Whitewares

Whitewares
Karl-Heinz Schuller, Fachhochschule N rnberg, Fachbereich Werkstofftechnik, N rnberg, Federal u u Republic of Germany Introduction . . . . . . . . . . . . . . . Denitions and Classication . . . . Porous Whitewares: Earthenware . Types of Earthenware . . . . . . . . . Structure and Properties . . . . . . . Raw Materials . . . . . . . . . . . . . . Fabrication of Tableware and Fancy Goods . . . . . . . . . . . . . . . . . . . . 3.5. Fabrication of Wall and Floor Tiles 3.6. Glazing of Earthenware . . . . . . . . 3.6.1. Composition and Properties . . . . . . 3.6.2. Glaze Stresses . . . . . . . . . . . . . . . 4. Vitried Whitewares: Porcelain and China . . . . . . . . . . . . . . . . . . . . 1. 2. 3. 3.1. 3.2. 3.3. 3.4. Types of China and Porcelain . . . . Physical Properties . . . . . . . . . . . Chemical Properties . . . . . . . . . . Raw Materials . . . . . . . . . . . . . . Special Types of China and Porcelain . . . . . . . . . . . . . . . . . . . . . Porcelain Structure: Theoretical Background . . . . . . . . . . . . . . . . Fabrication of China and Porcelain Standards . . . . . . . . . . . . . . . . . Technical Ceramics . . . . . . . . . . . Steatite Whitewares . . . . . . . . . . Cordierite Whitewares . . . . . . . . References . . . . . . . . . . . . . . . . .

1 2 4 4 4 6 7 8 8 8 9 9

4.1. 4.2. 4.3. 4.4. 4.5. 4.6. 4.7. 4.8. 5. 5.1. 5.2. 6.

9 9 11 11 13 14 14 16 16 16 16 17

1. Introduction
The term whiteware was originally applied to white tableware and artware. It is now used for all ceramic ware that is ivory colored or has a light grey appearance in the red state. Fine ceramic whitewares are conveniently divided into two classes: 1) Triaxial bodies, consisting primarily of the three components: clays, feldspathic materials, and quartz 2) Nontriaxial bodies made entirely or predominantly of other materials The whiteware group can be divided into ve categories: earthenware; stoneware; china; porcelain; and technical ceramics. This article covers mainly earthenware, china, porcelains, and technical ceramics (the latter in so far as they are based on clays and other silicates). Stoneware is mostly a colored type of ceramic ware and it is treated elsewhere ( Construction Ceramics). Technical ceramics comprise silicates and materials based on oxides, carbides, nitrides, and similar compounds ( Ceramics, Electronic).

2. Denitions and Classication

The ASTM standard C 242-92 gives the following denition of whitewares: Ceramic Whiteware. A red ware consisting of a glazed or unglazed ceramic body which is commonly white and of ne texture; designating such product classications as tile, china, porcelain, semivitreous, and earthenware. Some denitions taken from ASTM C 24292 and essential to this article follow: Body. The structural portion of a ceramic article, or the material or mixture from which it is made. Bone china. A translucent china made from a ceramic whiteware body composition containing a minimum of 25 % bone ash. Ceramic article. An article having a glazed or unglazed body of crystalline or partly crystalline structure, or of glass, which is produced from essentially inorganic, nonmetallic substances and either is formed from a molten mass which solidies on cooling, or is formed and simultaneously or subsequently matured by the action of heat.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a28 243

Whitewares Ceramic process. The production of articles or coatings from essentially inorganic, nonmetallic materials, the article or coating being made permanent and suitable for utilitarian and decorative purposes by the action of heat at temperatures sufcient to cause sintering, solid-state reactions, bonding, or conversion partially or wholly to the glassy state. Ceramics. A general term applied to the art or technique of producing articles by a ceramic process, or to the articles so produced. China. A glazed or unglazed vitreous ceramic whiteware made by the china process and used for nontechnical purposes, designating such products as dinnerware, sanitary ware, and artware when they are vitreous. China sanitary ware. Glazed, vitried whiteware xtures having a sanitary service function. Decoration. Inglaze decoration. A ceramic decoration applied on the surface of an unred glaze and matured with the glaze. Overglaze decoration. A ceramic or metallic decoration applied and red on the previously glazed surface of ceramic ware. Polychrome decoration. A multicolor decoration. Underglaze decoration. A ceramic decoration applied directly on the surface of ceramic ware and subsequently covered with a transparent glaze. Dinnerware. Ceramic whiteware made in a given pattern and in a full line of articles comprising a dinner service. Earthenware. A glazed or unglazed nonvitreous ceramic whiteware. Electrical porcelain. Vitried whiteware having an electrical insulating function. Frit. A product made by quenching and breaking up a glass of a specic composition, used customarily as a component of a glaze, body, or porcelain enamel. Glaze. A ceramic coating matured to the glassy state on a formed ceramic article, or the material or mixture from which the coating is made. Impervious. That degree of vitrication evidenced visually by complete resistance to dye penetration. Jasper ware. A vitreous, opaque, colored, unglazed ceramic ware having white or contrasting relief decorations and containing a substantial amount of barite. Majolica. Formerly an earthenware with an opaque luster glaze and overglaze colored decorations, but currently designating any decorated earthenware having an opaque glaze. Mullite porcelain. A vitreous ceramic whiteware for technical applications in which mullite (3 Al2 O3 2 SiO2 ) is the essential crystalline phase. Mullite whiteware. Any ceramic whiteware in which mullite (3 Al2 O3 2 SiO2 ) is the essential crystalline phase. Oven ware. Ceramic whiteware for culinary oven use. Porcelain. A glazed or unglazed vitreous ceramic whiteware made by the porcelain process, and used for technical purposes, designating such products as electrical, chemical, mechanical, structural, and thermal wares when they are vitreous. Porcelain process. The method of producing glazed ware by which a ceramic body and glaze are matured together in the same ring operation. Pottery. All red ceramic wares that contain clay when formed, except technical, structural, and refractory products. Semiporcelain. A trade term designating semivitreous dinnerware. Semivitreous (semivitried). That degree of vitrication evidenced by a moderate or intermediate water absorption. Stoneware. A vitreous or semivitreous ceramic ware of ne texture, made primarily from nonrefractory reclay. Tableware. All utensils and decorative articles used on the table for meal service. Vitreous (vitried). That degree of vitrication evidenced by low water absorption. Certain terms have developed different meanings in various countries. In the United Kingdom and the United States, ceramics comprises all

Whitewares inorganic nonmetallic materials. In Central Europe the term Keramik is restricted to materials which meet the following conditions [2123]. 1) They are inorganic and nonmetallic 2) They are partially or completely crystalline, 30 % crystallinity being the lower limit 3) They are insoluble in water 4) They are heated to high temperatures during production or use; in modern ceramic materials, heating above 900 C is necessary to produce the desired structure and properties In this article, ceramics has the meaning of the German term Keramik, i.e., it excludes glass and glass ceramics. Ceramics are classied according to grain size (body texture), vitrication, body color, translucency, and porosity. Bodies with grain size >0.1 mm appear inhomogeneous to the naked eye; the German term for products with this coarse body texture is Grobkeramik (= coarse ceramic). This generic term includes various groups of products, e.g., bricks, tiles, and refractories. In the eld of tableware, the nearest equivalent in English is common pottery, a term recognized internationally for tariff purposes. Bodies with grain size <0.1 mm appear uniform in texture, even when they are really inhomogeneous on a microscopic scale. The German term for products with this ne body texture is Feinkeramik (= ne ceramics). There is no equivalent in English. The term ne ceramics has been introduced in Japan to summarize materials based on oxides, carbides, nitrides, and other materials, used for advanced applications. This differs fundamentally from the German concept of Feinkeramik. The clay-based materials in the group Feinkeramik are further classied according to color and porosity: Common pottery: colored, porous Earthenware: white or at least bright, porous Stoneware: colored, vitried China or porcelain: white, translucent, vitried The distinction between porous and dense structures is made on the basis of water absorption; dense materials have water absorption < 2 wt %. In the United Kingdom, the terms china and porcelain are synonyms when applied to the clas-

sication of tableware. Bone china is dened simply as a special composition with a minimum tricalcium phosphate content within the china and porcelain classication. The key property requirements for tableware in this classication are a very low water absorption (corresponding to a high degree of vitrication), a white body, and translucency in thin sections. Thus, the same properties are recognized in the United Kingdom as in Germany in the denition of Porzellan. The denitions of ASTM C 242-92 are similar in scope to the German denitions, but distinctions between materials are not made on a quantitative basis, and difculties may arise in nding equivalent English and German terms. The term porcelain is also used for technical ceramics in the United Kingdom and the United States. For example, in the United Kingdom, it is used for electrical porcelain which is vitried, but not translucent. Porcelain, as dened in ASTM C 242-92, comprises certain special types of technical ceramics, e.g., cordierite, forsterite, steatite, titania (titanium dioxide), and zircon porcelain. In some countries, porcelain is generally classied as a luxury article for tariff purposes, regardless of the real type of ware; this can be a serious obstacle to international trade in some types of technical ceramics, and whiteware seems to be the preferable term. These materials can be dened as special types of ceramic whitewares, avoiding their classication as types of porcelain. A European standard for classication of materials used for tableware is in preparation. No generally accepted agreement has been reached so far, partly because of the uncertain classication of borderline materials, and partly because of traditional assignments of certain materials to special groups. Porcelains may have a residual porosity up to 0.5 % according to the draft European standard, although any porosity impairs translucency. Bruno Sanders [24] introduced the following German terms for the characterization of materials: Gef ge: u all characteristics which can be used for the description of a material, e.g., structure, including microstructure Struktur:

Whitewares characteristics which are independent of direction Textur: characteristics which depend on direction, e.g., orientation as limestone, chalk, or marble to the clay body. Dolomite is also sometimes used. Free silica is added as a further ingredient. Feldspathic earthenware contains 5 20 % feldspathic material, introduced as beneciated soda or potash feldspar, or nepheline syenite, or, in an impure form, as arcose sands; the remainder consists of ca. 50 % ball clays and china clays, and up to 45 % free silica. Feldspathic earthenware is the type preferred in England. Other types of earthenware depend on the use of special raw materials: talc earthenware with the addition of up to 60 % talc, and mixed earthenware which contains a mixture of lime and feldspar as a ux.

No systematic use of analogous terms can be observed in British or American English; texture may be used to describe properties that are independent of direction while structure is preferred to summarize properties which depend on direction. To avoid confusion, German terms are used here when they are more clearly dened than the English ones.

3. Porous Whitewares: Earthenware

Porous ceramics are often classied according to their body color. The colored types are sometimes called pottery, whereas the white-bodied types discussed here are classied as earthenware. Earthenware was developed by Josiah Wedgwood in the 18th century. He introduced china clay to obtain a cream-colored ceramic body. Nowadays earthenware is used for wall and oor tiles, and for tableware and fancy goods. Its main advantages are a broad range of decorative colors and low production cost. The lower mechanical strength compared with china can be a disadvantage for certain applications. For other uses earthenware has been replaced by stoneware or soft porcelain, avoiding problems associated with the porous structure of earthenware.

3.2. Structure and Properties

Firing of earthenware is executed at fairly low temperatures; the mixture of raw materials consolidates to a ceramic body, but does not vitrify completely, so that the red body has some porosity. For most applications the pores have to be sealed by glazing the body. Reliable sealing demands a glaze without any crazing, even over long periods; this requires a glaze well matched in its thermal expansion to the body. The mineral phases in the nal structure of earthenware (excluding residues of the minerals introduced in the crude body) develop partly by thermal transformation of the original minerals and partly by thermal reactions between them (Fig. 1). The mineral phase composition of the nal body, including the pores, controls the properties of earthenware. Glazes with a melting temperature <1100 C have a rather high thermal expansion coefcient, exceeding that of mullite or amorphous phases in the ceramic body. To match the thermal expansion coefcients of body and glaze, special measures must be adopted, either by actuating reactions in the ceramic body during ring (which result in phases of higher thermal expansion) or by addition of materials with high thermal expansion coefcients which are preserved during ring. Suitable reactions during ring include the formation of cristobalite or anorthite. Mineral phases introduced via the raw materials and capable of increasing the thermal expansion of

3.1. Types of Earthenware

Earthenware can be classied according to body composition. The main types are clay earthenware, lime earthenware, and feldspathic earthenware. Clay earthenware is the oldest type; it uses clays which are not too high in iron oxide, but fairly rich in uxing impurities. Flint or sand is generally added. Lime earthenware contains 5 35 % lime, introduced either by the use of natural marl (Mergel ) or by the addition of carbonates such

Whitewares

Figure 1. Reactions occurring in bodies of earthenware during ring

the body include quartz and especially cristobalite. Higher amounts of uxes in the crude body and increasing ring temperatures result in an enhanced formation of melting phases during ring. The process has to be balanced between sufcient consolidation of the body and controlled dissolution of minerals which have been added to yield high thermal expansion. Even when the glaze adheres initially under slight compressive stresses, the system can develop crazing over longer periods. This is a consequence of moisture absorption and of reactions of water vapor with the amorphous phases in the ceramic body, causing a slight volume increase known as moisture expansion. If this moisture expansion of the body puts the glaze under tension, it crazes. Complete sealing of the body can prevent it from absorbing moisture. The reactivity of the amorphous phase with water vapor depends on its chemical composition: alkaline earth oxides, iron and manganese oxide reduce the sensitivity to moisture expansion. Lime earthenware and the iron-bearing types of pottery are less susceptible to moisture expansion.

3.3. Raw Materials

Ball Clays. Clays are the essential raw materials for earthenware because they render the body plastic and thus suitable for ceramic fabrication processes; highly plastic clays are preferred. Other important requirements are that they develop a white or bright red color, i.e., they have low iron oxide content, and do not contain pyrite, which causes dark spots in the red body. Earthenware clays should not vitrify when red at ca. 1200 C. Suitable clays have restricted amounts of minerals which act as uxes. Kaolinitic clays of the sedimentary type containing some quartz are preferred for earthenware production. Some organic matter may increase their suitability for casting processes. China clays can replace ball clays up to around half of the total plastic component, contributing to the bright red color. To reduce costs, crude kaolins can be used instead of washed kaolins. Quartz and Flint. Quartz is used in earthenware bodies to control the drying sensitivity and to match the thermal expansion of the red material to that of the glaze. Flint tends to transform rapidly to cristobalite, even when red at rather low temperatures; transformation starts at

Whitewares subsequently dewatered in a lter press. The lter cakes are then homogenized in a deairing pug mill to obtain the plastic body for forming. Slips needed for casting processes are prepared from the lter cakes by adding an appropriate amount of water and deocculant. The more modern process of isostatic pressing needs granulates which are preferably produced by spray-drying batch slurries. Spraydried granulates are also used to reduce transport costs; they are redispersed in the tableware factory to form casting slips or plastic bodies.

ca. 1050 C. They are the preferred raw materials in earthenware production in England. Siliceous earth from Neuburg on the Danube is used occasionally as a raw material in earthenware for similar reasons. Feldspathic Raw Materials. Feldspar is used as a ux in earthenware. All types of sodium feldspar, potassium feldspar, and mixed feldspars are suitable. For reasons of cost, arcose sands (occasionally incorrectly named pegmatites) can be used as a source of feldspars. They have to re brightly, without spots. Sources of Alkaline Earth Oxides. Alkaline earth carbonates (e.g., limestone, chalk, dolomite) are the preferred sources of alkaline earth oxides; they have to be rather ne grained to stimulate complete reaction with other components during ring, anorthite (CaAl2 Si2 O8 ) and diopside [CaMg(SiO3 )2 ] being the main reaction products; free calcia and magnesia cause the subsequent formation of cracks because of their reaction with water. In the United States, natural wollastonite (CaSiO3 ) is sometimes used as a raw material in earthenware bodies. Attempts to use synthetic alkaline earth silicates in earthenware production have failed because of their high cost. In countries with suitable sources of talc [Mg3 Si4 O10 (OH)2 ] this mineral can be used as a source of magnesia in earthenware bodies, which leads to the special type of talc earthenware. Availability of Raw Materials. In temperate climates raw materials for earthenware production are generally available.

Figure 2. Principles of ram-presssing of earthenware articles Sequence of steps during ram-pressing: A) Insertion of a body lump into the mold; B) Pressing process for execution of forming, water removal by vacuum in the mold; C) Opening of the mold, vacuum at the upper part, pressure at the lower part of the matrix; D) Removal of the pressed part, pressure at the upper part of the mold a) Mold made from plaster of Paris; b) Lump of body; c) Mold with applied vacuum; d) Mold with applied pressure; e) Pipe system in the mold

3.4. Fabrication of Tableware and Fancy Goods

The preferred type of earthenware for tableware and fancy goods is feldspathic earthenware. Body Preparation. The feldspar and ller materials (quartz, sand, calcined int) are ground in wet ball mills or purchased in a suitable grain size. The clays and kaolins are suspended in a blunger. The slurry is mixed thoroughly with the ground nonplastic materials, and

Forming Processes. Casting is performed in the usual manner, with plaster molds. Plastic forming of earthenware comprises extrusion and jiggering and jollying with roller machines. A further forming process especially for earthenware, is ram-pressing (Fig. 2) which uses a porous mold. Water is sucked off by vacuum; removal of the pressed body from the matrix is assisted by compressed air. Isostatic pressing has

Whitewares also become an important forming process for earthenware. Drying and Firing. The drying process is equivalent to that for all ceramic articles. Firing of earthenware has its own characteristics: biscuit ring is executed at higher temperatures than glost ring. In biscuit ring, the ware is heated to Seger Cone 8 (ca. 1240 C) where the body develops its nal microstructure. Biscuit ring of plates can be executed in stacks because of the lack of molten phase at the surface. Subsequent glazing is easy because of the porous structure of the biscuitware. The subsequent glost ring is executed at Seger Cone 1a 5 (ca. 1100 1180 C). In order to avoid sticking of the articles to the saggars, they are placed on pins. The contact areas between articles and pins have to be ground smooth after ring.

used in the glaze, and by details of the application, e.g., thickness of the glaze layer. Important features are: 1) High resistance to crazing, even after long periods 2) Translucency and high gloss, especially for underglaze decoration 3) Hardness and wear resistance Resistance to the acids and caustic solutions encountered in household use 4) No health risk from release of toxic ingredients from the red glaze The low temperature of glost ring of earthenware necessitates the use of strong uxes in the glazes which also have to meet other requirements; lead oxide and boron oxide are usual components of earthenware glazes. Alkali oxides are strong uxes; they involve less health risk, and give a good appearance. However, they increase the thermal expansion of the glaze considerably; it becomes difcult to match it to that of the body, and they can be used only in restricted amounts. The chemical characteristics of earthenware glazes, as expressed by the Seger formula ( Ceramics, General Survey, Chap. 5.1.) can range within the following limits:
0.0 0.4 K2 O 0.0 0.4 Na2 O 0.0 0.4 CaO 0.3 1.0 PbO 0.0 0.1 MgO, ZnO 2.0 3.0 SiO2 0.2 0.3 Al2 O3 0.2 0.5 B2 O3

3.5. Fabrication of Wall and Floor Tiles

Body Preparation. The preferred production method for wall and oor tiles is dry pressing with spray-dried granulate. Forming Processes. The granulate is compressed in steel dies on special hydraulic presses. The pressing operation has to be adapted to the properties of the granulate to avoid crack formation. This is mainly a matter of experience. Drying and Firing. Owing to the low moisture content, drying can be rapid. Biscuit ring is preferably carried out in an oxidizing atmosphere, at Seger Cone 6a 8 (ca. 1210 1250 C), glost ring at 100 200 C lower. The tiles are laid on supports and red in one layer in fast-ring kilns. Single ring is being introduced to save energy.

Typically, earthenware glazes use frits as starting materials, offering certain special features: 1) The glost ring temperature is lower than with raw glazes 2) Water-soluble compounds can be xed in an insoluble frit, so that wet grinding becomes possible 3) Toxic components can be safely xed in insoluble frits Colored glazes are obtained by addition of suitable metal oxides, which are dissolved in the melt during ring. The inuence on glaze properties has to be considered in the Seger formula. Another possibility is the addition of pigments ( Ceramic Colorants) which are insoluble in the fused glaze.

3.6. Glazing of Earthenware

3.6.1. Composition and Properties Glaze is applied, e.g., by dipping (tableware), or by spraying (tiles). Multiple glazing can be applied to give patterned designs. Glaze properties are controlled by chemical composition, by the types of starting materials

Whitewares European attempts to develop an equivalent whiteware succeeded in the early 1700s when Johann Friedrich Bottger invented hard porcelain (the Chinese produced a softpaste type).

Opaque glazes are obtained by addition of special opaciers such as zircon (ZrSiO4 ) or by the selection of compositions in which certain components are insoluble, or at most sparingly soluble, in the fused glaze. In other types of glazes, crystallization occurs, which also causes opacity. In crystal glazes the crystals grow to a visible size. 3.6.2. Glaze Stresses The thermal expansion coefcients of ceramic body and glaze affect the properties critically. Crazing can be avoided when the glaze has a thermal expansion coefcient somewhat lower than that of the body. A suitable difference is a matter of experience. The stresses caused by differences in thermal expansion depend not only on the two thermal expansion coefcients, but also on the relative thickness of the two layers. Thermal expansion coefcients can be measured with a dilatometer, but it is better to measure the stresses in the combined system, because thermal expansion may be modied by reactions between the two layers during ring. An instrument to provide this information has been designed by Steger. It measures the bending caused by stresses resulting from the mismatch in thermal expansion.

4.1. Types of China and Porcelain

Two basic types of china can be distinguished: the classical type is based on kaolin, feldspar, and quartz. It is used for tableware as well as in technical applications. The other type, used only for tableware and artware, contains considerable amounts of bone ash as an essential raw material, ux (feldspar) and clay being the other main components. Special porcelains contain other components (e.g., alumina). According to the ring temperature two types are known. Hard porcelains are red at ca. 1400 C (ca. Seger Cone 14), soft porcelains at ca. 1250 C (ca. Seger Cone 8). The higher the ring temperature, the harder the glaze. The ring range of whitewares is controlled by the amount of ux in the batch.

4.2. Physical Properties

Translucency is an essential property of china. The less light scattered during transmission through the body, the more translucent the china. This depends on the amount and composition of crystals, and also on the number of micropores in the red structure. This in turn depends on the batch composition, on the purity of the raw materials, and on the ring cycle, which controls dissolution of crystals and removal of pores. Traces of heavy metal oxides impair translucency considerably [25]. To give a translucent red body, the raw materials should have as little iron oxide and titanium dioxide as possible; these oxides react to form the dark ilmenite (FeTiO3 ). Ilmenite formation seems to depend on the chemical bonding of iron oxide in the raw materials; iron oxide in the clay minerals seems to be less critical than that present as separate iron minerals, because it becomes incorporated in the mullite structure and does not form ilmenite [26]. Translucency also depends on the dissolution of quartz during ring, which is inuenced by

4. Vitried Whitewares: Porcelain and China

Porcelain and china are types of whitewares which have a white, translucent, dense body. The type used for tableware and artware is termed china or porcelain. The term porcelain is also used to cover those types used in technical applications. Chinas and porcelains are usually coated with a transparent glaze. China was developed by improving the color of stoneware to white, by an increasing use of white-ring raw materials. A ceramic body which can be considered real china was rst produced in China during the Tang Dynasty (9th century). The fabrication of extremely thin china reached perfection in the Sung and Ming Dynasties. Huge quantities of china were exported to Europe during late Middle Ages and early modern era.

Whitewares the geological origin of the quartz. Vein quartz is dissolved more rapidly than quartz sand, but its high price prevents its widespread use. The melt in the porcelain body picks up quartz during ring; it becomes depleted in alumina, and thus takes up mullite (alumina silicate) to reach equilibrium; this increases translucency. Oversaturation of the melt with silica causes the crystallization of cristobalite, increasing the number of scattering centers in the body, and thus reducing translucency [27]. Alumina, introduced as corundum, is scarcely dissolved in the melt during ring, and thus decreases translucency. Bone china is fairly high in translucency, despite its rather high crystallinity. The refractive index of the crystalline phases (-tricalcium phosphate and anorthite) approaches that of the glass phase, and thus scattering of light is low. Whiteness of chinas is affected mainly by the purity of the raw materials. Besides the iron oxide content, the titanium dioxide content has proved to be critical because titanium dioxide intensies the coloring effect of iron oxide, although colorless itself [27, 28]. The chemical bonding of iron oxide in the raw materials also affects the whiteness of porcelains. Another important feature for the color of the red body is the ring atmosphere. In a reducing atmosphere, the iron oxide present in traces in all raw materials is reduced to the divalent state, the color of which is negligible. When the atmosphere at maximum ring temperature is oxidizing, iron remains in the trivalent state which causes an ivory to yellow color of the red body. Thermal Properties. Porcelains and chinas are used mainly at room temperature. In principle, their use at elevated temperatures ends when the vitreous phase begins to soften, at ca. 800 C. An increase in mechanical strength is observed as porcelain is heated to this temperature range because of healing of microcracks. Thermal shock resistance determines the use of china as ovenware or cookware and in chemical engineering, as well as the suitability of porcelain insulators for outdoor use. Thermal shock resistance is controlled mainly by thermal expansion behavior. The thermal expansion coefcient of porcelains ranges around (4 6)106 K1 , which is rather low compared

with other ceramic materials or even metals or plastics. Thus thermal shock resistance is quite good. It is however impaired by the sudden volume change of quartz during its transformation at 573 C, or the cristobalite phase change above 200 C. Porcelains intended for applications where thermal shock can occur, e.g., in chemical engineering, should have low quartz content. The increase in volume of quartz and cristobalite during heating makes it easier to nd glaze compositions which ensure a lower thermal expansion coefcient of the glaze compared with the body, thus providing surface compressive stresses. This can be used to produce glazed porcelain articles with increased mechanical strength. Mechanical Strength (Table 1) is important, especially with porcelains used for electrical insulators. The various porcelain types used in this eld are standardized in IEC 672. Type C-110 is a traditional triaxial quartz porcelain. Type C111 is a triaxial porcelain produced by pressing, containing up to 3 % porosity, whereas otherwise porcelains have to be completely vitried to zero open porosity. Type C-112 is a porcelain which contains cristobalite instead of quartz in its red structure. Types C-120 and C-130 are alumina porcelains with different amounts of corundum in their structures. The higher the alumina content, the better the mechanical strength, but the fabrication process is more difcult. Type C- 120 is preferred for fabrication of electrical insulators and in other engineering applications. The gures in Table 1 are valid only for special test bars (see part 2 of IEC 672). Corrections have to be made if the mechanical strength of real components is to be estimated. Strength decreases as the diameter of the component increases. Mechanical strength is improved considerably by glazing when the thermal expansions of glaze and body are well matched (see above). A glaze somewhat lower in thermal expansion than the body causes compressive stresses at the surface, which improve mechanical strength. When an external tensile stress is applied, the surface compressive stresses in the glaze must to be overcome before a tensile stress of a magnitude

10

Whitewares

Table 1. Minimum bending strength of porcelains according to IEC 672 Type Bending strength, unglazed, N/mm2 Bending strength, glazed, N/mm2 C-110 50 60 C-111 40 C-112 80 100 C-120 90 110 C-130 140 160

sufcient to cause a catastrophic breakage can occur. No requirements for tensile or compressive strength are standardized in IEC 672 because of the high scatter of measurements of these properties. It is estimated that the tensile strength of ceramic components is about half the bending strength, and the compressive strength is about ten times the bending strength. This suggests the design of ceramic components which are preferably stressed by compression. The mechanical strength of various porcelain types is related to their batch compositions. In triaxial porcelains, a minimum strength is observed for the traditional types (ca. 25 % quartz); types of lower and higher quartz content have considerably higher strength [29]. The relationship between strength and quartz content can be explained by structural stresses resulting from the mismatch in thermal expansion of quartz and the vitreous phase in the porcelain body [3032]. The structural stresses in the vitreous phase are tensile stresses perpendicular to the surface of the quartz grains, but compressive shear stresses along the boundaries. Increasing the amount of quartz results in a decrease of the tensile stress and an increase of the compressive shear stress around each quartz grain. Taking into account the amount of quartz, it is possible to deduce that a minimum strength will occur at a medium quartz content [3032]. This agrees with practical experience [29]. The inuence of alumina on strength can be ascribed to another mechanism. Corundum has a high Youngs modulus; therefore, external stresses cause only little strain. The surrounding vitreous phase is relieved of deformation when external stresses are applied. As corundum crystals have a high internal strength, breakage occurs only at rather high external stresses. The mechanical strength of bone china ranges between types C-110 and C-120 (IEC 672). This can be explained by the lack of crystals which would cause structural stresses and cracks, as

well as absorbing external stresses by their high Youngs modulus. No values are standardized as bone china is used only for tableware and artware. Electrical Properties. Porcelain has been widely used for electrical insulators since the beginning of electric power transmission. Similar to other dense ceramic materials, porcelains have an excellent electric strength; the 1-min withstand voltage at 50 Hz under standardized test conditions is >30 kV. Another important feature of porcelains is the high leakage current resistance. Electric spark discharges do not cause damage which would result in a conductive surface layer. The electrical dissipation factor at 106 Hz is ca. 102 ; porcelains are not normally used as insulating materials in high-frequency electrical engineering. More suitable in this eld are special types such as the alkaline earth porcelains. (No other uses of these porcelains are known because of their narrow range of ring temperature, which restricts them to articles of small size.)

4.3. Chemical Properties

Porcelains are generally resistant to attack by acids (except hydrouoric) and organic liquids. Concentrated alkaline solutions attack porcelains; attack increases exponentially with concentration of the corrosive solution and with temperature [33]. A combination of chemical attack and mechanical abrasion may be more severe, and should be considered when using porcelain devices in chemical engineering.

4.4. Raw Materials ( Ceramics, General

Survey, Chap. 1.3., Ceramics, General Survey, Chap. 2.)

Whitewares Kaolins ( Clays). Kaolins (china clays) are residual clays, usually found in primary deposits. The kaolins used for the production of china and porcelain should have high plasticity, high dry strength, good deocculation behavior for use in casting slips, and high whiteness in the red state. Whiteness is controlled by low iron oxide and titanium dioxide, and by chemical bonding (Section 4.2). Dry strength and plasticity are inuenced by type and amount of mixed layer minerals, which are present in small amounts in many kaolins, especially in those suitable for use in porcelain fabrication. Deocculation behavior is closely related to ionexchange capacity. The broad variety of deocculants available makes it possible to nd a suitable one for most kaolins. The kaolins used in china and porcelain production are normally processed to remove sand and micas, which can be present in natural kaolins in large quantities. Small residual amounts are less critical than in ller applications so that a classication with a cut at 20 40 m and thus with less preparation steps gives a satisfactory quality. Normally, mixtures of various kaolins are used in china and porcelain batches to ensure reasonably constant composition and properties, and to adjust these to production requirements. To improve plasticity, small amounts of ball clays may be added; the amount is limited by the need to keep iron oxide and titanium dioxide low. In technical porcelains, this is less critical; the amount of white-ring ball clays can be increased up to ca. 15 % to improve workability of the crude body; kaolinitic secondary clays are suitable. Feldspars. The favored type of feldspar in china and porcelain production is potassium feldspar (KAlSi3 O8 ), which forms a melt of higher viscosity at a given temperature compared with sodium feldspar, and thus causes less deformation during ring. Moreover it allows a broader range of ring temperature [34, 35]. Calcium feldspars are scarcely used in ceramics because of their extremely narrow range of ring temperature. The high uxing effect of sodium feldspar is taken advantage of in glazes to assist their ow

11

at temperatures where the body has to remain rigid. The feldspars used in ceramics are preferably those generated in the pegmatitic phase of magmatic differentiation, because of their high purity and easy processing. Arcose sands, derived from granites by mechanical and chemical weathering, can be used when available in sufcient purity; their neness reduces the cost of crushing. Moreover they contain feldspars with higher potassium/sodium ratios because sodium feldspars tend to be kaolinized during weathering; these feldspars are even better in preserving stability against deformation during ring. Their quartz content has to be considered in calculating the batch composition. Nepheline syenite may be used in porcelain bodies instead of feldspar because of its higher alkali content and thus higher uxing effect; because of its lower availability its use is conned to special types. Quartz. The preferred silica raw material in china and porcelain production is quartz sand because of its granular structure which reduces crushing costs. Sands of sufcient purity are necessary. In countries with suitable int reserves, these are used as a silica source. On preheating, int becomes brittle which makes crushing easier. The quartz microcrystals are partially transformed to cristobalite which may offer certain advantages because of its inuence on thermal expansion. Vein quartz could be attractive as a raw material because it produces a more translucent china [27]. The high price and the need for expensive crushing processes restricts its use to special products. Bone ash is an essential ingredient in bone china. The source of supply is mainly ox bone, which has to be freed from organic constituents. The bone is then calcined at ca. 1000 C. The main crystalline phase in bone ash is hydroxyapatite [Ca5 (PO4 )3 OH]. For its use in bone china fabrication, it seems essential to retain a small amount of organic matter in the ash, but too much can be troublesome. Other Ingredients. Technical porcelains may contain free alumina up to 40 wt % to in-

12

Whitewares resemble the hard porcelains, but quartz is replaced by free alumina. The higher the alumina content, the higher the mechanical strength. Superior types contain up to 40 % free alumina. Consequently, fabrication is difcult and wear of fabrication equipment is high. Soft porcelains contain a higher amount of ux, so they can be vitried at ca. 1250 C. Increased ux means a reduction of the clay components, reducing plasticity. To ensure suitable fabrication properties, the kaolin has to be replaced partly by plastic, white-ring ball clays. Another consequence is the need for an oxidizing ring atmosphere to prevent precipitation of carbon in the body during ring (soft porcelains often have an ivory-colored body, but the lower ring temperature allows a larger range of decorative colors). A special type of soft porcelain is vitreous china. It contains distinct amounts of ball clays, which improves workability. Sanitary porcelains are a special type of vitreous china. They are designed for the fabrication of large pieces, which necessiates the partial use of ball clays and a single-ring technique. Sanitary articles are mostly formed by casting, which has to be considered when selecting the raw materials. Bone china is the usual type of china for dinnerware and artware in the United Kingdom, but it is also produced in the United States, Scandinavia, and more recently in Germany. Its special features are high translucency, high whiteness, and good mechanical strength. The batch of bone china contains about 40 50 parts bone ash, 20 30 parts feldspars, and 20 30 parts clays. Because of the rather low clay content, workability of the crude body is more difcult than with other types of porcelains. FritPorcelain. In frit porcelains, alkali-rich frits are used as ux, in combination with chalk and marls. Developed originally in 18th century Europe, they are used nowadays for buttons and costume pearls. Frit porcelains are self-glazing. Dental Porcelain. The composition of dental porcelains is designed to develop high translucency. This is realized by batches with a feldspar content up to 70 % or even higher, together with some quartz and lime.

crease mechanical strength. Alumina is supplied by a specialized chemical industry which offers various types adapted to the needs of the ceramic application. Zircon (ZrSiO4 ) has a similar effect on properties to that of alumina [36, 37]. Its use is restricted to special cases, especially in countries with large zircon resources.

4.5. Special Types of China and Porcelain

Hard porcelain is the preferred type produced and used in Central Europe. It is designed to be red at Seger Cone 13 16 (1380 1460 C). Its classical type, with ca. 50 % kaolin, 25 % feldspar, and 25 % quartz combines good mechanical strength, low deformation during ring, and good translucency and whiteness. For applications with thermal shock load, e.g., in cookware or chemical engineering, special types with low quartz content have been developed. Types with increased quartz content up to 40 % exhibit improved mechanical strength; they have tended to be replaced by alumina porcelains, with even higher strength. Cristobalite porcelain contains cristobalite instead of quartz in the red structure. This can be achieved by the use of special raw materials, such as chinastone (Japanese, toseki) which is available chiey in East Asia. Chinastone is a rock containing high amounts of micaceous minerals. This contributes to a high plasticity and causes the rapid transformation of the original quartz to cristobalite. Cristobalite porcelains have a mechanical strength exceeding that of quartz porcelains. The special properties can be explained as a consequence of the structural stresses, which are higher than in quartz porcelains, because of the greater mismatch of the thermal expansion of cristobalite crystals and the vitreous phase in the red body [31]. Cristobalite porcelains are quite common in East Asia because of the availability of chinastone; otherwise alumina porcelains are preferred. Alumina porcelains are characterized by high mechanical strength. This established their use in the eld of technical ceramics, especially for high-voltage insulators. In composition they

Whitewares

13

4.6. Porcelain Structure: Theoretical Background

The Kaolin Feldspar Quartz Phase Diagram. Kaolin, feldspar, and quartz are essential for the properties of triaxial porcelain bodies. The plastic kaolin promotes workability of the crude body. Feldspar acts as a ux, and allows full vitrication of the body at the selected ring temperature. Quartz ensures a reasonable drying behavior; it also controls the development of the structure (Gef ge) and thus the properties of the u porcelain. During ring, it is dissolved and thus compensates the drop in viscosity during heating, by inreasing the silica content of the melt. Porcelain bodies can be obtained only within a certain region of the kaolin feldspar quartz phase diagram (Fig. 3) [38]; the boundaries are 35 65 % kaolin, 20 40 % feldspar, and 0 45 % quartz.

The reactions occurring in bone china bodies can be deduced from the calcium phosphate anorthite silica system (Fig. 4) [42]. Tricalcium phosphate and anorthite are found as crystalline phases in the red body. Mullite and cristobalite do not occur, although stable according to the phase diagram; they react with impurities, e.g., alkaline oxides, forming a highly viscous melt, which solidies as a glass during cooling [42].

Figure 4. The Ca3 (PO4 )2 Al2 O3 SiO2 system The trapezoidal area to the right of center indicates the limits of the composition of bone chinas Isotherms ( ) are estimated (in C)

Figure 3. Properties of bodies in the kaolin feldspar quartz sytem when red to Seger Cone 14 Numbers indicate percentage porosity D = dense structure, porcelain type; S = softened, slightly deformed; M = molten, F = friable, brittle

Reactions During Firing. The reactions in the kaolin feldspar quartz system are partly the reactions of the single components during heating, especially at low temperatures, before a molten phase has been formed; at higher temperatures, the components react with each other to form new phases [39, 40]. The reactions are described in detail elsewhere [41].

Firing Atmosphere. It has been mentioned in Section 4.2 that hard porcelains are red in a reducing atmosphere to develop a white color, whereas soft porcelains are red under oxidizing conditions to avoid precipitation of carbon with its grey discoloration of the body. However, the reducing atmosphere for hard porcelain is also important to avoid secondary porosity which would result from partial reduction of trivalent iron at high temperature on release of gaseous oxygen.

4.7. Fabrication of China and Porcelain

( Ceramics, General Survey, Chap. 4.) Body Preparation. The preferred preparation of china and porcelain bodies is wet ball milling. Costs can be reduced by using preground raw materials, so that body preparation

14

Whitewares Glazing. Glazes for hard and soft porcelains are normally transparent crude glazes. Frit glazes are used when glost ring is executed at low temperatures (bone china and vitreous china). The Seger formula of the glazes has to be adapted to the body to adjust thermal expansion; the intended ring temperature is particularly important. Glazes are applied to the ceramic body by dipping, pouring, or spraying. Automatic spraying equipment has also been introduced for tableware. Processing After Firing. Further processes may follow ring, e.g., grinding and decoration. Grinding and polishing is used to smooth areas free of glaze, e.g., saggar contact areas from which the glaze has been removed to avoid sticking. High-quality polishing avoids scratching of plates when they are stacked. Articles for technical applications may be metallized or tted with metal mountings, e.g., the shackles which are cemented onto certain types of electrical porcelain insulators. Decoration ( Ceramic Colorants). Decoration on china can be achieved by relief, color, and decorative patterns. Reliefs are applied during the forming process. Colors may be added to the body or to the glaze. Decorative patterns are applied to the unred, biscuit-red, or glazed body by painting, printing, or transfer techniques. Coating of the decoration with a glaze protects it from mechanical or chemical attack. Decoration applied to the glazed articles is red under conditions where the glaze softens again; the decoration can sink into the glaze so that it is protected against attack. The variety of color is greater the lower the ring temperature, but decoration red at high temperature is more resistant to attack. The variety of colors capable of being red at higher temperatures has been extended considerably by the introduction of the fast-ring technique and by the development of special pigments. An essential requirement for decoration is resistance to attack by acids present in foods and beverages. They must not release toxic components such as lead or cadmium. A test with acetic acid is specied in consumer-protection standards.

is reduced to homogenization in the ball mill. Sieving and magnetic removal of iron contamination from the equipment are standard practice. Further treatment depends on the intended forming process. Casting bodies are immediately deocculated. Bodies for plastic forming are dewatered in a lter-press and homogenized in a deairing pug mill. Granulates for pressing are preferably obtained by spray-drying. Dry preparation of china and porcelain bodies has not proved successful, because of the impossibility of removing iron contamination other than by passing the slurry over a magnetic separator. Scrap from certain forming processes is redispersed, sieved, and added to the crude body. This not only saves raw material costs, but also improves plasticity and workability. Forming Processes. For the fabrication of china and porcelain all the various forming methods in ceramics can be applied. Casting is used for hollow ware and complicated shapes. Pressure casting is tending to replace normal casting. Plastic forming of china is mainly executed with roller machines. Extrusion is a major process for technical porcelains. Isostatic pressing is increasingly applied for the production of tableware. Joining of component parts is executed in the leather-hard state. Firing. Porcelain is usually red twice, rst at ca. 900 C (biscuit ring) and then after applying the glaze at ca. 1250 C (soft porcelain) or ca. 1400 C (hard porcelain, glost ring). Glazing of the crude articles and single ring is commonly used for technical porcelain articles, especially when they are large. Attempts are being made to use single ring for tableware; dry-pressing and application of the glaze by spraying are promising fabrication steps to reach this goal. The ring schedule of bone china and vitreous china is different: biscuit ring is executed at ca. 1250 C and glost ring at ca. 1100 C. Tunnel kilns are used as well as shuttle kilns for ring chinas and porcelains; the trend is toward fast-ring kilns with a minimum of kiln furniture. Hard porcelains are red in a reducing atmosphere, soft porcelains under oxidizing conditions for reasons already discussed (Section 4.6).

Whitewares Decorations can also consist of metallic patterns or ribbons of gold or platinum along the rim of plates or cups.

15

4.8. Standards
Requirements for porcelains used as electrical insulators are standardized in IEC 672. The standard comprises test methods and mechanical, thermal, electrical, and chemical minimum requirements for various types of materials. Porcelains form group C-100 of this standard. European standards for articles in contact with food are presently in preparation. For tableware, standards on nomenclature and test methods for lead and cadmium release, water absorption, thermal shock resistance, translucency, crazing resistance, mechanical strength, and dishwashing resistance are being developed.

Properties. Steatites have a dense structure with no water absorption, and a high mechanical strength approaching that of alumina porcelains. Among the electrical properties, the low dielectric dissipation factor is remarkable, especially for low-loss steatite (type C-221) which is the preferred type in use. Because of their thermal stability up to 1000 C and their good electrical properties at elevated temperatures, steatites can also be used for insulating devices in electrical heating technology. Among other properties, the high wear resistance is remarkable. Fabrication. The main raw material is the steatite, the ne-grained variety of talc [Mg3 Si4 O10 (OH)2 ]. Both types C-220 and C221 are composed of ca. 85 % steatite, 5 10 % plastic clay, and 5 10 % ux (feldspar in steatite whitewares type C-220, and barium carbonate in low-loss steatites type C-221). All common ceramic forming methods are used; the preferred method is dry pressing, because the excellent gliding properties of talc crystals aid compaction. Steatite whitewares are red at ca. 1300 C, mainly in oxidizing atmospheres. For some applications, steatite components are coated with metal layers, preferably as a base for soldering them to other components. Uses. Steatite components are widely used as electrical insulators, including high-temperature and high-frequency applications. Their use for high-voltage insulators of high mechanical strength has tended to disappear with the introduction of the alumina porcelains. Steatite has a high wear resistance, hence the application for grinding balls and mill linings.

5. Technical Ceramics
From the wide range of technical ceramics classied as whitewares, two types are briey considered here: steatite whitewares and cordierite whitewares. Lithium aluminum silicates are also of technological interest because of their extremely low or even negative thermal expansion coefcients ensuring excellent thermal shock resistance. However, they have an extremely narrow range of ring temperatures when produced by ceramic fabrication procedures; they are preferably produced by crystallization of glasses, and so are better considered as glass ceramics ( Glass Ceramics).

5.1. Steatite Whitewares (see also

Insulation, Electric, Chap. 3.1.2.2.) Steatite whitewares are included in IEC 672 in group C-200 materials based on magnesium silicates. Two types are important; type C-210, steatite, and type C-221, low-loss steatite. They differ in the kind of ux and thus in their properties.

5.2. Cordierite Whitewares (see also

Insulation, Electric) In IEC 672 two types of cordierite whitewares are standardized: C-410 dense cordierite and C520 porous cordierite.

16

Whitewares
2. A. Dinsdale: Pottery Science, Ellis Horwood, Chichester 1986. 3. T. Haase: Keramik, 3rd ed., VEB Deutscher Verlag f r Grundstofndustrie, Leipzig 1970. u 4. D. H lsenberg, H.-G. Kr ger, T. R thig, G. u u o Ferri` re: Maschinelle Formgebung von e Keramik, VEB Deutscher Verlag f r u Grundstofndustrie, Leipzig 1980. 5. G. Jackson: Introduction to Whitewares, Elsevier, Amsterdam 1969. 6. W. D. Kingery, H. K. Bowen, D. R. Uhlmann: Introduction to Ceramics, 2nd ed., Wiley & Sons, New York 1976. 7. E. Krause, I. Berger, J. Nehlert, J. Wiegmann: Verfahren, Rohstoffe, Erzeugnisse, Technologie der Keramik, 2nd ed., vol. I, VEB Verlag f r Bauwesen, Berlin 1985. u 8. E. Krause, I. Berger, T. Plaul, W. Schulle: Mechanische Prozesse, Technologie der Keramik, vol. II, VEB Verlag f r Bauwesen, u Berlin 1982. 9. E. Krause, I. Berger, O. Kr ckel, P. Maier: o Thermische Prozesse, Technologie der Keramik, vol. III, VEB Verlag f r Bauwesen, u Berlin 1985. 10. E. Krause, G. Doll, G. Kalich, W. Schulle: Gesamtproze, Technologie der Keramik, vol. IV, VEB Verlag f r Bauwesen, Berlin u 1988. 11. W. Lehnh user: Glasuren und ihre Farben, 3rd a ed., Wilhelm Knapp Verlag, D sseldorf 1973. u 12. W. E. Matthes: Keramische Glasuren, Rudolf M ller Verlag, K ln 1985. u o 13. F. H. Norton: Fine Ceramics, Technology and Application, McGraw-Hill, New York 1960. 14. A. Palatzky: Technische Keramik, VEB Verlag Technik, Berlin 1954. 15. P. Rado: An Introduction to the Technology of Pottery, Pergamon Press, Oxford 1969. 16. H. Salmang, H. Scholze: Keramik, part 1 and 2, 6th ed., Springer Verlag, Berlin 1982 and 1983. 17. F. Singer, S. S. Singer: Industrial Ceramics, Chapman & Hall, London 1963. 18. S. Stefanov, S. Batschwarow: Ceramic Glazes, Bauverlag, Wiesbaden 1988. 19. M. S. Tite, M. Bimson, Archaeometry 33 (1991) 3 27. 20. W. E. Worrall: Clays and Ceramic Raw Materials, 2nd ed., Elsevier, London 1966. Specic References 21. A. Dietzel, Ber. Dtsch. Keram. Ges. 41 (1964) 41. 22. H. W. Hennicke, Ber. Dtsch. Keram. Ges. 44 (1967) 209 211.

Properties. The main property of cordierite is its low thermal expansion, ca. 2106 K1 . This ensures very good thermal shock resistance. Cordierite ceramics have a narrow range of ring temperatures. To mimimize fabrication problems, cordierite whitewares are preferably produced with a porous structure. This offers certain additional advantages: avoidance of uxes in the body improves electrical resistance at all temperatures, the porous structure reduces the Youngs modulus, and thermal shock resistance is further increased. For certain applications, a vitried type of cordierite whiteware is preferred. It can be obtained by the addition of ux to the body. Fabrication. Natural supplies of cordierite are insufcient to meet the demand for cordierite whitewares. These are therefore produced from clay and steatite mineral in appropriate proportions. Fluxes are added when a dense structure is required. Feldspar has proved useful because it causes self-glazing of the body. Production of cordierite whitewares follows the usual paths of ceramic fabrication technology. All forming methods can be applied, but extrusion has become the preferred method. Firing is at ca. 1300 C. No glaze is available with a thermal expansion coefcient lower than that of the cordierite body; self-glazing is a valuable characteristic. Uses. Cordierite whitewares have been used for decades as insulators in electrical heating engineering because of the favorable combination of thermal and electrical properties. Cordierite components are used in huge quantities as catalyst supports for emission control; their excellent thermal shock resistance is the decisive property for this application. Dense cordierite whitewares are used for the production of oven-proof tableand kitchenware.

6. References
General References 1. H. Dettmer (ed.): Ceramic Monographs. Handbook of Ceramics, Supplement to Interceram, since 1979, Verlag Schmid, Freiburg i. Brg.

Whitewares
23. K. H. Sch ller, H. W. Hennicke, c/Ber. DKG u 62 (1985) 259 263. 24. B. Sander: Gef gekunde der Gesteine, Verlag u Julius Springer, Wien 1930, p. 143. 25. F. Krauss, Ber. Dtsch. Keram. Ges. 17 (1936) 125 131. 26. H. Kromer, K.-H. Sch ller, Ber. Dtsch. Keram. u Ges. 50 (1973) 15 19, 39 40. 27. A. Dietzel, N. N. Padurow, Ber. Dtsch. Keram. Ges. 31 (1954) 7 18. 28. R. Rieke, W. Faust, Ber. Dtsch. Keram. Ges. 10 (1929) 567 576. 29. T. Wiedmann, Sprechsaal Keram. Glas Email 92 (1959) 2 5, 29 30, 52 55. 30. K.-H. Sch ller, Ber. Dtsch. Keram. Ges. 39 u (1962) 286 293. 31. K.-H. Sch ller, Ber. Dtsch. Keram. Ges. 44 u (1967) 212 223, 284 293, 387 391. 32. K.-H. Sch ller, K. St rk, Ber. Dtsch. Keram. u a Ges. 44 (1967) 458 462. 33. H. J. Ullrich, Hermsdorfer Tech. Mitt. 1979, 53, 1705 1708.

17

34. H. Rasch, Ber. Dtsch. Keram. Ges. 54 (1977) no. 4, GW 1 4;no. 5, GW 5 8; no. 7, GW 9 12. 35. K.-H. Sch ller, H. J ger, Ber. Dtsch. Keram. u a Ges. 56 (1979) 29 35. 36. V. Frith, R. O. Heckroodt, K.-H. Sch ller, u c/Ber. DKG 64 (1987) 211 215. 37. V. Frith, R. O. Heckroodt, K.-H. Sch ller, u c/Ber. DKG 64 (1987) 379 383. 38. F. Zapp, Ber. Dtsch. Keram. Ges. 33 (1956) 358 362. 39. K.-H. Sch ller, Ber. Dtsch. Keram. Ges. 38 u (1961) 150 157, 208 211, 241 246; 40 (1963) 320 326; 41 (1964) 527 531; 42 (1965) 299 310. 40. K.-H. Sch ller, Trans. Br. Ceram. Soc. 63 u (1964) 103 117. 41. K.-H. Sch ller: Porcelain, Ceramic u Monographs, part 2.1, Verlag Schmid, Freiburg i. Brg. 1979. 42. P. D. S. St. Pierre, J. Am. Ceram. Soc. 37 (1954) 243 258; 38 (1955) 217 222; 39 (1956) 147 150.