conductive ceramics

Introduction

      advanced industrial materials that, owing to modifications in their structure, serve as electrical conductors.

      In addition to the well-known physical properties of ceramic materials—hardness, compressive strength, brittleness—there is the property of electric resistivity. Most ceramics resist the flow of electric current, and for this reason ceramic materials such as porcelain have traditionally been made into electric insulators. Some ceramics, however, are excellent conductors of electricity. Most of these conductors are advanced ceramics, modern materials whose properties are modified through precise control over their fabrication from powders into products. The properties and manufacture of advanced ceramics are described in the article advanced ceramics. This article offers a survey of the properties and applications of several electrically conductive advanced ceramics.

      The causes of resistivity in most ceramics are described in the article ceramic composition and properties. For the purposes of this article, the origins of conductivity in ceramics may be explained briefly. Electric conductivity in ceramics, as in most materials, is of two types: electronic and ionic. Electronic conduction is the passage of free electrons through a material. In ceramics the ionic bonds holding the atoms together do not allow for free electrons. However, in some cases impurities of differing valence (that is, possessing different numbers of bonding electrons) may be included in the material, and these impurities may act as donors or acceptors of electrons. In other cases transition metals or rare-earth elements of varying valency may be included; these impurities may act as centres for polarons—species of electrons that create small regions of local polarization as they move from atom to atom. Electronically conductive ceramics are used as resistors, electrodes, and heating elements.

      Ionic conduction consists of the transit of ions (atoms of positive or negative charge) from one site to another via point defects called vacancies in the crystal lattice. At normal ambient temperatures very little ion hopping takes place, since the atoms are at relatively low energy states. At high temperatures, however, vacancies become mobile, and certain ceramics exhibit what is known as fast ionic conduction. These ceramics are especially useful in gas sensors, fuel cells, and batteries.

Thick-film and thin-film resistors and electrodes

      Semimetallic ceramic conductors have the highest conductivities of all but superconducting ceramics (described below). Examples of semimetallic ceramics are lead oxide (PbO), ruthenium dioxide (RuO₂), bismuth ruthenate (Bi₂Ru₂O₇), and bismuth iridate (Bi₂Ir₂O₇). Like metals, these materials have overlapping electron energy bands and are therefore excellent electronic conductors. They are used as “inks” for screen printing resistors into thick-film microcircuits. Inks are pulverized conductor and glaze particles dispersed in suitable organics, which impart the flow properties necessary for screen printing. On firing, the organics burn out as the glazes fuse. By varying the amount of conductor particles, it is possible to produce wide variations in the resistance of thick films.

      Ceramics based upon mixtures of indium oxide (In₂O₃) and tin oxide (SnO₂)—referred to in the electronics industry as indium tin oxide (ITO)—are outstanding electronic conductors, and they have the added virtue of being optically transparent. Conductivity and transparency arise from the combination of a large band gap and the incorporation of sufficient electron donors. There is thus an optimal electron concentration to maximize both electronic conductivity and optical transmission. ITO sees extensive application as thin transparent electrodes for solar cells and for liquid-crystal displays such as those employed in laptop computer screens. ITO also is employed as a thin-film resistor in integrated circuits. For these applications it is applied by standard thin-film deposition and photolithographic techniques.

Heating (heat) elements

       Heating element ceramicsA longstanding use of conductive ceramics is as heating elements for electric heaters and electrically heated furnaces. Conductive ceramics are especially effective at elevated temperatures and in oxidizing environments where oxidation-resistant metal alloys fail. Examples of electrode ceramics and their temperatures of maximum use in air are shown in Table 1 (Heating element ceramics). Each material has a unique conduction mechanism. silicon carbide (SiC) normally is a semiconductor; suitably doped, however, it is a good conductor. Both SiC and molybdenum disilicide (MoSi₂) form protective silica-glass surface layers, which protect them from oxidation in oxidizing atmospheres. MoSi₂ is a semimetal with a high conductivity. Lanthanum chromite (LaCr₂O₄) is a small polaron conductor; substituting alkaline-earth ions (e.g., calcium, or Ca²⁺) for La³⁺ results in an equal proportion of Cr³⁺ being converted to Cr⁴⁺. Hopping of electrons between the two states of Cr ions yields high conductivity, especially at elevated temperatures.

      Conduction in zirconia (ZrO₂) is ionic, as opposed to the electronic conduction mechanisms described above. When zirconia is doped with Ca²⁺ or yttrium ions (Y³⁺), oxygen vacancies are produced. Above 600° C (1,100° F), oxygen ions (O²⁻) become mobile and fill these vacancies, and they are highly mobile at higher temperatures. Zirconia heating elements require a preheater to reach the 600° C threshold, but they can be used to achieve temperatures up to 2,000° C (3,600° F).

      Tin oxide (SnO₂) has a very specific application as the preferred electrode for specialty glass-melting furnaces (as for optical glass). This application requires high conductivity and resistance to the corrosive elements in glass melts; in addition, corroded electrode material must not discolour the glass. Tin oxide is the only material that satisfies these criteria. Pure tin oxide is a wide band-gap semiconductor, but inherent oxygen deficiency plus the substitution of antimony ions for tin result in high conductivity.

Thermistors (thermistor)

      Thermistors, or thermally sensitive resistors, are electric resistors whose resistive properties vary with temperature. They are made of materials that have high temperature coefficients of resistance (TCR), the value that describes resistance change with temperature. Negative TCR, or NTCR, ceramics are materials whose electric resistance decreases as temperatures rise. These ceramics are usually spinels based on oxides of iron, cobalt, and manganese that exhibit small polaron conduction. Under normal temperatures there is an energy barrier to moving electrons from site to site. As thermal energy rises with temperature, however, the ability of electrons to surmount this barrier increases, so that resistivity goes down—hence the NTCR behaviour. Extensive solid solutions are possible in these materials (that is, a large number of foreign ions can substitute for the host ions in the crystal structure), so that the resistances and temperature coefficients can be tailored over wide ranges.

      NTCR thermistors are used as temperature sensors and as temperature compensation resistors. The beam focus coil in cathode-ray tubes for televisions and computers relies on NTCR thermistors to compensate for the resistivity of the coil material. Thermistors also are used as fuel-level sensors in gas tanks. When a thermistor under constant voltage is immersed in fuel, it loses more heat than when it is surrounded only by vapour. The difference in heat loss results in a change in resistance, which in turn changes the flow of current through the fuel sensor.

Gas sensors

carbon monoxide sensors

      In addition to the heating electrode applications noted above, tin oxide also is used in carbon monoxide gas sensors for home and industry. Adsorption of carbon monoxide at contacts between particles of SnO₂ produces local charge states that alter the electric properties (e.g., resistance, capacitance) of the porous, polycrystalline material. When life-threatening concentrations of carbon monoxide are detected, an alarm is triggered. By changing the temperature of operation, the sensor can be made selective for a variety of reducing gas species (such as hydrogen, carbon monoxide, and hydrocarbons).

oxygen sensors

      Oxygen sensors are employed in industry to monitor and control processing atmospheres and also in automobiles (automobile) to monitor and control the air-to-fuel (A/F) ratio in the internal combustion engine. A prominent sensor material is zirconia, which, as noted above, can be an excellent high-temperature oxygen conductor if suitably doped with Ca²⁺ or Y³⁺. A tube or thimble made of zirconia can be exposed on its exterior to the hot atmosphere to be monitored and on its interior to air, with high-temperature seals preventing leakage between the two environments. Porous platinum electrodes on the two surfaces can be used to register a galvanic cell voltage across the solid zirconia electrolyte that is proportional to the difference in oxygen content between the exterior atmosphere and the interior air.

 Each automobile has a zirconia oxygen sensor such as that illustrated in Figure 1—> inserted into its hot exhaust manifold. The primary function of the oxygen sensor there is to control the A/F ratio through appropriate feedback circuitry to the fuel injection system. Control is necessary to protect the catalytic converter elements from being poisoned at A/F ratios that are too high or too low.

Batteries (battery) and fuel cells (fuel cell)

      Two other galvanic applications of conductive ceramics are in batteries and fuel cells. A battery is a device that converts chemical energy into electricity. In its simplest form it consists of two metal or metal oxide elements, called the anode and the cathode, immersed in a liquid or solid chemical compound called the electrolyte. Ion flow in the electrolyte is accompanied by a compensating movement of electrons from the anode; the electrons flow through an appropriate conductor to the cathode, and the electric circuit is complete. Batteries are ubiquitous in modern life, finding use in toys, portable appliances, and motor vehicles.

      Fuel cells produce electric power like a battery, except that power production is prolonged by supplying a gaseous or liquid fuel to the anode and air or oxygen to the cathode. Fuel cells have been developed for load-leveling in electric power plants, but they also may be employed in motor vehicles. Batteries and fuel cells are described in detail in the articles battery and fuel cell.

Batteries

      High-energy-density batteries based on sodium beta-alumina have been developed for vehicular applications. Beta-alumina has the ideal formula Na₂O · 11Al₂O₃. It has a complicated structure consisting of spinel blocks sandwiching conduction planes in which sodium cations (Na⁺) can rapidly migrate. It is therefore known as a fast sodium ion conductor. A related structure is beta″-alumina, Na₂MgAl₁₀O₁₇, where magnesium cations (Mg²⁺) stabilize the structure and require additional Na⁺ in the conduction plane for charge compensation. These materials must be carefully processed in order to achieve uniform microstructures combining optimal strength and ionic conductivity. They are used as the solid electrolyte in the sodium-sulfur storage battery. Although this battery exhibits high energy density, corrosion problems and the requirement that the battery operate at elevated temperatures are drawbacks, especially in motor vehicles.

Fuel cells

      Of the several fuel cell types, ceramics play key roles in the molten carbonate fuel cell (MCFC) and the solid oxide fuel cell (SOFC). In the MCFC, nickel oxide (NO) ceramics serve as porous anodes for the molten salt (carbonate) electrolyte. In SOFCs, ceramics serve not only as the solid electrolyte (in this case, zirconia) but also as anodes and as conductive connections between adjacent cells (cobaltites, manganites, and chromites of various transition metals). Anode materials must be excellent electronic conductors. In the case of the SOFC anode, conductivity is accomplished by small polaron conduction between two valence states of the transition metal constituent.

      The processing of SOFCs is an extremely difficult proposition. Anode, electrolyte, cathode, and interconnecting layers must be suitable for firing together. Thermal expansion mismatch therefore must be minimized. Parts of the structure must be dense and gas-impervious (the electrolyte), whereas others are made intentionally porous (the electrodes).

Superconductors

  superconductivity is the complete disappearance of electric resistance in materials that are cooled to extremely low temperatures. The temperature at which resistance ceases is referred to as the transition temperature, or critical temperature (T_c). T_c is usually measured in degrees kelvin (K)—0 K being absolute zero, the temperature at which all atomic motion ceases. The best ceramic conductors are the so-called high T_c superconductors, materials that lose their resistance at much higher critical temperatures than their metal alloy counterparts. Most high T_c ceramics are layered structures, with two-dimensional copper-oxygen sheets along which superconduction takes place. The first of these was discovered in 1986 by the Swiss researchers J. Georg Bednorz and Karl Alex Müller. Within a year an yttrium barium copper oxide ceramic, YBa₂Cu₃O₇, had been discovered to have a T_c higher than 77 K, the boiling point of nitrogen (−195.8° C, or −320.4° F). This finding raised the possibility of practical superconductors being cooled by liquid nitrogen—as opposed to conventional superconducting materials, which have to be cooled by more expensive liquid helium. (The crystal structure of YBa₂Cu₃O₇ is described in the article ceramic composition and properties: Crystal structure (ceramic composition and properties), where it is illustrated in Figure 2—>D .)

      Although still higher transition temperatures have since been achieved, ceramic superconductors are difficult to process (in contrast to metal alloy superconductors), and they are notoriously brittle—properties that have limited their application. In hospitals and clinics small superconducting magnets are used in magnetic resonance imaging (MRI) apparatuses, where they generate the large magnetic fields necessary to excite and then image atomic nuclei in body tissues. Potential applications include wires for highly efficient superconducting magnets and low-loss electric power transmission lines, as well as advanced devices such as Josephson junctions and so-called SQUIDs (superconducting quantum interference devices). Josephson junctions, formed at contacts between two superconductors, can convert a direct voltage into an alternating current whose frequency rises with applied voltage. Frequencies in the superhigh frequency (SHF) range can be achieved. SQUIDs are highly sensitive magnetic-field sensors based on a superconducting ring with a weak link, a point where the material reverts to its normal, nonsuperconducting state at a small current relative to the rest of the ring. SQUIDs are widely used in geophysics for measuring magnetic field oscillations of the Earth. They also are used to record magnetograms of organs in the human body.

 Conductive ceramics are only one of several types of electroceramics. For a survey of all advanced electromagnetic applications, see electroceramics. For a directory to all the articles covering both traditional and advanced industrial ceramics, see Industrial Ceramics: Outline of Coverage—.

Additional Reading

Materials on conductive ceramics may be found in A.j. Moulson and J.M. Herbert, Electroceramics: Materials, Properties, Applications (1990); Larry L. Hench and J.K. West, Principles of Electronic Ceramics (1990); and the section titled “Electrical/Electronic Applications for Advanced Ceramics,” in Theodore J. Reinhart (ed.), Engineered Materials Handbook, vol. 4, Ceramics and Glasses, ed. by Samuel J. Schneider (1991), pp. 1105–66.A good introduction to ceramics in general is provided by David W. Richerson, Modern Ceramic Engineering: Properties, Processing, and Use in Design, 2nd ed., rev. and expanded (1992). The processing of both traditional and advanced ceramics is described in James S. Reed, Introduction to the Principles of Ceramic Processing (1988); I.J. McColm and N.J. Clark, Forming, Shaping, and Working of High Performance Ceramics (1988); George Y. Onoda, Jr., and Larry L. Hench, Ceramic Processing Before Firing (1978); and four sections of the Reinhart book cited above: “Ceramic Powders and Processing,” pp. 41–122; “Forming and Predensification, and Nontraditional Densification Processes,” pp. 123–241; “Firing/Sintering: Densification,” pp. 242–312; and “Final Shaping and Surface Finishing,” pp. 313–376.Thomas O. Mason

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