Ceramics

1.0 Overview Stone and granite are the oldest known ceramics. Their use in the construction industry has been largely replaced by two other ceramics, cement and concrete. The last 10 years has seen a significant development in the area of ceramics with the advent of an exciting range of high performance engineering ceramics which have the potential to replace and possibly improve on metals in many demanding applications. These ceramics are very wear resistant making them suitable for tools, their inertness makes them ideal for biocompatible applications like hip replacement joints. Their high melting temperature has resulted in a development programme looking into applications in turbines and turbo chargers. Modern body armour is made from a ceramic sewn into a fabric vest. One way of classifying ceramics is into 5 groups:1. Glasses 2. Vitreous ceramics (clay products, brick etc.) 3. High performance ceramics (alumina, zirconia etc.) 4. Cement and concrete 5. Rock and minerals Although the properties of ceramics do differ, they have one common and undesirable feature. They are all brittle. Most ceramic materials are cheap as the main constituents of many include silicon, aluminium, oxygen and nitrogen which occur abundantly. However, it is the processing costs that make ceramics expensive. Self-test activity – Write a list of the advantages and disadvantages of using ceramics materials. Include processing, properties and in service use. 1.1 Crystal Structures The bonding in a material determines many of its properties. The brittleness and electrical conductivity of ceramics is due to the type of bonds present. Ceramics can either be purely ionic or purely covalently bonded, but most are a mixture of the two types. The crystal structures of ceramics can be complicated so only some simple examples are used here. Glasses are considered in a separate section. Ceramics, like other materials, will contain structural defects and impurities. We can exploit these defects to give electrical conductivity via ionic diffusion. An example of this is the solid oxide fuel cell. Metals can be added to glasses to get amber, blue and green glass. Lead and silver in glass can give a range of reflected colours.

1.1a Ionic Ceramics These typically occur between a metal and non-metal e.g. alumina Al2O3 and zirconia ZrO2. Like the ionic bond between sodium and chlorine in sodium chloride the metal atoms have a positive charge (electropositive) and the non-metal a negative charge (electronegative). The strong attraction between these unlike charges results in an ionic bond. The simple ceramic structure based on a general formula AB has what is called the 'rock salt' structure based on sodium chloride. Here, to achieve the maximum electrostatic interaction each Na+ has 6 Clneighbours and no Na+ and vice versa. This is the most efficient way of arranging single charged species. The NaCl crystal is made up of a face centred cubic arrangement of sodium ions interlocked with a face centred cubic chlorine crystal. Other ceramic structures of general formula AB2, for example, have more complicated structures determined by the requirement for overall electrical neutrality and ion size. 1

each grain is more or less a perfect crystal meeting its neighbours at grain boundaries. Diamond is extremely hard with exceptional wear resistance and is very strong. high temperature bearings and engine parts and has a structure close to that of diamond and is one of the hardest known substances. e. they bond together reducing the surface area of the particles and increasing in density. Perhaps the ultimate covalent ceramic is diamond which has a 4 coordinated arrangement of carbon atoms within the cubic unit cell. as there is some residual porosity in the form of small rounded holes. 2. It is not a close packed structure (close packed structures have 12 neighbours = co-ordination number of 12) so its density is low. The structure of covalent ceramics are that they are not so densely packed and are often non-crystalline. commercial glasses are amorphous networks based on silica.1b Covalent Ceramics These are compounds of two non-metals e. diamond and graphite from carbon. Under these conditions the particles 'sinter'. Crystalline ceramics form polycrystalline microstructures similar to metals. usually by introducing a low melting point glassy phase. The drawback is that the dies and process are expensive. A different technique is used called 'sintering' where the ceramic in powder form is compressed at a temperature usually around 2/3Tm.1.2 Forming of Engineering Ceramics 1. Fig.g. 1. Full density is not achieved by this technique.g. which usually cannot be seen but are nevertheless present in most ceramics as a result of the processing. “hot pressing or hot isostatic pressing”. Self-test question – How does the interatomic bonding and crystal structure of a ceramic relate to some of the advantages and disadvantages on your list from Section 1. The shorter process time compared to normal sintering gives no opportunity for grain growth and as a consequence the mechanical properties are good.0? Self-test activity – Compare the atomic arrangement of carbon as diamond to that of carbon as graphite and a buckyball.g. although for rounded pores this can be small. the simultaneous application of temperature and high pressure to a ceramic powder. Fig 1. pore a) particles after pressing b) pore formation as sintering begins c) pores grow smaller as sintering proceeds Figure 1. Particle coalescence during sintering 2 . Very hard structural ceramics like silicon carbide SiC are used for load bearing components. silica SiO2 or are just pure elements e. The powder is squeezed in a die or pressure vessel while it is at its sintering temperature. More serious is the presence of cracks.2a Powder Pressing and Sintering Because of their high melting points ceramics cannot be processed by techniques used in polymers and metals. Higher densities and smaller grains are obtained by a different technique. This porosity can be as high as 20% and the pores tend to weaken the ceramic by inducing stress concentrations. Sintering aids can be added to the raw ceramic powder to achieve maximum density. Die pressing allows precision products to be manufactured without any subsequent finishing. that is. Longer sintering can reduce porosity but inevitably there will still be some residual porosity. Full density can only be reached by pressure sintering.

2 A typical crystalline ceramic microstructure 1. extruded or pressed as in normal polymer processing. clay and water. On the plus side the dimensional stability after sintering is usually of the order of 0. such as tape making and the production of films. The mould material is then dried and the ceramic part is then removed from the mould and then 'fired' at the appropriate temperature to give the final ceramic. especially in the electronics industry.1% which makes finishing operations unnecessary. However. Note: There are many other specialised ceramics processes. The polymer is 'burnt out' at high temperature where the silicon and carbon react. This process is cheaper that sintering and gives good precision. and then convert it to a ceramic. Another novel route to form some ceramics is to start with a special polymer. 1. Variations of this technique include pressure and vacuum casting where the 'slip' is shaped under vacuum or pressure. usually plaster of Paris. Pouring out the remainder of the 'slip' leaves this semi-hard layer on the surface of the mould. If the silicon and carbon powders are sintered together a simultaneous reaction takes place forming silicon carbide. Another way of 3 . It is also used as an economical means of producing development parts and on short production runs.2c Slip Casting Ceramic shapes can be cast by a technique called 'slip casting'. like all good ideas there is a penalty to be paid and that is the porosity is high. This is then poured into a porous mould. formed from voids left by the polymer. Glasses and ceramics can also be produced in fibre form. This technique has the advantage of forming thin walled and complex shapes of uniform thickness. silicon carbide SiC. One way to produce thin films that has been extensively researched and developed at Brunel is ink jet printing. Si + C = SiC Occasionally the silicon/carbon mixture is mixed with polymers to make it plastic allowing it to be rolled. called a pre-ceramic polymer.3 Ceramic Materials and Applications Ceramic materials are most useful in high temperature applications because of their mechanical and physical properties.Grain boundaries where two crystals meet Microcracks caused by thermal or mechanical stress Pores left by processing Grains (crystals) of the ceramic Fig. corrosion resistance and inertness.2b Reaction Bonding Some ceramics are produced by what is called 'reaction bonding' e. In this way complicated shapes can be achieved. allowing the water to be absorbed near the surface and leaving a semi hard layer. This process consists of a stable suspension or 'slip' of the ceramic. Self-test questions – Why are ceramics so difficult to process? What sort of problems can occur in a ceramic material because of the processing route? 1.g.

cements. abrasives. detailed below. Zirconia (ZrO2) * Can be transformation toughened * Used as a thermal barrier coating on superalloy aircraft turbine engine components Silicon carbide (SiC) * Hard refractory carbide * Outstanding oxidation resistance at high temperatures * Used as a protective coating on other ceramics and metals against extreme temperatures Silicon nitride (S3N4) * Most useful combination of engineering properties * Oxidation and high temperature strength lower than silicon carbide * Used in automotive and gas turbine engines providing higher operating temperatures for less weight compared to metals. Alumina (Al2O3) * Operates at high temperatures where good strength is required * Used in electrical applications where high electrical and thermal resistance is required * Classic example is the motor car spark plug insulator * Used in replacement body parts like hip joints because of its inertness Aluminium nitride (AlN) * Good electrical insulator but has a higher thermal conductivity than alumina because of its simpler atomic structure so it is a suitable replacement for alumina particularly where electrical insulation and good thermal conductivity is required.4 Joining of Ceramics Ceramics cannot be bolted or riveted as the contact stress would cause a brittle failure. nitrides and oxides. The last group. includes carbides.classifying ceramics is into one of six groups: glasses. refractories. Titanium diboride (TiB2) * Good conductor of heat and electricity * Excellent toughness * Used for body armour Sialon (Si3Al3O3N5) * Good stiffness and fracture toughness * Low thermal expansion * Used in engine components * Used for high temperature and wear environments Urania (UO2) * Nuclear reactor fuel * Excellent dimensional stability * Crystal structure can accommodate the products of the fission process Self-test questions – What are the advantages of using ceramic components in internal combustion engines? What factors are limiting the development of the ceramic engine? 1. Its thermal expansion coefficient is close to that of silicon making it useful as an integrated circuit substrate. For this reason ceramics tend to be bonded to other ceramics or metals using techniques which minimise these stress concentrations. borides. clay products. advanced ceramics. Diffusion bonding of ceramics is a result of the parts being heated and compressed until they 4 .

chemical and glass industries.K-1 and air is 0. The inherent brittleness of ceramic materials is further exaggerated by the presence of cracks. Ceramics used in insulation are usually porous. An example is yttrium barium copper oxide (YBa2Cu3O7). The chemical composition and microstructure of electrical grade ceramics must be closely controlled. porosity. Ceramics have a well defined Young’s modulus which is generally higher than those of metals (elastic deformation of metallic bond compared to an ionic or covalent bond) and this is one of the reasons why ceramics and glasses are used as reinforcing agents in composite materials. 1. At higher temperatures.. Many ceramics are hard and have low impact resistance. The crack propagates and leads to failure of the ceramic. The ionic and covalent bonding in ceramics restricts their electron mobility which gives them excellent insulating properties.m1 . similar to 'sintering' the parts together. σa ∀ 2 σ √a/r Where σa σ a r actual tip stress applied tensile stress length of the crack radius of the crack The stress at the tip of the crack is therefore large when the radius of the crack is small or the 5 .7 Mechanical Properties Ceramics are brittle and the strength of ceramics varies considerably. The metal part is then brazed to the treated ceramic surface. Heat transfer across pores is low as they contain air. Because of their high heat resistance they are used as refractories where hot liquid and gaseous environments are encountered. A simple relationship has been formulated by Griffith. Some ceramic materials become superconducting at higher critical temperatures than metals but still below room temperature. foreign inclusions. The inherent brittleness of the materials is limiting its fabrication into some useful superconducting shapes. Epoxy resins can also be used to join parts at low temperature. which states that for a flaw or crack the stress at the tip of the crack is given by. glassy phases and large grain sizes which may be introduced during manufacturing. The parts are pressed together and the temperature raised to the melting point of the glass. such as wires.g. Liquid nitrogen is cheaper then liquid hydrogen and liquid helium. This limits the ceramic to withstand a tensile stress as a crack or flaw will tend to concentrate the applied stress. molybdenum to the surface of the ceramic to be joined. Glaze bonding is achieved by coating the parts in a low melting point glass (600 oC). shape and orientation within a single component and from component to component. It becomes superconducting at 92K which means it can be cooled with liquid nitrogen. thermal conductivity by radiant heat transfer can occur.5 Electrical Properties Ceramics are used in many electrical and electronic applications such as electrical insulators and capacitors. This is more pronounced with optically clear materials. Fig 3. 1. Room temperature thermal conductivity of ceramics is between 2 and 50 W.K-1. Ceramics can be joined to metals by using adhesives or by brazing.02 W. Even dissimilar materials can be bonded in this way. These flaws vary in size. particularly in the metal. Brazing the two together is achieved by first applying a thin metal coating e. 1.fuse together.6 Thermal Properties In general ceramics are good thermal insulators.m-1.

Because of their rigid ionic and covalent structures ceramics do not undergo appreciable elastic deformation and as a consequence the modulus of elasticity (Young’s modulus) is large. chemical composition. r σ Fig.4.length of the crack is large. Grain boundaries are an important surface defect in ceramics where the smaller the grain size the stronger the ceramic as the finer grains help to reduce stresses that develop at grain boundaries. flaws and cracks. Fig. microstructure.0012 . 250 Aluminium Oxide Stress (MPa) Glass 0 0 strain 6 0. 3 A Griffith flaw in a ceramic component A typical stress/strain curves for ceramics is that of a brittle material. If the actual tip stress exceeds the yield strength of the ceramic then the crack will propagate and cause failure even if the applied stress may be small. if any. The strength of ceramics as we have seen is determined by many factors. Failure of the ceramic occurs with little. σ a Radius. temperature and environment. Smaller grain sizes are a result of using finer ceramic raw materials. Little or no plastic deformation is typical of a brittle fracture. plastic deformation and no localised reduction in area 'neck' as seen on ductile materials.

no long range order. electric bulbs.e. 3. silicon and sodium in soda glass. soda lime glass 69GPa. There is no long range order so glass has an amorphous structure. 4. good thermal shock resistance and chemical stability. Self-test question – Why are ceramics so weak when bond strength suggests they should be strong? 1. There are a number of different glasses. They have a high refractive index and are used in some optical glasses. usable to 1000oC. it is difficult to process because of its high melting point and is expensive.Figure 4: A stress/strain curve for alumina and glass. also called the elastic modulus. has a high spectral transmission and is not subject to radiation damage which causes 'browning' in other glasses. The higher the modulus. silicon dioxide (SiO2). used in windows. There is short range order in that every oxygen forms two bonds to a silicon and every silicon has four bonds to an oxygen. widely used in the chemical industry. This makes it an ideal glass for space vehicle windows and optical systems in spectrophotometric devices. the most important single component glass. Borosilicate (trade name Pyrex in cookware) Low expansion. The common ones are listed here. Low alkali (E-glass) Widely used as fibres in composites. Its chemical and heat resistance is poor. 5. NaO. containers. 7 Figure 5 shows the arrangement of oxygen. to reduce the melting temperature and make the glass much cheaper. Lead silicate Readily melted and fabricated with good electrical properties. 2. 1. Unlike crystalline ceramics. Both fail in a brittle manner. Steel has a value of 207 GPa. However.8 Glasses Glass is a ceramic material based on silica. Fused silica glass. Glass used in bottle manufacture contains additives such as soda. The Young’s modulus for alumina is one of the highest at 393GPA. very low expansion and high thermal shock resistance. . Used in low melting solder sealing glasses. The sodium ions penetrate the network and lower the melting point. Fused silica Difficult to melt and fabricate. Fused silica glass 73GPa. The modulus of a ceramic decreases as porosity increases. fluorescent lamp envelopes. High lead absorbs X-rays. the stiffer the material. the constituents of glass are heated to fusion and cooled to a rigid state which is amorphous in structure i. making the glass easier to work with. Used in optical systems and specialist windows. radiation windows. Soda lime Easily fabricated. widely used in varying grades. The slope of the curve represents Young’s Modulus.

What are the advantages and packaging material? disadvantages of using glass as a 1.10 A Few More Applications of Advanced Ceramics Application Bearings Cutting blades Property required Excellent surface finish Wear resistance Excellent surface finish 8 Ceramic Zirconia. particularly with metals * take into account batch to batch variations * be aware of the effect processing can have on the structure and properties of a component 1. Smaller particle size and accurate characterisation of particle shape is essential to decrease the possibility of microcracks and porosity. the strength of a particular ceramic can vary significantly even with supposedly identical pieces. So what can the engineer do to improve the variability in strength of components? DON'T DO * use sharp corners or notches which can act as stress raisers * ensure good surface finishes * utilise compressive joints and connections rather than flanges etc. Techniques have been developed based on injection moulding which squeezes the powders together under high pressures and leads to better consolidation. Alumina Silicon carbide Sialon. This type of material is referred to as a CERMET.Self-test question . tougher matrix material into the brittle ceramic matrix. structural defects and impurities that can exist in a ceramic structure. Most ceramics fail at an intermediate applied stress with some failing at lower and higher applied stresses. zirconia . high purity raw materials and complex processing is essential which makes the final product expensive. particularly where they are going to be used to carry load. But there is still the problem that there is a good probability of failure at low stresses and it is this uncertainty that limits the use of ceramics in critical applications. An example is the incorporation of a cobalt metal matrix into tungsten carbide (WC) which is used for cutting tools and abrasives. One is to incorporate a softer. It is this phenomenon that poses a serious problem to designers.9 Strengthening Ceramics Ceramics have a very poor fracture toughness which can limit the scope of their application. Because of the inherent porosity. The material retains the hardness and cutting ability of tungsten carbide while the softer ductile cobalt deforms and absorbs energy. * allow for thermal expansion mismatch. How does the designer evaluate the strength of ceramics with such a scatter in strength values? The Weibull distribution is a statistical means of describing the fraction of ceramic samples that will fail under a particular applied stress. There are a number of ways of improving the toughness of ceramics. In order to produce more reliable ceramics.

11 Summary Ceramics are brittle materials but very strong and wear resistance. Ceramics break well below the strengths predicted by their atomic bonding. zirconia Gas turbine blades Silicon nitride Engine components Thermal insulation.High strength Abrasive wheels Prostheses High strength. can be very expensive. Alumina Silicon carbide Alumina. They can be used at high temperatures and don’t corrode easily. biocompatible High temperature strength Creep resistance. 9 . wear resistance Good toughness High strength. which weakens the structure. wear resistance Zirconia. wear resistance excellent surface finish. The powders are compressed into the desired shape and then sintered at high temperature. like superconductors. The powders consolidate but small pores and cracks can remain. 1. Most ceramics occurring naturally are crystalline. thermal shock resistance. Sialon. Their processing is difficult and expensive and usually involves a powder route. They can be cheap as in building materials but special ceramics. except for the glasses which have an amorphous structure. alumina silicon carbide.

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