Silicon boron carbide ceramics

All the above primarily refers to materials containing relatively small amounts of impurities. However, boron carbide ceramics usually contain 7-20% A1 or AI2O3 to increase hardness and 6-13% silicon to improve mechanical characteristics [98]. Aluminum- and silicon-doped materials often exhibit structural nonuniformity. They have areas of pure boron carbide, and silicon- and aluminum-doped areas [107]. 

On heating in air at 10°C per min, poly(m-carborane-siloxane) shows typically only 4% mass loss at 450°C and 7% mass loss at 600°C (see Fig. 4). In comparison, siloxanes without carborane units, show an approximate 50% mass loss at 450°C. As a consequence of the relatively high boron and carbon content of these materials, pyrolysis is expected to generate ceramic residues of boron carbide/silicon carbide. 

Boron-containing nonoxide amorphous or crystalline advanced ceramics, including boron nitride (BN), boron carbide (B4C), boron carbonitride (B/C/N), and boron silicon carbonitride Si/B/C/N, can be prepared via the preceramic polymers route called the polymer-derived ceramics (PDCs) route, using convenient thermal and chemical processes. Because the preparation of BN has been the most in demand and widespread boron-based material during the past two decades, this chapter provides an overview of the conversion of boron- and nitrogen-containing polymers into advanced BN materials. 

Ceramics (qv) such as those in Table 12 find high temperature use to over 800°C (32). Advanced ceramics finding interest include alumina., partially stabilized zirconia, silicon nitride, boron nitride, silicon carbide, boron carbide, titanium dibofi.de, titanium carbide, and sialon (Si—Al—O—N) (33) (see... 

The carbides and nitrides are well known for their hardness and strength, and this section will briefly compare a number of these properties with those of the pure metals. Concentration will be placed here on the first row compounds, since these constitute a complete series, and Mo and W, since these are the most commonly studied metals. As will be shown, the physical and mechanical properties of carbides and nitrides resemble those of ceramics not those of metals. Comparisons will be made with boron carbide (B4C), silicon carbide (SiC), aluminium nitride (AIN), silicon nitride (Si3N4), aluminium oxide (A1203), and diamond, as representative ceramic materials. 

Metals and ceramics (claylike materials) are also used as matrices in advanced composites. In most cases, metal matrix composites consist of aluminum, magnesium, copper, or titanium alloys of these metals or intermetallic compounds, such as TiAl and NiAl. The reinforcement is usually a ceramic material such as boron carbide (B4C), silicon carbide (SiC), aluminum oxide (A1203), aluminum nitride (AlN), or boron nitride (BN). Metals have also been used as reinforcements in metal matrices. For example, the physical characteristics of some types of steel have been improved by the addition of aluminum fibers. The reinforcement is usually added in the form of particles, whiskers, plates, or fibers. 

Although few applications have so far been found for ceramic matrix composites, they have shown considerable promise for certain military applications, especially in the manufacture of armor for personnel protection and military vehicles. Historically, monolithic ("pure") ceramics such as aluminum oxide (Al203), boron carbide (B4C), silicon carbide (SiC), tungsten carbide (WC), and titanium diboride (TiB2) have been used as basic components of armor systems. Research has now shown that embedding some type of reinforcement, such as silicon boride (SiBg) or silicon carbide (SiC), can improve the mechanical properties of any of these ceramics. 

In addition to the initial work in the alumina and mullite matrix systems previously mentioned, SiC whiskers have also been used to reinforce other ceramic matrices such as silicon nitride,9-13 glass,14 15 magnesia-alumina spinel,16 cordierite,17 zirconia,18 alumina/zirconia,18 19 mullite/zirconia,18-21 and boron carbide.22 A summary of the effect of SiC whisker additions on the mechanical properties of various ceramics is given in Table 2.1. As shown, the addition of whiskers increases the fracture toughness of the ceramics in all cases as compared to the same monolithic materials. In many instances, improvements in the flexural strengths were also observed. Also important is the fact that these improvements over the monolithic materials are retained at elevated temperatures in many cases. 

Ceramic fibers of the nonoxide variety such as silioon carbide, silicon oxycarbide such as Nicalon, silicon nitride, boron carbide, etc. have become very important because of their attractive combination of high stiffiiess, high strength and low density. We give brief description of some important nonoxide fibers. 

Besides silicon carbide based ceramic fibers, there are other promising ceramic fibers, e.g. silicon nitride, boron carbide, boron nitride, etc. 

Silicon carbide, widely employed as an abrasive (carborundum), is finding increasing use as a refractory. It has a better thermal conductivity at high temperatures than any other ceramic and is very resistant to abrasion and corrosion especially when bonded with silicon nitride. Hot-pressed, self-bonded SiC may be suitable as a container for the fuel elements in high-temperature gas-cooled reactors and also for the structural parts of the reactors. Boron carbide, which is even harder than silicon carbide, is now readily available commercially because of its value as a radiation shield, and is being increasingly used as an abrasive. 

Included in the term nonoxide ceramics are all non-electrically conducting materials in the boron-carbon-silicon-aluminum system. The industrially most important representatives, apart from carbon (see Section 5.7.4), are silicon carbide (SiC), silicon nitride (Si3N4), boron carbide (B4C), boron nitride (BN) and aluminum nitride (AIN). 

In nonoxide ceramics, nitrogen (N) or carbon (C) takes the place of oxygen in combination with silicon or boron. Specific substances are boron nitride (BN), boron carbide (B4C), the silicon borides (SiB4 and SiBg), silicon nitride (SisN4), and silicon carbide (SiC). All of these compounds possess strong, short covalent bonds. They are hard and strong, but brittle. Table 22.5 lists the enthalpies of the chemical bonds in these compounds. 

Compare oxide ceramics such as alumina (AI2O3) and magnesia (MgO), which have significant ionic character with covalently bonded nonoxide ceramics such as silicon carbide (SiC) and boron carbide (B4C see Problems 19 and 20) with respect to thermodynamic stability at ordinary conditions. 

As a pronounced contrast, in the field of high performance non-oxide ceramics, currently only binaries are in use. Thus, the manifold opportunities for creating new and ever more capable nitride or carbide ceramics offered by the use of multi-component systems seem to have remained essentially unexplored. The main chemical reason for this lagging behind of non-oxide ceramics are clearly the extremely low self-diffusion coefficients of silicon or boron in their nitrides or carbides [6, 7]. Although the experimental data available are rather limited, the numbers presented in Table 1 [8] suggest that the temperatures needed to complete a solid state reaction between SiC and Si3N4 in an acceptable length of time reach, or even exceed, the decomposition temperature of at least one of the reactants. 

During their genesis all precursor derived ceramics pass through an amorphous state which in certain cases is stable up to the respective decomposition temperature. The propensity to crystaUize is strongest for the binary silicon and boron nitrides and carbides, while in particular quaternary materials out of the Si/B/N/C system show the strongest resistance towards crystallization. It is interesting to note that in any case investigated, so far, the amorphous multinary ceramics decompose into the binary border phases upon crystallization - crystalline ternary silicon boron nitrides or carbides are not known to date cf. [9]. 

Silicon carbide (SiC) is the most widely used nonoxide ceramic. Its major application is in abrasives because of its hardness (surpassed only by diamond, cubic boron nitride, and boron carbide). Silicon carbide does not occur in nature and therefore must be synthesized. It occurs in two crystalline forms the cubic P phase, which is formed in the range 1400-1800°C, and the hexagonal a phase, formed at >2000°C. 

Silicon carbide is noted for its extreme hardness [182-184], its high abrasive power, high modulus of elasticity (450 GPa), high temperature resistance up to above 1500°C, as well as high resistance to abrasion. The industrial importance of silicon carbide is mainly due to its extreme hardness of 9.5-9.75 on the Mohs scale. Only diamond, cubic boron nitride, and boron carbide are harder. The Knoop microhardness number HK-0.1, that is the hardness measured with a load of 0.1 kp (w0.98N), is 2600 (2000 for aAl203, 3000 for B4C, 4700 for cubic BN, and 7000-8000 for diamond). Silicon carbide is very brittle, and can therefore be crushed comparatively easily in spite of its great hardness. Table 8 summarizes some typical physical properties of the SiC ceramics. 

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