Le i cur ’eas | journal Porcelain—Raw Materials, Processing, Phase Evolution, and Mechanical Behavior New York New Porcelain represents the foundation of the ceramics disel- pline and one of the most complex ceramic materials. Com- posed primarily of lay, feldspar, and quartz, porcelains are heat-treated to form a mixture of glass and crystalline phases. This review focuses on raw materials, processing, heat treatment, and mechanical behavior. Because of the complexities of the porcelain system and despite the sub- stantial amount of research already conducted the field, there remain significant opportunities for research and study, particularly in the areas of raw material under- standing, processing science, and phase and microstructure evolution, 1. Introduction (ONTEMPORARY whitewares produced worldwide represent the foundation of much of the ceramic industry, as well as fone of the comerstones upon which the American Ceramic Society was founded in 1898. Porcelains comprise some of the ‘most complicated of all ceramics in almost all aspects of the ‘manufacturing process: from raw materials, processing, and forming, to the kinetic limitations and complexities of the mi- crostructure and phase development. Even temperature mea: surement of porcelain firing has requited the development of its ‘own unique system—pyrometric cones—because therino- cuples simply do not provide sufficient information to indi- cate the heat work associated with the porcelain firing process. From an economic perspective, the commercial whiteware industry accounts for ~7% of the entire ceramic market world- ‘wide, at sales levels of $6.1 billion in 1994! and $8.5 billion in 1996. In 1994, industrial production was divided into floor and wal ile (31%), artware and pottery (14%), dinnerware and ~ TEESE h osm, esne Qos 1,197; proved ace 1197 ate Center for Advanced Ceramic Technology—Whiteware Rest ‘ork State College of Ceramics a alfred University, Allred. New York 14802 William M. Carty” and Udayan Senapati” carch Center fine china (13%), sanitaryware (124), foodservieeware (11% and other (19%)." Between 1984 and 1993, the whitewares industry experienced a steady net sales increase from $4.55 billion to $8.21 billion. (These numbers can be used only. as indicators, because the statistical uccuracy is dependent on the response fo a survey by the industry.) "A (ceramic) whiteware is defined as “a fred ware consisting of a glazed or unglazed ceramic body that is commonly white and of fine texture. designating such product classifications a5 tile, china, porcelain, semivitreous ware, and earthen A whiteware is formed from natural raw materials of which the ‘major portion is clay. Porcelain, stoneware, china, and earth enware bodies historically have been distinguished by their firing temperature and compositions (Table 1).* Porcelains aso are distinguished by the lack of open porosity in the fired body.” Compositions for the various types of industrial por= celains are presented graphically as a portion of the K,0-Al,0,-Si0, phase diagram in Fig. 1. “The nanie "'porcelain’” is believed 10 have originated from the Portuguese word “Porcellana’” and presumably first de noted products manufactured from the shell mother-of-pearl.” In the 20th century, porcelain products have received wide application in a variety of fields ranging from electrical insu lators to dinnerware: hence, the 20th-century connotation ot porcelain suggests a product more appropriately defined as a fine-crystaline, stéong, impervious ceramic product and re- late(d) to the structure and type of product rather than to any particular composition." This review addresses porcelains via four topical areas: raw ‘materials: processing, including colloidal aspeets; fring, in cluding chemical reactions, phase development, und micro: structural evolution; and mechanical properties, Within each context, the discussion of porcelain refers primarily to triaxial blends of clay. feldspar. and a filler material (usually quart or alumina) and. consequently. ignores stoneware and earthen: ware bodies, as well as glazing and decorating issues. TL, Historical Perspective ‘The high level of intrinsic plasticity in cluys and elay-based systems and the resulting ease of forming objects precipitated4 Journal of the American Ceramic Societs—Carty and Senapati Vol. 81, No. 1 Table 1. Tra = ASTM ston” Tiaras eae Boreain” A glaved or unglaved vitreous ceramic whiteware made by the procelain process, and used Nepheline syenite 2-6 {or technical purposes, designating such products as electrical, chemical, mechanical structural, and thermal wares when they are vitreous Sanitaryware:§ Electrical: $12 Hard 10-18 Hotel: 10-13" China A glazed or unglazed vitreous ceramic whiteware made by the china process, and used for Sonica purposes, esgting ich prota dhnervae, ohare, nd aware when they are viteous Stoneware A vitreous or semivitreous ceramic ware of fine texture, made primarily from nonretructory 610° fire clay Eanhenware A glazed or unglazed nonvitreous ceramic whiteware 06-05" Levee 1588 K0-Alz05°48i0. = Malte 3Alg04°28i0 Fig. 1, Levcite-mullite-cristobalite portion of the KO-Al,Ox-SiO, phase diagram. Metakaolin is identified on the diagram, representing the Tosition ofthe elay portion of porcelain batch folloving dchydroxylaion. Ranges for typical commercial porcelain compositions are ideniied Pouash feldspar incongruent melting and the eutectic liquid formation temperature is 990°C the development of pottery skills more than 14 centuries ago. ‘Whitewares were formed entirely by hand prior to the devel- ‘opment of moder automated forming techniques early in the 2Oih century. The first hand jiggers were introduced around 1925,* and the development of automated jiggers did not be come commonplace in the dinnerware industry until the late 1940s, Roller-tool jiggers are now the most commonly used method for forming Tatware, The tile industry is by far the ‘most automated within whiteware manufacturing. led by equip- ment developments ia laly!™ that provide for aimost entirely ‘uuiomated production (other than maintenance workers); i ‘once the process is initiated. the only human input is in the final inspection stages, Currently, automation continues apace Within the dinnerware industry, with movement toward dry pressing and pressure casting." It is likely that dinnerware. Sanitaryware, and electrical insulator production will remain second t0 tile production in terms of automation For some time because of the complexity of the shapes being produced. Corresponding to the increase in automation is the improve: ‘ment in process control Prior to automation, dinnerware pro- duction loss rates of up to 60% were not uncommon. Today, loss rates within a modem dinnerware production facility are 15%-20%e. This higher level of productivity is accomplished partly through improved understanding of the underlying Forces governing the rheology and plasticity of porcelain bod ies, In the preautomation era, it was necessary to have rela- tively soft bodies with plasticity suitable for hand forming. ‘With the introduction of automated forming techniques. it be came necessary to create stiffer bodies with more controtled plasticity through the use of dispersants and increased particle packing, Prior to the introduction of dispersant, casting slips were "scooped into the mold" and the resulting casts were tineven and difficult ro handle,"* Dispersants—initilly KsCO, in 1844, then Na,COs, sodium bicarbonate, and NaySi0. ‘were introduced as a means of decreasing the slip viscosity and thus improving the drain-casting process." 7?Sanuary 1998 Porcelain—Raw Materials, Processing, Phas ‘Table Il, Temperature Equivalents for Standard-Sized ‘Orton Pyrometric Cones Tapani Tengen Tasso a Corre ore enema oe 39 COSCO 13 ot e381 1485 oo fe 1120 ele 1506 19 os of | 1719 1528 os 735 1 bs 20 1549 ony 782 ee ieee 1569 16 788 3 ek 1590 os sor 3 18626 1605 ols S31 5 196? 1627 3 859 6 ee 7) 1633 on Sot 7 Wao 29 1645 on Sst 8 126330 1654 10 804 Op et 1679 93 10130532 m7 9 LIS, 32% 180 oh 213633 ial 9913 TMG 3k 1759 101k 136535 1784 ogo atte Ses IANS 1796 Teme a oane ae | TC ee e Te Rael aa apa 2 Tpetre Cone Seaton cone ¥ be coony sed {Ste eta age of thier bos From the firing perspective, commercial porcelain produe- tion initially relied on periodic “beehive™” kilns, using coal as the primary fuel, In small potteris, the kilns were fired infre- ‘quently, dependent on the production of sufficient ware to fill the kiln volume, and firing cycles on the order of several days. were used," As the industry progressed, so did the firing cx Pabilties, and circular tunnel kilns designed to fit into the footprint of the bechive Kiln were developed." Eventually, linear tunnel kilns were developed that allowed significant in= creases in production volumes. The most advanced firing pabilities are the current roller-hearth kilns, which can produce farge quantities of high-quality porcelain dinnerware or viti- fied tle with firing cycles as short as one hour.'* ‘Most of the reactions occurring in porcelain bodies are ki netically governed processes that do not reach thermodynamic ‘equilibrium, Hence, measurement of temperature alone does hot provide a true indication ofthe heat work done on the body able I, Primary Raw Materials Used in the Ball (paste) clay ‘Kaolin (china) clay ‘ALO, 2510,-2H,0 ‘A1,0;-28i0:-2H,0 Tein companion ce Evolution, and Mechanical Behavior 5 and its degree of maturity. Instead, heat work recorders. such as rometric cones and other similar devices (e.g.. rings and Eheck’” Keys), have been developed to follow the firing prog- ress as it responds to time and temperature variations. demon- Strating the appropriate heating rate for maturation. Pyrometric cones have been the most commonly used method for thermal ‘work determinations, and, although less commonly used today in industry, bodies continue to be designated by their “cone value."” Pyrometric cones are thre-sided pyramids made from mixtures of kaolin, feldspar, quartz, and other rew materials resembling the body composition that function as true indica tors of chemical reaction kinetics in porcelain bodies. The tirst standard and regularly used pyromettic cones were introduced by Seger:"® in the United States, Orton pyrometric cones!™'* are the norm, Table Il lists the Orton pyrometric cone desig- hations and their temperature equivalents. Modern commercial firing processes are monitored with thermocouples and often are checked with pyromettic cones or keys for verification of the heat work accomplished. II, Raw Materials Because of their three-part composition of clay. feldspar, and quartz, porcelains are referred to as triaxial whitewares. Alu mina ean be substituted for quartz to increase the mechanical Strength of the fired ware, and nepheline syenite can be sub. stituted for feldspar. These primary raw meterials are listed in ‘Table IIL less commonly used raw’ materials are listed as sec ondary raw materials in Table IV. (Excellent introductions t0 these and other common raw materials are published annu: ally.) ‘Another important raw material. although one less com monly monitored or controlled within manufacturing. is the process water, It is common to use tap or potable water, which ‘sually contains a wide range of cations, including Ca™, Ms. ‘Na’, and K*, Table V provides typical tap water cation levels from several locations, Even with well-controlled urban water supplies, the level ofthese ions can vary. leading to substantial fluctuations in suspension rheology and plasticity. Also. be- cause the ionie concentration can Vary dramatically with a geo- fraphic location, water chemistry generalizations are dificult. ‘Although itis important to realize that water quality ean impact the mdnufacturing process and substantially affect the repro: ducibility of rheological measurements the contribution of Io- cal water sources is not addressed here. Manufacturing of Commerical Whitewares ‘Quanz” TiO,, Fe.0, Montmorillonite quartz Soda fldpae NEOALO. 680. Koo, C20, Me. sane Potash feldspar K,0-Al,0y°65i03, ‘Na,0, CaO, MgO. quartz Nepheline syenite K0:3Na,0-4A1,0,98i0, C20, MzO. quartz Alums Ahoy Na6 Quaree Soe Ti), Fe.0. “Guan apr al Say may bow gh wT ‘Table IV, Secondary Raw Materials Used in the Manufacturing of ‘Commerical Whitewares iT Toma eeprom Conon rapes ‘Bontonitefmonmoritionite™ (MPI )a(Si-AD,Osg( OF), Not applicable Glass rts ‘Company specific Not applicable Petalite (lithium feldspar) T,0.A1,0, 6510, Na,0. KO, Bono ash" CAPO.) Unknown Tale 3Ng0-3810,2H,0 Chrysotile, CaO Whiting aco, MgC, Zircon 2:0s$i0; [Not applicable “Fas angrenoa fore For pretng te gampsion va Tae aan A) a ue bon Ten Fete