1 CERAMIC PIGMENTS AND GLASSES Marco Verit Stazione Sperimentale del Vetro Murano (Venezia) Italy Glass: nature

and properties Glass is an amorphous, solid material made of oxides, which forms by progressive solidification (viscosity increase) of a liquid obtained by melting crystalline minerals. The main difference between a crystalline and a vitreous solid is in the transition from the solid to the liquid state and vice versa. In a crystalline solid it occurs instantaneously at a well-defined temperature (melting/solidification temperature), whereas the transition in glass occurs progressively from complete rigidity to decreasing viscosity states. Crystalline silica (quartz) melts at 1710C. On cooling, the volume of the melt contracts because the relative mobility of molecules is reduced. Once the solidification temperature Tf is reached, a sudden decrease in volume occurs upon very slow cooling, as a result of the disorder-order transition. For furtherly decreasing temperatures the volume contracts continuously but at a slower rate (slope of the line:expansion coefficient) as compared to the liquid state. Let us assume now a more rapid cooling of the liquid, so that crystallization is not allowed the time necessary to occur. Its viscosity increases progressively; when the temperature Tf is reached, the volume does not vary abruptely, it decreases instead constantly with the same slope as the liquid and a supercooled liquid is obtained. Another phenomenon occurs on further cooling: at a temperature Tg, called glass transition temperature, the curve shows a decrease in slope which becomes then constant and parallel to the line of the crystalline solid phase. Tg, indicates the beginning of the transformation of a supercooled liquid into a vitreous solid, cannot be defined with the same accuracy as the melting point of crystalline materials, Tf. Indeed, the value of Tg depends on the cooling rate of the liquid: the highest the cooling rate, the highest the Tg value, owing to the lower time available for the molecular structural re-arrangement. The ability to form a vitreous material with normal cooling rates is a feature of very viscous liquids in the vicinity of their solidification point (silica and boric oxide are the most important). These are liquids (polimer into solution) whose considerably large molecules move not so easily relative to one another; therefore, all shifts and mutual re-arrangements that should let the molecules form a regular crystalline structure are slown down. These results can be interpreted in terms of materials structure. Within the region of the supercooled liquid, the molecules manage to re-arrange in an equilibrium configuration at the different temperatures. Below Tg, glass has about the same expansion coefficient as the corresponding crystalline material (quartz), so that it can be inferred that the molecules are trapped in a rigid structure also in glass (vitreous network), though without attaining the same order as the crystalline structure. In the crystalline forms of silica (quartz, trydimite, cristobalite) and in several silicates as well, the basic structural unit is the silica tetrahedron [SiO4], which consists of a Si atom in the centre

linked to four oxygen atoms disposed at the corners. The SiO bond is of the covalent-polar type, very strong. The tetrahedra are jouned by a bond from a corner to the corner of an adjacent tetrahedron, giving a three dimensional structure. In crystalline silica and silicates the continuous, regular network is formed by tetrahedra linked at their corners, such as to form always constant bond angles and hexagonal structure on the plane. In vitreous silica and glasses there is a continuous three dimensional random network, showing a certain order which is repeated at intervals (Zachariasen model of glass). In vitreous silica, the tetrahedra are linked at their corners in a continuous network, whose bond angles differ within a certain range (disordered network). Thus, an irregular structure arises, with four to eight tetrahedra linked at their corners. As a result, the strength of interatomic bonds will vary from one point of the structure to another. This model accounts for the absence of a well-defined melting point and the progressive transformation into the liquid state through a gradual decrease of viscosity (depolimerisation). The high viscosity makes it difficult for the orderly pattern required for crystal to form. When an alkali oxide (Li2O, Na2O, K2O, etc.) is added to a silica glass the network continuity breaks down partially, for the oxygen introduced by the oxide modifies the ratio between the silicium and oxygen ions, so that each oxygen atom cannot be strongly linked with two Si atoms as before. This oxygen will modify a Si Si bond into two SiO- units. Therefore, oxygen O atoms will exist belonging to only one tetrahedron and, consequently, also a number of tetrahedra with a non-linked corner. The oxygen ions linked to only one silicium ion are called non-bridging oxygens, to distinguish them from the remaining bridging oxygens. They will have a negative charge neutralized by the positive charge of alkali cations located in the holes in the network in the vicinity of non-bridging oxygens, so as to form ionic bonds weaker than the silicon-oxygen bond. The breakdown of the network in several points (also called depolymerisation of the vitreous network) weakens it and affects the properties of the glass. Particularly, viscosity at high temperatures decreases, thus allowing the glass to be melted at considerably lower temperatures than pure silica glass. This effect is more marked for increasing alcali oxides amounts. Network modifiers include alkalis and alkaline earths (alkaline earth oxides), the most common of which is CaO. The incorporation of CaO into the glass structure can be described in a way similar to the introduction of an alkali oxide. The CaO bond however, is stronger than the NaO bond, because of the valence 2 of the Ca2+ ion, so that the two non-bridging oxygens are both linked to the cation. Ternary glasses facilitate glass formation considerably and give stable glasses that will be discussed later. Intermediate oxides can act both as formers and as modifiers: Al2O3, ZnO, PbO, TiO2. The two dimensional[BO3] triangle is the basic unit of the B2O3 glass. Three of such triangles aggregate to form [ B3O6] boroxol groups, which in turn form an irregular network, as shown schematically in Figure ... Because of the differing B B angles projecting out of the O planme, collectively a spatial network arises. The stability of this network compared to that of vitreous silica is distinctly less, which will be reflected in the corresonding properties. Boric oxide facilitates glaze melting processes. When B2O3 is added to an alkali-silica glass it can enter the silica network. The formation of [BO4]- Na+ tetrahedra increases the chemical durability and decrease the thermal expansion of glass. Various types of silicate and borosilicate glasses containing lead oxide are frequently employed

3 as glaze coatings. In some cases the PbO content is very substantial, accounting for 70wt% or more. It is amazing how easily such compositions vitrify. Apparently lead glasses develop a state of equilibrium between Pb2+ and Pb4+ which enters the space lattice as a [PbO4] complex, thus facilitating glass formation. It should be kept in mind that Pb4+ ions have a much smaller radius than Pb2+ ions and they have a higher field strengh (see Table 1). To summarise: Glass structure have a random network in three dimensions but no unit repeats itself at regular distances. The basic unit is a tetrahedral or triangular co-ordination of a glass former with oxygen. The glass formers are few elements (Si, B, P, Ge, and few others). The ionic potential (valency versaus ionic radius) must be seven or more, thus indicating a very strong cation-oxygen bond; the oxygen atoms are linked to two glass forming cations (bridging oxygen) or with a ionic bond to modifiers cations (non-bridging oxygen); The interstices of this network are filled with elements which modify the physico-chemical properties of the glass (fusibility, hardness, chemical durability, etc). These stabilisers or modifiers are elements with ionic potential less than seven. They are relatively large compared with the glass formers (Table 1); Because of the random structure of glasses, no chemical formula can be devised. Physico-chemical properties The properties of glass are due to the strong intensity of interatomic bonds which form its structure. For example, high resistance to heat or to chemical attacks, but also a negative feature of this material, i.e., its fragility. The glassy state features a number of properties that are independent from the nature of the material. For instance, glass is an isotropic material, that is, its physical properties (optical, mechanical, etc.) exhibit constant values in any direction they are measured. Viscosity This is one of the most important properties of glass, because it determines the possibility of obtaining the glassy state on the one hand and, on the other hand, it is of greatest practical relevance during the forming processes of glass. Glass in the molten state can be regarded as a series of macromolecules formed by the rupture of network bonds and with a limited motion possibility. As temperature increases, the amount of broken bonds also increases, thus giving rise to smaller fragments with higher mobility and the viscosity of the melt will decrease. On cooling, the inverse phenomenon will occur, that is, a continuous re-building of new bonds between the fragments, a formation of more and more complex structural units and a consequent increase in viscosity.. With a viscosity of 104 poises, for instance, glass is viscous enough to be taken with the blowing pipe from the pot and shaped, while when the viscosity reaches 107.6 poises the glass is so viscous as to maintain the given shape and no further working is possible. Viscosity is strongly influenced by the chemical composition of the glass: for instance, it is evident that the introduction of modifier oxides and the consequent depolymerisation of the network following the breakage of the SiO Si bonds will lead to a marked decrease of viscosity. Alkaline-earth oxides introduced together with alkali oxides lower the viscosity of the glass that can be melted at lower temperature (i.e. 1200C insted of 1700C of silica). But a too

large addition of modifiers will reduce dramaticaly the chemical resistence of glass, that is its durability in contact with the atmosphere. Thermal expansion Nearly all solids expand upon heating; the thermal expansion coefficient of a body indicates the increase that a volume unit of the body undergoes on the increase of one degree of its temperature. Usually, the linear expansion coefficient (expressed in C-1) is adopted, referred to the elongation of the body in one direction on heating between 0 and 300C. At temperatures near the transition temperature Tg , increases suddenly, for the expansion of a liquid is about three times higher than that of the corresponding solid. The expansion coefficient depends on the glass composition; from the atomic point of view, the temperature increase leads to increasing amplitude of atomic vibrations in the network. It is clear that the introduction of network modifiers that break stronger primary bonds will yield glasses with higher values; also, for a same added amount of modifiers the cation which gives weaker bonds (for instance, potassium more than sodium, lead, calcium) will cause the highest increase of . The linear expansion coefficient varies between 130 x 10-6 C-1 for low melting enamels (containing several modifiers) and 55 x 10-6 C-1 for silica glass in which the bonds are stronger. If we consider an artifact made of a ceramic body and a glaze, it is clear that during cooling of the artifact, mechanical strains will appear. The two materials tries to contract diferently. Permanent and irreversible stresses will arise and make the artifact extremely brittle. Any variation in the temperature lead to an increase of the stress Termal conductivity and annealing In insulating amorphous solids, such as glass, thermal conductivity is extremely low. Compositional effects on the behaviour of glass relative to this property are neglectable. Low thermal conductivity is the reason for stress to arise between the surface and bulk glass in case of rapid temperature variations. Similarly, low thermal conductivity require a careful annealing process of glass artifacts. If a glass artifact is cooled rapidly enough after shaping, the outer layers will cool more rapidly and attain the solid state before inner ones. At the same time, a volume contraction will occur and the surface will tend to shrink more rapidly, yet hindered by the hotter inner layers which occupy a larger volume. Upon cooling under the transition temperature Tg permanent stresses will arise between outer and inner layers: the surface will be in a compressive strain, while the bulk will be in tensile strain. This unstable situation makes the glass more brittle and may lead to spontaneous fracture at any time. These stresses can be removed by a thermal treatment called anneling. The artifact is kept at a temperature close to Tg for a time long enough as to bring the surface and the inner layers to a thermal equilibrium. It is then cooled slowly, thus allowing the outer and inner layers to maintain an equilibrium with the external temperature. The cooling will be slower as the thickness of the glass article increases. Mechanical properties Glass is a perfectly elastic solid: the strain it undergoes when a load is applied remains constant in time and totally reverses immediately after the load is removed. If the stress is higher that the elasticity limit of the glass, the network bonds break down suddenly and the artefact undergoes catastrophic failure (glass is a brittle material). Fragile fracture is due to the breakdown of

5 bonds, and is generated by a much lower stress than the theoretical strength value of the glass. To explain this particular behaviour, Griffith suggested the hypothesis that fragility should be ascribed to microscopic defects associated with microcracks resulting from mechanical or chemical damage of the surface, such as small cracks, abrasions, deteriorated areas, devitrification, etc.. Certain defects would form as soon as the object is shaped, due to the contact of the surface with the atmosphere or solid bodies (moulds). This hypothesis is supported by the fact that glass objects shaped in a vacuum show a much higher mechanical strength than those shaped in the atmosphere. Moreover, if they are conserved in a vacuum their mechanical strength doesnt decay in time, as happens instead if objects are kept in normal atmosphere. Surface defects weaken a material because when even a modest stress is applied, it concentrates at the tip of the microcracks corresponding to the defects, thus generating an extremely high load in a localized point. The rapid fracture propagation is peculiar to glass and is associated with its homogeneity and structural continuity. In brittle crystalline solids, microcrack propagation to the bulk may be slow down by discontinuities existing at the crystalline interphase; on the contrary, such discontinuities are absent in glass and rapid fracture propagation is possible. Griffiths theory on surface microcracks explains also the poor resistance of glass to tensile or shear loads (less than 10 kg/mm2) and its high resistance under a compression load (more than 50 kg/mm2). Compression tends to close microcracks, while tensile stresses tend to enlarge the defect. The surface ability to withstand extremely concentrated loads is defined as the hardnessof glassy materials. In the Mohs scale glasses are not scratched by apatite crystals (hardness 5) but are scratched by quartz crystals (hardness 7). Hence, their hardness ranges between 5 and 7 according to their chemical composition: Lower values correspond to glasses containing high percentages of modifiers, or of lead oxide (lead crystal glass); higher values pertain to high silica glass, or glass high in other network formers such as boron (borosilicate glass). The cleaning of surfaces with abrasive materials of hardness higher than 6 (for instance, quartz powder) not only weakens glass from the mechanical point of view, it also leads to the formation of microscratches which will be the starting points of severe chemical deterioration processes, as will be discussed later. Chemical resistance and alteration processes Glass is a chemically inert, stable material. Glass is also a non-porous material as demonstrated by the smooth, shining surface. This is another aspect that reduce dramatically the specific surface and consequentely the reactivity of glass. In spite of its inertness, any glass artifact exposed along hundreds of years to not always favourable conservation environments undergoes surface transformations and alterations. These processes are extremely slow in time and involve thin surface layers. The attack by acids or aqueous solutions with a pH below 9 (neutral or acid) can be regarded as reaction of ion exchange (leaching) between the alkalis in the glass and H+ (or H3O+) ions in water. Durability improves with time; this phenomena is due to the formation of a hydrogenated silica-rich layer which is alkali-free, contains silica and stabilizing alkaline-earth oxides and H+ (or H3O+) bound in the network. This layer is protective because it slows down the interdiffusion of protons from the solution and of alkalis from the glass. A second kind of reaction (corrosion) occurs when the glass surface is in contact with basic

solutions, that is, with a pH higher than 9. This reaction is more and more rapid as the pH increases, it is not selective but attacks the silicon-oxygen bonds in the network, destroys it and brings all components into solution. In this case no protective layer is formed. Therefore, the difference in durability according to chemical composition to be discussed soon after refers only to the leaching reaction occuring at pH values lower than 9, whereas all glasses are low durable or even soluble in case of a corrosive basic attack. The degradation of a glass surface due to interaction with the atmosphere is referred to as weathering. The extent and type of alteration processes on glass surfaces are mainly affected by the chemical composition of glass and the environmental and microclimatic conditions in which the material is conserved. The glass composition is important in that it allows us to distinguish between four groups: inert, durable glass scarcely reactive to the environment and with a consequently high chemical resistance, and low durable or even soluble glasses. Pure silica is the most durable glass. In general, glass durability decreases for increasing amounts of network modifiers. The presence of alkaline earth modifiers such as CaO markedly increases the chemical resistance of alkali silicate glass. Also, small amounts of alumina improve chemical resistance. Glazes: General Considerations Glazes form a special section of a larger group of vitreous substances called glasses. A glaze is a thin, glassy layer on a ceramic body that results from applying a special mixture and fusing it on in a high-temperature firing process. The main difference between a ceramic glaze and a glass is that the glaze melts to form a thin layer with a strong bond to the ceramic substrate. The glazes are less homogeneous because of the presence of bubbles, incompletely reacted batch constituents and chemical disomogenety particularly at the glaze-body interaction zone. Probably the first glazes appeared 5-6 thausand years before Christ. Ancient Egyptians had priority in the use of glazes. Alkaline and lead glazes were already mass produced as early as the fourth millennium B.C. for decoration of pearls, statuettes, vases, etc. While the thickness of the glazes is negligeable compared to that of the body, they improve a number of exploitation parameters such as: Glaze eliminates the water permeability of porous bodies, enhance the aesthetic-artistic worth of the finished ceramic product, avoid the soiling of the body surface, eliminte surface irregularities, make the surfaces more resistant to mechanical loads and increase the strength of the product. Glazes are compouned in order to produce a covering of ceramic bodies which shall be among other things: suitable for producing decorative effects (colour, crystal development, with a gloss or matt surface, etc; fusible at predetermined temperature ranges. insoluble in water and the acid and basic solutions likely to be met in use; resistant to scratching; resistant to crazing, peeling and similar faults;

Classification of Glazes Many methods of classification have been adopted, all of empirical nature, according to: glaze composition: lead containing/leadless (low/high melting), boric, feldspathic, tin, zirconium, .... main fluxing agent: lead, lead-alkaline, lead-alkaline earth-alkaline, alkaline earth (CaO, MgO, BaO, SrO), boric, zinc, ... type of body: pottery/majolica/eartheware/sanitary glazes (ware to which it is applied); firing (or maturing) temperatures: majolica/earthenware/fireclay/porcelain (Table 2). preparation method: raw (obtained by fine grinding), fritted (quenching of the melt in water), grs, ... optical properties (effect produced on the finished article): transparent/opaque glazes, or depending on the appearance of the surface: glossy; matt; semi-matt; ... The term maturing implies that the glaze is not only melted, but it has flowed smoothly over the surface of the ceramic body and all bubbles, pinholes, etc, have disappeared leaving a flawless surface. The firing temperatures is the most common method of classifying glazes nowadays in use. Majolica and earthenware can be leadless or lead containing; they usually contain boron. Fireclay and porcelain are leadless (above 1150C lead compounds start to vaporise) and contain little or no boron. Glaze Fit The main requirement of a good glaze is perfect adaptability to the body to which it has to adhere firmly. The glaze and body must harmonise to such an extent that during firing they become as one. Not every glaze is suited to any one body. It is not enough to take just any glass and fuse it to the body. Usually, cooling would develop innumerable crazes or would cause peeling and carry off fragments of the body. The thermal expansion and contraction of solids are function of their chemical composition and thermal history. Thus, when a glass in the form of a glaze is fused on a ceramic body with greatly different coefficient of expansion, contraction takes place upon cooling and stresses are set up between the two. The composition of the ceramic body and glaze must be such that their thermal expansions are adjusted to each other. Usually is the composition of the glaze is altered to be adjusted to the body. Thermal expansion, as many properties of glasses (viscosity, density, ...), is approximately additive. The determination of the physical constants for the oxide is a matter of difficulty and different workers have given different values. These give only the order of magnitude of the expansion. Nevertheless these values are usefull in indicating how changes in composition can affect the expansion or contraction of the glaze. In practice the contraction of the body shall be slightly greater; in this way the glaze is compressed and this is a valuable insurance against crazing in service. In practice, a glaze might have a coefficient of linear expansion of 6.4x10-6 for a body having a value of 7.8x10-6 (20-500C). Whether or not crazing occurs, depends on: the strain set up in the glaze by differences in thermal expansion; the formation of the buffer layer (i.e. an intermediate zone between gaze and body); moisture expansion of the body (high in porous bodies, negligeable in vitreous b. as porcelain); the effect is to release the compression on the glaze slowly and to put it into

tension (crazing in service). From a too great difference in the expansion of the body, can lead to bowing of the article (the body forms the concave side, if glaze is on one side only). If the glaze is put into too great a compression it may crack and sheer off (peeling of the glaze, which occurs most likely on curved surfaces such as the rounded edges). The experimental determination of the fit between glazes and bodies is done by studying the bending of thin bars of the body glazed on one side. Preparation, Application and Melting of Glazes Raw materials There are many factors to be considered in choosing glaze raw materials. It is possible to arrive at the same chemical composition of the glaze by using different ingredients. Some ingredients are ciper than others: thus china clay, which brings in Al2O3 and SiO2, is likely to be cheaper than the separate oxides. Feldspar are a way to introduce low melting Al2O3 and save energy. Application A transparent gloss glaze can be obtained by firing a ceramic body coated with a thin layer of fine ground frit. Alternatively, the mixture of the raw materials can be applied (sanitary ceramics), or only a fluxer (for instance PbO) which reacts with the body minerals to form the glaze. Glaze frits are normally ground to a very thin diameter (50m). Coarse grinding makes it difficult to apply the slip glaze. A coating of sufficient thickness is taken up by dipping the articles in a slip glaze (a suspension of frit added of few % of caolin in water) or by spraying the slip. When flat wares such tiles are to be glazed only on one side, they are fed mechanically through a curtain of slip glaze. The amount of glaze taken up on dipping depends on a number of factors such as: viscosity, porosity of the were, time of immersion, etc. The viscosity is usually adjusted by additions of colloidal materials (gum, starches, derivatives of cellulose, ...). Firing The fusibility of glazes is of extreme importance. The aim is to produce a glaze which can be fired at as low temperature as possible consistent with the craze resistance. After the application of the slip glaze the ware is dried and than placed for firing. The firing operation must not only melt the glaze, but also maturing that is allow it to flow evenly over the surface of the article and all gas bubbles must be released. The expansion characteristics of the ceramic body determine to some extent the type of glaze which can be used. Increased alkali oxide markedly lowers the firing temperatures of glazes but in addition it gives increased expansion which leads to crazing if the addition is overdone. PbO and B2O3 are strong fluxers and lower the firing temperature. The alkaline earth oxides, CaO and BaO, tend to lower the firing temperatures but if the addition is overdone they can behave as refractory materials. Increasing SiO2 raises the melting point as also does Al2O3. The formation of eutectics can play a valuable part in melting mixtures of substances which in themselves may be quite refractory. During the heating of a glazed article gas escapes, either as a result of chemical reactions such as the decomposition of carbonates and the dehydration of clay, or from the escape of air trapped in the powdered glaze and in the biscuit. As soon as the glaze begins to melt, the escape of gases becomes more difficultend eventually it must bubble through the molten glaze. The speed with which it does this depends on the fluidity and thickness of the glaze. When the

9 bubbles reach the surface they will burst, leaving craters. The aim of subsequent heating is to fill these, otherwise pinholes may result. Cooling of the glaze may be done quickly. The devetrification (crystallisation) is greatest in the range 700-850C for most glazes; cooling should therefore be rapid over this range. Optical Properties Opaque Glazes A light beam crossing a transparent glass will propagate with a uniform stright-line motion. If the glass contains a microscopic phase uniformly distributed whose composition is different from the glassy matrix, the incident light beam will be scattered and reflected in all direction (light diffusion). The opacification process can be due to: the separation of a crystalline phase during coolong of a homogeneous melt (devitrification); the introduction of finely dispersed refractory non-soluble crystalline compounds into the batch or during melting (primary crystals); the separation of two non-miscible amorphous phases; the formation of bubbles. The degree of opacity in the glaze depends on: the concentration of the scattering particles; the particle size close to that of the wavelength of the light; the difference between its refractive index and that of the glassy phase; irregular surface shape. The most commonly employed opacifiers and their refractive indices are reported in Table 3. The purpose of opacification is to make the glaze nontransparent in order to hide the color of the body. A uncolored opaque glaze has a milky white appearance. The earliest known opaque glazes were made in Mesopotamia (Niniveh, Babylonia, 6th century B.C.) where lead glazes applied on bricks (glazed architectural ceramics) were opacified with stannic oxide. Later (9th century A.D.) Samaran potters used opaque glazes on ceramic vessels. The first opaque glazes appeared in Europe around the 1300 and were made by adding a calcine-mixture of stannic and lead oxides (tin ashes). The famous florentine ceramist Luca Della Robbia (1399-1482) widespred use of opaque glazes during Renaissance. The opacifier my be less soluble in one glass than in another. Common opacifiers are SnO2, the best opacifier for glazes becouse of the low solubility, and ZrO2. Stannic oxide used (no calcine is used today) to be introduced in the form of a calcine, i.e. a lead stannate produced by calcining lead and tin together. The Pb/Sn ratio ranges between 1/3 and 1/1, depending on the desired opacity. Zircon (zirconium silicate) is often use in place of zirconia. In a zircon opacification process, nucleation occurs at about 800C; ZrO2 crystals forming at temperatures up to 1050C remain stable up to about 1150C. Other substances like titania (TiO2), antimony oxide (Sb2O5) and certain fluorides have very little use in glazes. Poor opacifiers are air bubbles, undissolved quartz and feldspar inclusions and colourless crystalline silicates which develop during the firing such as acicular crystals of wollastonite (Ca silicate) and diopside (Ca,Mg silicate).

Excessive crystals growth can be avoided by milling the glaze to a fine consistency, allowing the surfaces of the frit particles to serve as additional nuclei in the melting glaze, providing an adequate number of nuclei. TiO2 usually crystallizes out in the form of rutile or anatase, the latter being preferable because of the white color it imparts. Rutile has tends to incorporate other ions into its crystal lattice, such as iron and chromium, which cause yellow discoloration. In the ceramic glazes which almost always contain same CaO, crystallization produce titanite (sphene) CaO.TiO2.SiO2 or 2ZnO.TiO2 less inclined to cause yellow discoloration. Phosphate glazes (bone ash is the least expensive opacifying agent) get their opacity from a secondary liquid phase that separates out in the form of tiny droplets. Coloring of glazes In Egypt and Mesopotamia (turquoise-blue glazed bricks from the Ishtar-portal in Babylon) decoration and coating of ceramic bodies were developed using a glassy base (glass making + ceramic firing). These glazes are based on alkali copper oxide free of lead and boron. It is not known exactly when lead as a raw material was first introduced in the glazing process. It is important to remember that the application of decorated glazes on ceramic bodies was developed empirically, in just the same way as ceramic objects were developed through the millennia. It was only after the 19th century that ceramic paints became objects of scientific study. At the end of the 19th century some chemical plants started the special production of ceramic paints (pigments and stains for under-glaze and on-glaze application). Today the palette includes glazes frits, ceramic glazes, inorganic pigments; ceramic paint plants offer today assortments of 300-7000 individual pigments, each one differing in tint and shade, for all kinds of applications, temperature ranges and chemical resistance. Ionic coloration is given by various oxides which dissolve in the glassy melt. The color depends on the: type of ion and its coordination number (Table 4), ion concentration, the glaze composition (the coordination of the ion is a function of the composition of the glaze, thus determining the hue); the firing conditions (oxidation or reduction of the ion). For instance, Fe(III) added in quantities of 1-3% under oxidizing firing conditions, imparts a yellow color, while 3-8% provide a reddish-brown color that develops well in lead glazes. Light cream hues can be obtained by adding stannic oxide. Adding less than 1% of Fe(II) produces a pale blue color; 2-5% a dark bluish green and 8-10% a dark-brown to black coloration. Copper oxides are strong colorants and enhance the gloss. Cu(II) give the glaze a blue color, Cu(I) a green one. Copper oxides were used by antique Egyptian potters; later, becames the most important coloring agent in Islamic ceramics. Co(II) oxide has the strongest coloring effect: as little as 0.2% suffices to color a glaze blue. It is stable both in reducing and oxidizing firing conditions. Only 1.5% of Chromium oxide dissolve in the glaze melt, and the remainder acts as an opacifier. Cr(III) impart a green color. Added in a high lead glaze chromium yelds a red coloration that changes to brawn at temperatures exceedeng 950C. Manganese oxide gives glazes a brown color, a reddish-brown in lead glazes and a violet color

11 to alkaline glazes. Colloidal suspensions in a glassy matrix of Cu, Au, Ag and pigmenting materials such as Cd sulfoselenides produce strong colors (yellow-orange, red). A thermal process is employed. The requirement in the production of such glasses (silver stain yellow and gold and copper rubies) is the ionic dissolution of the oxidised metal in the base glass at the melt stage, followed by its reduction to metal (addition of Carbon, sulphides, iron, etc.) with precipitation of metallic colloid particles during either the forming stage or on subsequent reheating. Development of the glass colour correspond to the aggregation of the metal atoms into colloids; normally it requires post-heating tretement. The glass formed and cooled (uncolored), is reheated to a temperature where nuclei are formed and grow to an optimum size for the development of a particular color (stricking process). Ceramic stains (pigments) are designated as firing-resistant materials (heat resisting between 500 and 1500C) used for colouration of ceramic materials, glasses and enamels. Their are applied as paints made of the inorganic pigments, fluxing agents (premelted glaze frits used as binders), inorganic additives (kaolin, alumina, zinc oxide, etc) and organic media volatilizing in ceramic firing. They can be used both for coloring glazes and for decorative purposes. Depending on where the colored layer is applied, differentiation is made between under-glaze (applied directly on the body and than covered with the transparent glaze), in-glaze and overglaze decoration. Underglaze colors are the more resistant to dissolutive effects of the overlying glaze during firing (they contain more alumina, quartz and zirconia) and to the weathering. The on-glaze decorations are fired at 750-850C, i.e. low enough to enable a wide selection of colors. They must contain a fluxing agent to ensure that the stain particles become embedded in a surface coating. The fluxing agent (usually lead and/or boric frits) are suppose to fully envelop the stain particles (not more of 20 wt%) without attack them chemically during firing. Glaze stains are mixture of metallic oxides and compounds that have been subjected to hightemperature calcination. They are classified into several groups, following their crystal systems. They constitute colored artificial minerals that result from solid-state reactions occurring within 800-1400C. The most commonly employed are reported in Table 5. Many ceramic stains show close similarity to natural mineral spinel. Its stable, chemically inert lattice contains ions of different valence, in both octaedral and tetrahedral coordination, wich enables the materialization of bright, stable stains. The general formula for spinels is RO.R2O3, containing a di-valent and a tri-valent oxide in a 1:1 mole ratio (mixed-crystals) with R as Zn, Mg, Co, Cd, Mn etc., and R2 as Al(III), Cr(III) or Fe(III). Mixed-crystals ceramic stains comprise an important group of ceramic pigments. The zircon based pigments are important because they contain only a small amount of the costly colouring substances and because they are thermally and chemically very stables. Introducing small amounts of rare elements into the crystal lattice of zircon produces ceramic stains characterized by high thermal resistance, chemical stability and covering power. The manufacture of ceramic stains requires strict process control. Today the market offers highquality stains at moderate prices. The finelly ground constituents are carefully proportioned and homogenized. The soluble constituents are added to the dry material in the form of concentrated solutions. The resultant paste is dried, ground down, re-homogenized and fired at high temperature in a refractory crucible. The prescribed firing temperatures should be closely adhered because the final color is partially dependent on the firing grade. After firing, the stains

are finely ground in ball mills and washed in order to remove the soluble salts. The analyses The analysis of glazes is a difficult operation and is not often undertaken. X-ray microanalysis associated to a SEM on polished cross-sections of the glazes is the best technique to determine the chemical composition of the vitreous and crystalline phases. This method allows to detect compositional gradients at the body/glaze interphase and to study the weathering phenomena (leached-corroded layers). WDS spectrometers are required to detect light elements such as boron. Examination by XRD yeld a definite information only on the nature of the crystalline pigments and opacifiers, while the glassy, random, amorphous structure give no peaks. Various colorimetric techniques based on spectral sensitivity and brightness are applied in the field of ceramics. In general, a given color can be adequately described according to its three main attributes: hue (differences in hte absorbed spectrum and in wavelength), saturation (degrees of paleness/fullness) and brightness. Bibliography Stefanov S., Batschwarov S., Ceramic Glazes. Chemistry, technology and practical application. Bauverlag GmbH, Berlino, 1988. Encyclopedia of Glass, Ceramics and Cement, Ed. by M. Grayson, Jhon Wiley & Sons, New York, 1985 Process Mineralogy of Ceramic Materials, Ed. by W. Baumgart, A.C. Dunham, Ferdinand Enke Publishers, Stuttgard, 1984 Scholze H., Glass, Nature, Structure and Properties, Springer-Verlag, New York, 1990 Tozzi N., Smalti ceramici. Considerazioni teoriche e pratiche, Gruppo Editoriale Faenza editrice, Faenza (Italy) 1992

13

Glossary Classification of glazes Lead glazes: low-melting, low viscosity, wide firing intervals, low surface tension, high refractive index, a glossy, smooth and well-fused surface; can be colored or opacified (SnO2). Lead ions are toxic and lead release by glazes is subject to stringent regulations; Boric glazes: low-melting, high resistence to crazing and chemical attack, gloss hard surface; Large amounts of B2O3 have negative effects; Alkaline glazes: used in Egypt and Mesopotamia as early as 4000 B.C. Low-melting, gloss surface, can be colored, high thermal expansion and are prone to crazing (crakled glazes); are obtained from alkaline frits. Alkaline-earth glazes: high melting, hard, resistant to crazing and acidic attack; Pottery: very porous bodies, fired prior to glazing. The glaze fired in the 800-1100C temperature range reacts weakily with the body and form a very thin intermediate layer. Majolica: colored porous body covered with a opaque glaze. The name derives from the Spanish island of Majorca, were the product reached its zenith in the 14th and 15th centuries. The Arabian brought the art to Northen Africa, from where it later sread to Europe. The classic majolica is glazed exclusively with SnO2 glazes (lead-alkaline); are used on biscuit-fired, porous bodies, melting points situated between 850-1150C. The relatively high Ca content of the body favors the formation of an intermediate layer between the glaze and the body. Are suited for coloring. Earthenware tiles: a wide range of glazes is necessary. Modern glazing methods are characterized in: reduced amount of frit, use of unfritted raw glazes (instead of fritted glazes), improved wear resistance and durability (achieved through saturation with crystal phases), dry application instead of wet glazing, ..... Vitreous china: single-fired (1150-1200C), consists of sanitary and tableware characterized by a well-sintered body, less than 0.5% water absorption capacity. Raw or partially fritted glazes, most frequently opacified with zirconium silicate, are used. Stoneware: sintered body, absorbs less than 3% water, single-fired at 1200-1300C. A very well-developed intermediate layer that give the article high strength is formed. Porcelain: Porcelain glazes originated in China during the Han dynasty, 185 B.C. Scientific investigations conduced on antique Chinese glazes show that the composition were closely related to those of the bodies, with the difference of more calcium oxide and less silica and alumina. (54% SiO2, 14% Al2O3, 4.4% Fe2O3, 19% CaO, 2% MgO, and 4.4% alkaline oxides). They were made of a natural mixture of mica, albite and quartz. It was not until 1710, after long years of experimentation that Meissen Porcelain Manufacture succceeded in producing Europes first genuine raw porcelain glazes with good gloss and transparency. Raw alkaline-earth glazes made of natural raw materials, fired at 1260-1450C on a biscuit-fired (850-950C) body. Thich-walled articles can also be glazed after drying and subsequently single-fired. The tipical porcelain glaze has a composition similar to that of body and develops a good glaze/body intermediate layer. Matt glazes: the difference between a mat and a glossy glaze is that the former has a large number of uniformely dispersed, very small crystals situated on the glaze surface. Zinc oxide and rutile (TiO2) are matting agents.

Crystalline glazes: are used to achieve special decorative effects in art ceramics. The transparent basic glaze contains crystals with interesting shapes and various colors. During cooling crystals separate out of the glaze melt (devetrification) at about 700-900C. The main difference with the opaque glazes are the fewer individual crystals, sometime visible to naked eye (chromium, aventurine, ....). Luster (iridescent) glazes: a metallic iridescent glittery surface, developed in the Near Est (Islamic ceramics). The effect is due to the formation of small metallic particles (silver, copper) under the effect of reducing atmosphere. Defects of glazes Exfoliation When the body shrinks more than the glaze, the glaze (under compressive stress) may spall off small particles. Crazing appearance of a network of fine hairline cracks after firing (occurrence of tension between the body and the glaze); the TEC (thermal expansion coefficient) of the body is lower than that of the glaze, the glaze shrinks more during cooling and is subject to tensile stress. If the TEC is large enough, the glaze begins to craze. Another factor with an influence on crazing is the elasticity of the glaze; adding boric oxide improves the elasticity. If the glaze is sufficiently elastic, the glaze remains under stress, so that any additional stress occurring subsequently (moisture expansion, thermal shock, etc) can trigger crazing. Contraction (crawling) of glazes This defect consist of irregular unglazed areas appearing on the fired ware. The glaze is seen to have contracted to form droplets before solidifying. Causes: dust on the surface (grinding time too long), use of set-up agents, accumulation of water-soluble salts, etc.

15 Table1 Valency Ionic radius 1 1 1 2 2 2 2 4 3 3 4 4 4 5 0.68 0.98 1.33 0.71 0.99 1.35 1.21 0.84 0.50 0.20 0.41 0.80 0.71 0.34 1.0 0.75 2.8 2.0 1.4 1.2 4.8 6.0 15.0 9.8 5.0 5.6 14.7

Cation Li Na K Mg Ca Ba Pb Pb Al B Si Zr Sn P

Ionic potential (Val./I. rad.) 1.5

Classification Pottery Majolica Earthenware

Table 2 Classification of glazes Maturing Wares Temp. (C) 800 - 1100 tableware, tiles, bricks, ... 900 - 1050 1000 - 1150 1150 - 1250 1300 decorative ceramics, tableware, tiles tableware, tiles, sanitary, decorative c. tableware, tiles, sanitary, decorative c. tableware, decorative c. engineering bricks, decorative

Fireclay, Vitreous China Porcelain Stone Ware

c., chemical apparatus Technical Ceramics corundum, cordierite, steatite articles

17

Table 3 Refractive indices of opacifiers Opacifier Cassiterite Zirconia Zircon Anatase Rutile Titanate (sphene) Calcium fluoride Sodium fluoride Hydroxyapatite Ca pyroantimonate Lead oxyarsenate Quartz Glazes SnO2 ZrO2 ZrSiO4 TiO2 TiO2 CaO.TiO2.SiO2 CaF2 NaF 3Ca3(PO4) 2.CaF2 Ca2Sb2O7 3Pb3(AsO4)2.PbO SiO2

Index of refraction (nD) 2,04 2,20 1,94 2,52 2,76 1,90 1,43 1,32

1,55 1,5 - 1,6

Table 4 Main glass ionic colors Co(II) blue Cu(II) Cu(I) Cr(III) Cr(III),Co(II) Fe(II) Fe(III) Mn(III) Ti(IV) light blue green green blue-green brown yellow brown-violet brown

Ni(II) Co(II),Mn(III)

gray black

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Table 5 Mineralogical composition of ceramic stains; in dark are indicated the coloring ions

Mineral
Baddeleyte Borate Corundum-hematite

Formula
(Zr,V)O2 (Co,Mg)B2O5 (Al,Cr)2O3 (Mn,Al)2O3 (Fe,Cr)2O3 Co3(PO4)2 Pb2Sb2O7 PbSnO3 (Ni Sb Ti)O2 CaO.SnO2.SiO2.Cr2O3 CoAl2O4 Co2SnO4 CoCrO4 Co2TiO4 Fe2TiO4 CuCr2O4 (Co,Fe)(Fe,Cr)2O4 (Y,Cr)AlO3 (Zr,V)SiO4 (Zr,Pr)SiO4 (Zr,Fe)SiO4 (Zr,Cr)SiO4 (Zr,Mn)SiO4 (Zr,Ce)SiO4 (Zr,Nd)SiO4 (Zr,Ce,Pr)SiO4 (Zr,Pr,Mo) SiO4 (Zr,(CdSSe))SiO4

Coloration
yellow bluish red pink pink blackish green violet yellow yellow yellow pink blue blue green green brown black black red blue yellow red green pink ivory pink-violet yellow-orange yellow pink

Phosphate Pyrochlore Rutile cassiterite Sphene Spinel

Perowskite Zircon

Zircon