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Ceramics

From Academic Kids

The word ceramic is derived from the Greek word Κεραμεικος (the name of a suburb of Athens), and in its strictest sense refers to clay in all its forms. However, modern usage of the term broadens the meaning to include all inorganic non-metallic materials. Up until the 1950s or so, the most important of these were the traditional clays, made into pottery, bricks, tiles and the like, along with cements and glass. The traditional crafts are described in the article on pottery. A composite material of ceramic and metal is known as cermet.

The Venus of Dolni Vestonice is the oldest known ceramic in the world. Historically, ceramic products have been hard, porous and brittle. The study of ceramics consists to a large extent of methods to mitigate these problems, and accentuate the strengths of the materials, as well as to offer up unusual uses for these materials.

Contents

Examples of Ceramic Materials

Properties of Ceramics

Mechanical properties

Ceramic materials are usually ionic or covalently-bonded materials, and can be crystalline or amorphous. A material held together by either type of bond will tend to fracture before any plastic deformation takes place, which results in poor toughness in these materials. Additionally, because these materials tend to be porous, the pores and other microscopic imperfections act as stress concentrators, decreasing the toughness further, and reducing the tensile strength. These combine to give catastrophic failures, as opposed to the normally much more gentle failure modes of metals.

These materials do show plastic deformation. However, due to the rigid structure of the crystalline materials, there are very few available slip systems for dislocations to move, and so they deform very slowly. With the non-crystalline (glassy) materials, viscous flow is the dominant source of plastic deformation, and is also very slow. It is therefore neglected in many applications of ceramic materials.

Electrical properties


Semiconductivity

There are a number of ceramics that are semiconductors. Most of these are transition metal oxides that are II-VI semiconductors, such as zinc oxide.

Whilst there is talk of making blue LEDs from zinc oxide, ceramicists are most interested in the electrical properties that show grain boundary effects.

One of the most widely used of these is the varistor. These are devices that exhibit the unusual property of negative resistance. Once the voltage across the device reaches a certain threshold, there is a breakdown of the electrical structure in the vicinity of the grain boundaries, which results in its electrical resistance dropping from several megaohms down to a few hundred ohms. The major advantage of these is that they can dissipate a lot of energy, and they self reset — after the voltage across the device drops below the threshold, its resistance returns to being high.

This makes them ideal for surge-protection applications. As there is control over the threshold voltage and energy tolerance, they find use in all sorts of applications. The best demonstration of their ability can be found in electrical substations, where they are employed to protect the infrastructure from lightning strikes. They have rapid response, are low maintenance, and do not appreciably degrade from use, making them virtually ideal devices for this application.

Semiconducting ceramics are also employed as gas sensors. When various gases are passed over a polycrystalline ceramic, its electrical resistance changes. With tuning to the possible gas mixtures, very inexpensive devices can be produced.

Superconductivity

Under some conditions, such as extremely low temperature, some ceramics exhibit superconductivity. The exact reason for this is not known, but there are two major families of superconducting ceramics.

Processing of Ceramic Materials

Non-crystalline ceramics, being glasses, tend to be formed from melts. The glass is shaped when either fully molten, by casting, or when in a state of toffee-like viscosity, by methods such as blowing to a mould.

Crystalline ceramic materials are not amenable to a great range of processing. Methods for dealing with them tend to fall into one of two categories - either make the ceramic in the desired shape, by reaction in situ, or by forming powders into the desired shape, and then sintering to form a solid body. A few methods use a hybrid between the two approaches.

In situ manufacturing

The most common use of this method is in the production of cement and concrete. Here, the dehydrated powders are mixed with water. This starts hydration reactions, which result in long, interlocking crystals forming around the aggregates. Over time, these result in a solid ceramic.

The biggest problem with this method is that most reactions are so fast that good mixing is not possible, which tends to prevent large-scale construction. However, small-scale systems can be made by deposition techniques, where the various materials are introduced above a substrate, and react and form the ceramic on the substrate. This borrows techniques from the semiconductor industry, such as chemical vapour deposition, and is very useful for coatings.

These tend to produce very dense ceramics, but do so slowly.

Sintering-based methods

The principles of sintering-based methods is simple. Once a roughly held together object (called a "green body") is made, it is baked in a kiln, where diffusion processes cause the green body to shrink. The pores in the object close up, resulting in a denser, stronger product. The firing is done at a temperature below the melting point of the ceramic. There is virtually always some porosity left, but the real advantage of this method is that the green body can be produced in any way imaginable, and still be sintered. This makes it a very versatile route.

There are thousands of possible refinements of this process. Some of the most common involve pressing the green body to give the densification a head start and reduce the sintering time needed. Sometimes organic binders are added to hold the green body together; these burn out during the firing (at 200-350?C). Sometimes organic lubricants are added during pressing to increase densification. It is not uncommon to combine these, and add binders and lubricants to a powder, then press. (The formulation of these organic chemical additives is an art in itself. This is particularly important in the manufacture of high performance ceramics such as those used by the billions for electronics, in capacitors, inductors, sensors, etc. The specialized formulations most commonly used in electronics are detailed in the book "Tape Casting," by R.E. Mistler, et al., Amer. Ceramic Soc. [Westerville, Ohio], 2000.) A comprehensive book on the subject, for mechanical as well as electronics applications, is "Organic Additives and Ceramic Processing," by D. J. Shanefield, Kluwer Publishers [Boston], 1996.

A slurry can be used in place of a powder, and then cast into a desired shape, dried and then sintered. Indeed, traditional pottery is done with this type of method, using a plastic mixture worked with the hands.

If a mixture of different materials is used together in a ceramic, the sintering temperature is sometimes above the melting point of one minor component - a liquid phase sintering. This results in shorter sintering times compared to solid state sintering.

Other applications of ceramics

A couple of decades ago, Toyota researched production of an adiabatic ceramic engine which can run at a temperature of over 6000 ?F (3300 ?C). Ceramic engines do not require a cooling system and hence allow a major weight reduction and therefore greater fuel efficiency. Fuel efficiency of the engine is also higher at high temperature. In a conventional metallic engine, much of the energy released from the fuel must be dissipated as waste heat in order to prevent a meltdown of the metallic parts.

Despite all of these desirable properties, such engines are not in production because the manufacturing of ceramic parts in the requisite precision and durability is difficult. Imperfection in the ceramic leads to cracks, which can lead to potentially dangerous equipment failure. Such engines are possible in laboratory settings, but mass-production is infeasible with current technology.

Work is being done in developing ceramic parts for gas turbine engines. Currently, even blades made of advanced metal alloys used in the engines' hot section require cooling and careful limiting of operating temperatures. Turbine engines made with ceramics could operate more efficiently, giving aircraft greater range and payload for a set amount of fuel.

Since the late 1990s highly specialized ceramics, usually based on boron carbide, formed into plates and lined with Spectra, have been used in ballistic armored vests to repel large-caliber rifle fire. Such plates are known commonly as small-arms protective inserts (SAPI). Very similar technology is used for armoring of cockpits of some military airplanes, because of the low weight of the material.

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