers . - Excellent thermal shock resistance : it is possible to heat them up to 1,100 C and cool quickly in water without change.

metallic fibers
Have the disadvantage that their charge density and thus are more expensive than fiberglass (except steel ) . These are the most used and their main characteristics : - Iron and alloys: high resist . and mod. elast . Ferromagnetic . - Stainless steel: corrosion resistance - Nickel and cobalt superalloys : resist . Mechanical and chemical at high temperatures. - Titanium , Tantalum , Nickel : refractory resist . corrosion . - Copper and copper alloys : electrical and thermal conductivity - Aluminium and aluminum alloys : low density , elec driver . and heat . - Silver, Gold and precious metals : electronic driver . and term. Not corrode

Thermoset matrix
Thermoset liquid resins comprise a series of liquids or semi precursors which must be cured in order to achieve the solid state by chemical, thermal (high temperatures) or by radiation (UV, gamma, electron or microwave). Once cured, have lots of cross-links, and can not be remelted without suffering serious degradation. The resins used are: epoxy resins The importance of the epoxy matrix is the ability of the epoxide radical to react with a variety of other organic radicals and crosslink without the appearance of a condensate . Epoxy resins are characterized by low shrinkage , good resistance to high temperature ( 180 C ) and good resistance to chemicals . We can distinguish two main types of epoxy resins , according to the chemical structure are based on : - TGMDA ( methylene tetraglicil dianiline ) : this molecule is the most important component of epoxy resin formulations for high-tech applications . Exhibits high crosslink density . - DGEBA ( diglycidyl ether of bisphenol A) : cure at lower crosslinking density than the last. The difference between the density of crosslinks in the cured will be determined by the different properties of the resins. Besides these two , we can find other epoxy resins with characteristics according to the above , such as novolacs , trifunctional epoxy resins and bisphenol F epoxy resin In epoxy resins is very important to the choice of curing agent , as this determines the final mechanical and thermal properties of the resin. There are basically three types : - Amine : aliphatic amines cure the resin at room temperature but have low temperature; the aromatic provide resins with improved properties , but require curing temperatures of 120-175 C , and cycloaliphatic have properties intermediate between the two above. - Anhydrides : Bisphenol A epoxy resins cured at 120-175 C Unsaturated polyester resins They are the most important family of thermosetting resins used in composites . The curing of these resins can be accomplished in many ways, with chemical additives , heat or radiation. Moreover, the configuration and chemical composition of the polyester resin hardened determine its characteristics and properties (flexibility, toughness, mechanical, chemical , etc . ) , So that through an appropriate choice of these parameters, can vary substantially the characteristics of

the resin chosen . In sum, the unsaturated polyester resins are the most versatile and can be adapted to a multitude of processes and needs. As mentioned, in this family there is great variability of properties , here the range of values that can be found : - Flexural strength ( MPa ) : 80-140 - Tensile strength (MPa): 40-85 - Traction Module ( GPa ): 2 - 3.5 - Percent Elongation : 1.2 - 4.8

Thermoplastic Matrix
Moreover, it is possible to find matrices reinforced with high performance thermoplastics . These matrices have been developed with the dual purpose of obtaining suitable high temperature materials having high impact resistance. The result of advances in this field are tougher matrices , with more than thermostable resistance and lower water absorption. Furthermore they have a certain time needed for molding and curing , which means lower costs , and the recycling process is easier. Arrays are the most important eterketona polyether (PEEK) , polyphenylene sulfide (PPS) and polyetherimide (PEI ) and polyamideimide (PAI ) . Its main characteristics are: PEEK : PEEK is partially crystalline thermoplastic material which provides a unique combination of high mechanical properties , resistance to temperature (range of temperatures between -60 C and 250 C) and excellent chemical resistance . Other Features: - High limit fatigue and high toughness - Very good wear resistance - Intrinsic resistance to flame - Very low smoke during combustion - Good dielectric properties and electrical insulation PPS : As above, this material has thermoplastic properties even in the final composite . It has a remarkable chemical and thermal resistance ( 232 C continuous) and excellent resistance to low temperature . Furthermore it is inert to most chemicals in a wide range of temperatures. High temperature required for processing. PEI : Feature Highlights: inherent flame resistance , low smoke , high temperature resistance long , dimensional stability, chemical and hydrolytic stability . EPI : This matrix is molded as a thermoplastic material but after post partially cured thermoset has properties , which increases resistance to high temperatures. .