Inorganic fibers

General remarks
Inorganic fibers, both metal and non metal ones, are more resistant, more rigid, have an higher melting point and are more heat resistant than traditional fibers. They are also totally uninflammable, but, except for the metal ones, they are fragile. Their textile importance is also limited, whereas they are widely used as reinforcement in composite materials. They are usually excellent in high temperatures and in a corrosive surrounding. Real fibers with an area transversal section lower than 0,005 mm2 and a thickness lower than 0,25 mm are carried out. We can get them as wiskers (= mono crystalline materials) and as real fibers, both continuous and cut in cluster. Their diameter changes from 5 to 15 nm, but other ones are much thicker, like the ones got through vapor deposition on the fibers, such as borate fibers and silicon carbide fibers (100-150 n). The diameter of the fiber is critical compared to its resistance: like all fragile materials their resistance increases when their transversal size reduces. Fibers in cluster can be produced directly or through the cutting of continuous filaments. We can get them as wadding (wool), mat and felt. Continuous fibers are carried out with a process of spinning through melting, that can be used with fibers that come out from melting materials (glass, mineral fibers). Carbon fibers and ceramic ones are made from organic fibers, and these precursors are thermically degraded. Precursors are prepared with the same technologies used to prepare

Static Load

Dynamic Load Impa ct Fatigu e

Thermic resoistan ce

Densit y

Tenacity Tensil Flexur Compressi e al ve Glass Aramid c

Modulus Tensil Flexur e al Compressi ve

+ =

= -

+ -

+ =

= -

conventional organic fibers. When used as a reinforcement, yarn with 3000-12000 fibers is used (it is shortly called 3-12 K). For some fibers we need CVD (Chemical Vapor Deposition) and a substrate of highly melting fibers: SIC or B4C on borate, TIN, SIC on carbon.

Inorganic Fibers Abbreviation CARBON GLASS METAL BORON SILICA SILICA CARBIDE CERAMIC (CF) (GF) (MTF) (BF) (SiC) (SiC) (CER)

Kind of Fiber density (g/cm3) Tenacity (MPa) Modulus GPa Min Glass Carbon SiC Oxides 2,5 1,76 2,55 3,9 Max 2,62 2,1 3,5 3,9 Min 3400 2000 2000 1200 Max 4500 7000 3700 1400 Min 70 240 200 340 Max 70 700 420 400

Carbon

Glass Density (g/cm ) Tenacity (MPa) Modulus (GPa) Elongation (%)

3

Aramidic 1,45 3000 70-130 2+4

Carbon 1,8 (2,1) 30005000 200-500

2,5 20004000 50-80 4+5

Chemical composition and properties

Properties of glass fibers are bound to the chemical composition of the mixture, but they are also influenced by the spinning way. Usually, they are divided into:

Use

Type of Glass glass E, glass A, C, CR, glass R, S glass R, S glass D.

Multipurpose fibers Acid resistant fibers

Alkali resistant fibers High strength fibers Fibers with good dieletric properties

Carbon fibers (CF)

Carbon fibers, appeared on the market in 1960, are produced through alteration of organic fibers (rayon, acrylics etc) or from remainings of petroleum or tar distillation. The first ones are called Carbon-Pan, the others, Carbon from pitch (pitch). Carbon fibers can be considered as a transition between inorganic fibers and organic fibers. The rigid structure of the strip cyclic links molecules or ladder ones of the carbon PAN or carbon-pitch fibers has

suggested how to create aromatic organic molecules to get fibers with high performances. Carbon fibers, discovered in 1879 by Edison, have been commercially produced only since 1960 following a process put right by William Watt for Royal Aircraft in UK. They represent the separation point between organic and inorganic fibers, being produced through modification of organic fibers or organic pitch. Carbon fibers, together with glass fibers, have started the era of composite materials. Carbon fibers in particular have started the era of advanced composite materials, that were firstly used in the army and in aeronautics and later in automobile industry and in free time. Carbon fibers can be produced through heat treatment and pyrolysis of different polymeric precursors such as rayon, polyacrylonitrile, aromatic polyamide, phenolic resin etc. Recently carbon fibers and graphite fibers gotten from pitchy materials have been introduced. The words graphite fibers are improperly used, because these fibers dont come out from graphite, but from heat treatments over 2000C of carbon fibers, when the carbon atoms place in a way similar to the graphite structure.

Carbon fibers from PAN

The precursor that has really started the era of carbon fibers (1960) is the polyacrilonitrile fiber, PAN, characterized by an adequate chemical composition, by a particular molecular orientation and by a specific morphology. The chemical composition is important in order to moderate the exothermicity of the cycle reaction of CN, 18kcal/mass, heated to 220-260C for some hours. The result of the cycle reaction is a black colored, glow-proof material, oxidized PAN, that owns modest mechanical properties, and that is used for protective clothes, for glow-proof cotton-wool or in carbon-carbon composites, and for breaks requiring high performances (planes, race cars and high speed trains). The following carbonization process (400-1000C) is usually made in inert atmosphere or vacuum sealed and it removes atoms from the

structure and it develops the graphitic structure. From 400 to 1000C, HCN, NH3 and N2 develop, also CO, CO2 and H2O can develop, according to the quantity of O2 that the oxidized precursor has bound when treated in air at a temperature of 220-260C. After the treatment at 1000C, a fiber contains more than 90% of carbon and about 5% of nitrogen. It is very important to check the retraction of the fiber during the cycle phase at 220-260C, because in this phase the alignment of the molecular segment along the fiber is fixed and the final elastic forms depends form this orientation. The molecular orientation given to the original acrylic fiber influences the toughness and the elastic form of the resulting fiber. An excessive orientation is negative because it brings surface and internal faults in the fiber.

Carbon-pitch fibers
Pitch, or tar residue, is the residue of the tar or petroleum distillation and it is made of thousands of aromatic hydrocarbons with a molecular weight from 200 to 800, which form a multi eutectic system with softening temperatures between 50 and 300C, that are by far lower than the melting temperatures of pure aromatic components. A mesophase is formed through a thermic treatment between 400 and 450C. It is liquid crystals with a molecular order that is intermediate between that of crystals and of liquids. The molecules of the mesophase are oriented along the fiber by the flowing gradient during the extrusion from a capillary. The process of carbon fiber production through pitch mesophase is reduced to essentials as follows: the pitch or tar precursor is thermically treated over 350C to be converted in mesophase containing both phases, the isotropic and anisotropic one. After extrusion, at about 380C, the isotropic phase is made unmeltable by thermo fixing in air at

a temperature that is lower than the softening point at about 300C. Fiber is finally carbonized at 1000C or it is treated at temperatures over 2000C in order to produce graphite fibers with a highly elastic form. The main advantages of this process are that no filament tension is requested during the carbonizing and graphitizing phases and times of the individual phases are much shorter than those of the PAN process. The structural analysis of the fiber shows that the carbon layers are parallel to the fiber axis. In the following table the main properties of carbon fibers made from PAN and pitch are synthetized.

Characteristics Tenacity (Gpa) Modulus (Gpa) Elongation at Break (%) Density (g/cm3)

Fibers from PAN 1,8-7,0 230-540 0,4-2,4 1,75-1,95

Fibers from pitch 1,4-3,0 140-820 0,2-1,3 2,0-2,2

Productive capacity
The productive capacity of carbon fibers is valuable in about 12000 yearly tons. Changes, even important ones, are under way. To restrict all in the last 10 years we must mention the stop of the BSM-BASF production in USA for 1350 tons a year and of Grafil for 320 tons a year. In Europe Courtaulds stopped their production in 1990 for 350 tons a year. In spite of crisis times, the consumer course is definitely positive.

Fig. 1 Course of the world producing capacity

Fig. 2 evolution of the main markets (Europe)