us00610722 United States Patent 1) (uy) Patent Number 6,107,223 Koga et 45] Date of Patent: Aug. 22, 2000 ig. 22, [Sf] METHOD FOR PREPARING HIGH S372976 121994 Matsuno souse ENCITILAND HIGH THERMAL SHOCK- Nore AND/IGH THERMAL FOREIGN PATENT DOCUMENTS WHITEWARE 24001591990 pan SSeste 31004 Joan [75] loventors Neokd Koga; Masakl Tan; Toshiya Nosilawas Aklo Matsumoto, all of OTHER PUBLICATIONS Kitakyushu, Japan Chemica! Dictionary vol. 5, pp. 54 Apr. 1961 (cited in [73] Assignee: ‘Toto Ltd, Kitakyushu, Japan IPER). 7 , Primary Examiner—Jaes Derington [21] Appl No 08809,451 ‘Attorney, Agent, or Fm-Cusiman Duby & Cushman IP oes rey Group of Pillsbury Madison & Suro LLP Related US. Application Dat (7 eet ‘A metbod for preparing high strength and high thermal {68} Conimaton of apcion No, PCTIISOUH2, Sep. 25, Shoes cna for ceramic eva which com " prises the steps of molding a china-forming raw material [20] Foreign Application Priority Data Athich mainly comprise a natal oe malo cayeleof reeerrerreeeer penne calcining the natural ore material to form corundum, & fst] imc (C046 3424 natural re material capable of foming. mullite though eeustal Sou Deuogoesouties fring of s materal obeicd by calcining the natural ere Si Sv S01 a SSH a orm mali lp mater ad ach nee Jouocesousiia, © ekipar, epheline or dooney and) ton firing the SOT, tee, ON, Bolded isa fonning rv materia Th metho pers tbe proshoton of cheapest ciaa for count whee hang, Pa pore) High stag and excellen ibemal shock resistance 3 compared with those prepared by the conventional tech- US. PATENT DOCUMENTS niques. 4717095 11988 ob ea sounes {arse 91000 Maes Deas 9 Claims, 2 Drawing ShootsU.S. Patent ‘Aug. 22, 2000 Sheet 1 of 2 6,107,223 FIG. 1A FIG. 1BU.S. Patent ‘Aug. 22, 2000 Sheet 2 of 2 6,107,223 FIG.2A FIG. 2B6,107,223 1 METHOD FOR PREPARING HIGH STRENGTH AND HIGH THERMAL SHOCK- RESISTANT CHINA FOR CERAMIC WHITEWARE, ‘This is « Continuation of International Appla. No. PCT 11P95/01942 filed Sep. 26, 1995 which designated the US. TECHNICAL FIELD OF THE INVENTION ‘The present invention relates to a method for preparing ‘china for ceramic whiteware exhibiting high mecbanical strength and high thermal shock resistance, ata low pro- duction cost PRIOR ART ‘There has been known that chin for ceramie whiteware ‘exhibiting high slrength can be obtained by replacing the ‘quartz component preseat in china for ceramic whiteware ‘comprising a thiee component system of quartz, fekispar and clay with conundum, ‘The quartz in the crystalline phase present inthe china for ‘ceramic whiteware can be replaced with corundum through the use as a raw material of alumina which comprises ‘corundum crystal instead of quartz or pottery stone used as 8 quar source material and including quari, feldspar and ‘lay, The amount of alumina to be added in general ranges from 10 to 50% by weight based on the total weight of the ‘china-forming raw material ‘The quartzifelisparjclay three component china for ceramic whiteware comprises quartz and mullite erysials| dispersed in a glass matrix mainly comprising SiO, On the other hand, a a conventional technique for improving the strength ofthe ching the use as a raw material ‘of alumina which comprises corundum crystal instead of “quartz or pottery stone used a8 a quartz souzce material and inchiding quartz, feldspar and clay permits, as has been iscussed above, the production of china for ceramic ‘whiteware which comprises corundum, quartz and mullite particles as a erysalline phase and which exhibits improved strength through the addition of alumina particles. An alu- ‘mina Source used herein is alumina which comprises corun- ‘dum crystal and which i industrially produced generally by the Buyer's process, because of ils quality and stable avail- ability, To addition, there has also been used alumina pro- duced by the fusing process. “These alumina sources used in the conventional tech- niques are quite expensive as compared with the raw mate~ rials commonly used in the china for ceramic whiteware and hhence the resulting china is likewise expensive. This largely limits the applications thereof andl such china has presently been used only in certain high grade tablewares and some industrial ceramic whitewares, Moreover, the high srength china for ceramic whiteware produced by the foregoing conventional techniques suffers {rom a problem of low thermal shock resistance. ‘The quartzifeldsparlclay three component china for ‘ceramic Wwhiteware exhibits quite excellent thermal shock resistance. For this reasoo, large-sized ceramic whiteware products such as sanitary-wares can be produced from the ‘china without causing any crack even by the thermal shock ‘encountered during the cooling process after firing. In ton, the china can likewise be used for the production ‘of sanitary-wares such as wash-bowls whieh require high thermal shock resistance ‘The china exhibits this excellent thermal shock resistance ‘due to the effect of microcracks present inthe china and it 0 3s 2 is assumed that the microcracks, quartz particles and the thermal shock resisiance have the following relationship, ‘As has already been discussed above, the quartzfeldspar ‘lay three component china for ceramic Whiteware has texture comprising quartz and mullite particles dispersed 4 glass matrix. The thermal expansion coellicient of quartz is substantially greater than that of glass matcix and accordingly, microeracks are formed at the boundary between the quartz particles and the glass matrix de tothe sites originated from the difference of volume change of these components observed during cooling. process after firing. This phenomenon can be observed by SEM (scanaiag ‘electron microscope). Moreover, the amount of the mice ‘racks thus formed is proportional to the amount of quartz, particles, The presence of such microcracks pezmits absorp- tioa of the stress due o thermal shock andl hence prevents any propagation of breakage or eracks. Therelore the higher the amount of microcracks, the higher the thermal shock resistance of the china (On the other hand, the high strength china for ceramic whiteware of the conventional techniques in which alumina is substituted for quartz as a caw material for the china inferior in the thermal shock resistance 10 the quartz) feldsparilay three component china for ceramic whitewar. In sue a high strength china for ceramic whiteware, almost all of the quartz particles in the china is replaced with lumina particles. The thermal expansion coeflcient of lumina particles is approximately equal to that of glass matrix and therefore, microcracks are not formed at the boundary therebetween. Accordingly, the amount of micro- ‘racks inthe china is reduced and this leads ta decrease of the thermal shock resistance thecco. Such a low thermal shock resistance of the high strength ‘china for ceramic whiteware produced by the conventional techniques would be an obstace inthe application thereof to large-sized ceramic whiteware products and other ceramic “whitewares which require high thermal shock resistance. ‘As has been discussed above, the high strength china for ‘ceramic whiteware produced by the conventional techniques Sullers from the following (wo major problems. More specifically, it requires an inereased cost as compared with the quartafeldspariclay three component chins for ceramic ‘whiteware and it is iferioe in the thermal shock resistance to the latter. DISCLOSURE OF THE INVENTION ‘Accordingly, the object of the present invention is gen ‘erally 1 solve the foregoing wo problems and more spe- ‘ically to previde « method for prepasing china for ceramic Whiteware having excellent sttength and thermal shock resistance at a Tow production cos According to an aspect of the present invention, there is provided a method for preparing china for ceramic whitew~ are which comprises the sieps of: molding a ehina-formiog ‘aw material mainly comprising a natural ore material which forms corundim through firing or a material obtained by calcining the natural ow material to form corundum, a natural ore material which forms mullite through fring or & material obtained by calcining the natural ore material 10 form mullite, a clayey material and flux, and then firing the ‘molded china-forming raw material ‘According to another aspect of the present invention, there is provided a method for preparing china for ceramic ‘whiteware which comprises the steps of: molding a china- forming raw material mainly comprising 4 natural ore mate~ rial which forms corundum and mullite through firing or6,107,223 3 material obtained by calcining the natural ore material to form corundum andl mullite; a clayey material; and Mu, and then fring the molded china-forming raw material ‘The flux is preferably selected from the group consisting ‘of feldspar, nepbeline and dolomite. BRIEF DESCRIPTION OF THE DRAWINGS FIG, 1 shows an elevational view and a plan view of ‘sanitary-ware (wash bow) prepared according fo the method ‘of the present invention. FIG. 2 shows an elevational view and a plan view of a sanitary-ware (Water closet) prepared according 10 the method of the present invention, PREFERRED EMBODIMENTS FOR CARRYING. ‘OUT THE INVENTION ‘The strength ofthe china for ceramic whiteware prepared by the conventional technique in which alumina, as a raw material therefor, is substituted for quartz is improved by increasing the amount of slumina tobe substituted for quartz ‘or the amount of alumina to be added. However, if the Amount of akumina to be substituted for quartz increases, the Amount of microcracks formed by quartz particles decreases and accordingly, the thermal shock resistance of the resull- ing china is impaied. Under such circumstances, it has ‘conventionally been devised that an appropriate amount of ‘quartz particles is retained so that the thermal shock resis= tance is not impaired so much, However, if quart particles and hence mierocracks are retained, the resulting china ‘exhibits low strength. Accordingly, i is impossible to pre~ pare china having high strength and excellent thermal shock fesistance simply by controling the amount of quartz par ticles and that of alumina to be added like the conventional techniques. As has been discussed above, the preparation of| the foregoing china requires such a device that the thermal shock resistance of the china is improved without impairing the strength thereof ‘The inventors of this invention have conducted various ‘studies to develop a mothod foe improving the thermal shock resistance of china without impairing the strength thercof ‘while taking gote of the difference in te thermal expansion ‘coeficiet between crystal particles in the china ‘The thermal shock resistance of china can in general be ‘expressed by the following relation: AT o(.-v)xietE wherein ATT represents thermal shock resistance, o repre= sens the strength, v represents the Poisson's rali, « repre= sents the thermal conductivity, represents thermal expan= sion coefficient and E represents the Young's modulus, This felation indicates thatthe thermal shock resistance can be improved if only the thermal expansion coellicieat is reduced while remaining other physical properties unchanged, The inventors have investigated crystal particles having a thermal expansion coefficient smaller than those of | lumina and quartz particles in the light of the foregoing finding and as a result, it has been found that the thermal shock resistance of the china ean be improved by the Addition of ‘mullite particles to the china ‘The thermal ‘expansion coellcient of mullite is 55x10 C. which is ‘smaller than those of quartz and alumina (corundum) (25x 107°C, and S10" C,, respectively). Mullite exists also in the quartzjeldspar/clay three com= ponent china for ceramic whiteware and inthe high strength china for ceramic whiteware whose quartz component is replaced with alumina, in an amount on the order of several m 2s hi 4 to ten-odd percent. In this case, however, mullite does not ‘exist in the raw material per se for the ehina, but is formed through erysallization from Al,0, and SiO. components in the glass phase of the china during firing the same. The mullite particles thus erysallizd has a particle sizeof about 1 yen and are usually in the form of needle crystals. The amount of mullite ultimately formed in the china is deter- ‘mined by the composition of the raw material forthe china and the conditions for fring the china ‘The thermal shock resistance of china can be improved by increasing the amount of mullite which forms erystal pa icles. Therefore, it is possible to obtain high strength and high thermal shock resistant china for ceramic whiteware by easing the amount of mullite i high siength china for ‘ceramic whiteware wherein alumina is used instead of quarz There would be two methods for increasing tbe amount of mullite. One method is simple and comprises using mullite as a raw material forthe china. This isthe simplest method for preparing a desired china. However, if mullite is used as a raw snaterial forthe china, an artificially prepared mullite must be used since mullite is not a naturally occuring substance. Therefore, itis more expensive than commonly used raw materials for ceramics and the use thereof resulis in an increase inthe production cost The other method comprises controling the composition ‘of the raw material for the china to the range in which mullite is easily erystallized. This method bas been applied forthe preparation of mullite porcelain, but it is difficult 10 funer increase the amount of mullite heyond that presently achieved, when raw materials for the china and the condli- tions for firing thereof are considerably limited. ‘A problem to be solved at present is to develop a method for preparing cheap china for ceramic whiteware exhibiting strength and high thermal shock resistance. To this end, is necessary to devise a cost-saving method for increasiog the content of mullite inthe china or for substituting alumina (corundum) for quartz present in the china. Ten, the inven= tors ofthis invention have devised the following two meth- oc ‘One method for inereasing the mullite content is to use & natural ore material sueh as aluminous shale, bauxite, andalusite, Kyanite or sillimanite which forms mullite through firing or a material obtained by calcining the natural ‘ore material fo form mullite, as an ingredient for the china forming raw material, Tis method for increasing the mullite ‘content through the use ofthe foregoing natural ores permits the proxluction of cheap china for ceramic whiteware exh iting impeowed thermal shock resistance “The other method for replacing quartz present inthe china “with alumina (corundum) is to use, inthe raw material for preparing the china for ceramic whiteware, a natural ore material which forms coeundum through firing such as luminous shale or bausite, of 4 material obtained by fiiog the natural ore material to form corundum. The method for replacing quartz present in the china with alumina (Corundum) while making use of the foregoing natural ores permits the production ofa desired china ata cost lower than that required forthe production ofthe high strength china for ‘ceramic whiteware by the conventional method in which Purified alumina is used. ‘Moreover, the simullancous execution of the foregoing two methods permits the production of more cheaper, bigh ‘strength china for ceramic whiteware exhibiting more exeel- Jeot thermal shock resistance 2s compared wi the china produced by the conventional techniques in which alumina is substituted for quartz6,107,223 5 ‘The foregoing wo methods can likewise be simulta neously carried out if using 4 natural ore material such as luminous shale or bauxite which forms both corundum and ‘mullite through firing or a material obtained by calcining the natural ore material to form both corundum and mullite “The present invention will hereinalier be described in mote detail, Raw materials used for the production of the china for ‘ceramic whiteware prepared by the method of the present invention are as follows: ‘at least one member selected from the group consisting ‘of aatueal ore materials whieh form coruodium through firing such as aluminous shale, bauxite, white bauxite and diaspore; and eaw materials obtained by calcining the foregoing natural ore materials to form corundum, as a taw material for forming corundum in the china (bereundler referred to a8 corundum source material); 2)at least one member selected from the group consisting ‘of oatural ore materials which form mullite through firing such as andaluste, kysnite, sillimanite, alumi- nous shale, bauxite and white bausite; and raw mate~ rials obtained by firing the foregoing natural ore mate~ als to form mullite, as 4 aw material for increasing the content of mullite in the china (hereunder referred to as mullite source material): 3) clayey materials such as ball clay, Gaome clay china clay or kaolia including clay minerals, for iostance, kaolinite and dickite asa plastic materials 4) at leas one flux such a feldspar, nepheline, dolomite, calete or magnesite, which include alkali or alkaline cath metal oxides; 5) raw materials including quartz such as pottery stone and silica sand; and 6)at least one member selected from the group consisting ‘of natural ore materials which form both coruadum and ‘mullite through firing such as luminous shale, bauxite, white bauxite andl diaspore and raw materials obtained by calcining the foregoing natural ore materials to form corundum and mullite, as a raw material for forming corundum and for increasing the content of mullite in the china (hereunder referred 10 as corundum-mulite source material) ‘The foregoing raw materials 1) to 4) and optionally the raw material 5) ate used as principal components. Alternatively, itis also possible to use the raw material 6) instead of the raw materials 1) and 2) ‘Almost all of the natural ore materials used as the ‘corundum, mullite and corundam-mallite source materials undergo a volume change due to dehydration andlor erys- line conversion encountered when forming. corundim and/or mullite through firing. Bauxite isan ore mainly comprising gibbsite, and gibbsite loses erystal water and is converted into eoruacium through firing and this is accompanied by a substantial volume ‘change. For this reason, if bauxite is used as a raw material, the resulting ehina-forming raw material isnot easily sintered and this often resulls in the formation of china having low Strength. Therefore, if bauxite is used asa raw material preferably calcined in advance. On the other hand, aluminous shale i an ore mainly ‘comprising diaspore and diaspore loses water and is eon ‘verted into corundum through firing like bauxite, Gibbsite is y-Al,0, trihydrate, while diaspore is «-AI.O, monohydrate. Therefore, the amount of water removed is ‘smaller when sluminous shale is fired. For this reason, in 0 3s 6 luminous shale per se may be used as a raw material and ‘can provide china superior to that obtained using bauxite as ‘such. However, the fring of aluminous shale is accompanied by a slight volume cbange and accordingly, it is also preferred to caleine aluminous shale prior to use as a raw ‘material. If bauxite and aluminous shale are calcined in advance, both of them undergo dehydration ata temperature ranging fiom 60 to S00" C. and cause the maximum volume reduction at tha temperature range, Therefore they are preferably ealeined at temperature of pot ss than 800° more preferably ata temperature of 1000-1500" C. “The natural ore aw materials which form mullite through fving such as andalusit, kyanite and sillimarite form mule lite erytals at a temperature ranging from 1100 1500" C., although the emperstre slightly varies depending on the kind ofthe ore materials. AL his stage, hey underg a light wolume change. For tis reason itis preferred to caine these raw materials in advance forthe same reason already discussed above. The oatral ore materials which form corundum through fring sic as aluinovs sate and bauxite also form mite depending on the compositions thereof This is beeause, these raw materials include glassy substances or ores mainly comprising SIO, and ALO, in ation to principal compo tents such as diaspore and gibbsite, For ths reson, multe formed fom thse components wien cing tem, "The use ‘of such natural ore materials permis the elimination of the tse of a mullite source materia, ‘Moreover, puried alumina andor purified mullite may be used as part ofthe china-forming raw material forthe purpose of stabilizing physical properties of the china and of Adjusting the composition thereof “The foregoing aw tateriae ae used for forming shaming (corunum) pariles andor mullite particles in the china and therefor, the price sizeof the raw materials plays an important ole. The strength of the china is greatly affected bythe size ofthese particles present in the china, Therefore, if they can uniformly be dispersed in a gess phase, the smaller the particle size the higher the strength of the resulting china. However, if its too smal, the aggregate Patticles ae insuficiently disperse and the strength thereof conversely reducod For this reason, the average particle sizeof these caw materials preferaly ranges from 1 to 50 jm and more preferably 1/10 20 pan in onder to further fiprove the siength of the china Then the composition and component ratio ofeach china forming rw material are preferably seleted or established insu a manner tat the china has the folowing texture aad ‘composition G) The china for ceramic whiteware prepared by the ‘method of the present invention comprise, based on the total weight ofthe chin, 15 to 70% oferytalline particles and 30 10 85% of & glass mutex mainly comprising Si0 © The exytllne parictes comprise, based onthe tat ‘weight of the chin, 10 t0 659% of corundum and 5 10 0% of eullte and. may optionally comprise other caystal particles of, for instance, uri, ctisobalte, andaluse,kyanite, rircon, zirconia and tian, The china has boon designed so as o have the foregoing texture and composition, forthe Tllowing reasons. The china preferably comprises corundum in an amount of ot Jess han 10% to improve the siengih eter. Moreover, the china preferably comprises mullite in an amouot of not Tess than 5% which x higher than that observed io the igh stength china for ceramie whileware prepared by the con6,107,223 a ‘ventional technique in which alumina is substituted for ‘quartz for the improvement of the thermal shock resistance and not less than 10% for achieving the thermal shock resistance comparable to that of the quartz/feldspariclay three componeat china for ceramic whiteware, This is because, if the amount of the crystalline particles is too high, in panicular, if it exceeds 70%, tbe sinterabilty ofthe raw material is extremely impaiced and the firing temperature ‘correspondingly is beyond the practical range. In respect of the choice of the raw materials to be used, in particular, the choice of the natural ore raw materials serving as corundum and/or mullite source materials, pre~ ferred are those capable of forming a large amount of | ‘corundum andior mullite through firing. If the amounts of ‘corundum andlor mullite formed are too small, itis difficult, to obiain china for ceramic whitewace having the foregoing iexture and composition, I aluminous shale is used as a corundum source material, the content of Al.0, is preferably not less than 50% for the foregoing reasons. If the content of Al,O, is less than 50% (weight basis), the amounis of raw materials serving as plastic material for molding or flux to be used are limited nd the resulting china-forming raw material exhibits poor ‘moldabilty or sinterability Morcover, if aluminous shale is used as a conundum- ‘mullite source material, it preferably hasan A1,O, content of | not less than 50% by weight and an SiO, content of not less than 5% by weight. The presence of SiO, permits the formation of mullite through fring. Ifthe amount of SiO. is too small, a suficient amount of mullite is aot formed and luminous shale does aot function as the mullite source ‘material “The china for ceramic whiteware can be obtained by rixing the foregoing raw materials in the rate defined above, ‘optionally pulverizing the mixture to a desired particle size, ‘molding and then fring the mixture ‘The raw materials may be mixed and pulverized at the ‘same time or a part or the whole of these materials may be separately pulverized and then mixed together. In this respect, the overall average particle size of the forming raw material preferably ranges from 1 to 20 gum. “This is because ifthe particle size of the raw material is 100 lange, the sinterability of the aw material is impaired and it ‘cannot be sintered within the practical fring temperature range, On the other hand, ifthe particle size thereof is too ‘smal, itis dificult (0 mold the raw material. The raw material may be pulverized by a dry or wet pulverization ‘method or any other method. “The raw material whose particle size is controlled can be treated depending on the molding method, for example slurring to add water, or powdering by spray dry process fnd then formed into a desired shape by a varity of molding methods such as pressing, casting, injection molding, slip casting in which a gypsum mold or a resin mold having ‘water absorption properties is used ‘The china-forming raw material is preferably fired at a firing temperature of not less than 81K C. under atmo- spheric condition, or oxidizing or reducing atmosphere 10 ‘obtain sufficiently dense chin The firing method may be ® batchvvise or continucts method. Any firing furnace such fs electric furnace or a gas furnace may be used for the firing. (COMPARATIVE EXAMPLE 1 ‘There were prepared, by way of comparative examples, china for ceramic whiteware comprising pottery stone, fel spar and clay as raw materials; a high strength china for in 0 3s 8 ‘ceramic whiteware according to the conventional technique; and china for ceramie whiteware to Which silica sand was addled to improve the thermal shock resistance (hereunler referred to as comparative china (or C.C) 1, 2 and 3, respectively) and these comparative china were inspected for physical properties. The raw materials, the composition alier blending and the examined physical properties of each ‘china ate listed in the following Table 1 In the comparative china 2 and 3, the alumina (corundum) source material used was AM-21 purified by the Bayer's method and available from Sumitomo Chemical Co., Lid. ‘The sluming has an ALO, purity of 99.7% and an average particle sie of about 4 jan, In the comparative china 3, Masuda silica stone pulver- ined ton average particle sizeof about 10m was used. The crystal thereof is quartz and it has an SiO. purity of 99.5%. Each china was prepared by the following method. To the ‘chini-forming raw materials other than silica sand, there Were added water in a volume identical to that of the whole raw materials and an appropriate amount of water-glass, followed by pulverization ina ball mill, addition of silica sand alter the completion of the pulverization and then mixing in a ball mill for about 30 minutes to give a starting ‘slurry. In respect ofthe pulverization, the comparative china 1 was pulverized to an average particle sizeof about 8 jm, while the comparative china 2 and 3 were pulverized to an average particle size of about 5am. ‘Then each starting slurry was poured into a gypsum moll and then demolded to give @ green test piece baving a ‘diameter of 15 mm and a length of 150 mm, ‘Then each green test piece was dried at 40° C, whole day and aight, followed by firing according to the following heating schedule: heating up to 1000" C; over 4 hours and thea up 10 1200° C, over 2 bows, maiataining at 1200° C. for one hour in an electric furnsee and then allowing 10 natural cool Physical properties were determined as follows: Bending strength was determined according to the three= point bending test using Autograph available from Shi- madzu Corporation under the following conditions: a span ‘of 100 mm and a cross bead speed of 2.5 mnvmim. “Thermal shock resistance was determined by the follow: ing method ‘Afier maintaining each test piece at a predetermined temperature for about one hour in a heating device, the test picce was immediately immersed in water and allowed to ‘Stand for several minuies, Thea the test piece was immersed in an ik for ink-chock for the evaluation of cracks thus formed by the thermal shock, The thermal shock resistance ‘of each test piece was expressed in terms of the cillerence between the eaek-forming temperature and the temperature ‘of the water used for quenching ‘The data listed in Table 1 inicate that the use of alumina as im the comparative china 2 permits an increase in the Sirength of the material on the order of not less than 2 times that observed forthe china for ceramic whiteware compris- ing pottery stone, feldspar and clay as raw materials, but the thermal shock resistance thercof i impaired. On the other hhand, the use of silica Sand as in the compacative china 3 permits the improvement in the thermal shock resistance of | the china, but the resulting china is inferior in the thermal shock resistance to the comparative china I and is inferior in the strength to the comparative china 26,107,223 Bien compotion tery Sone @ = Cay = % Felpas BOS (Cote Minn Compoion ‘conndun Pees ants ma ia Malte e Se St Phil Properties © mw wo nd EXAMPLE 1 Cina was prepared by the method of the present iaven= tion, The raw materials used, the composition after blending and physical properties are summarized in the following “Table 2, Alumina, silica sand, clay and feldspar used as the raw materials were the same as those used in Comparative Example I. The purified mullite used was Electrofused Malte RM-80 available from Showa Denko, K-K. having «8 mullite purity of not less than 99%. “The chemical composition and mineral composition ofthe natural ore raw material used as a conundum or mullite ‘ouece are listed in Table 3, “These natural ore raw materials and the purified mullite ‘were pulverized to an average particle size of about 5 yam (unless otherwise specified in Table 2) using a ball mill CCalcined saw material was calcined at 1500° C. price to the pulverization “The results of the china 11 and 1-2 indicate that the addition of mullite permits the improvement in the thermal ‘hock resistance of the resulting china, Although silica sand also shoves the same effect, but the effect of mullite dilfers from that of silica Sand in thatthe resulting china does not ‘exhibit any reduction of the strength through addition of ‘mullite. Thus, the addition of mullite permits the improve- ment of the thermal shock resistance without impairing the ‘strength of the resulting china In the china 2-1 to 2-4, a raw material obtained by ‘calcining aluminous shale was used asthe corundum source ‘material. The added amount thereof and physical properties ‘of the china ae listed in Table 2. The resulis of these ehina| indicate that the strength of the china is improved by increasing the added amount of the caleined luminous shale, while the sinterability thereof is impaired. The sirength of the china observed when aluminous shale is used is slightly inferior to that observed forthe china in which the purified alumina raw material is used. This is because the ‘corundum conteat of the caleined aluminous shale is low and therefore, the higher the corundum content of ealcined luminous shale used, te higher tbe strength ofthe resulting chins On the other hand, the thermal shock resistance of the china ia which alumioous shale is used (china 2—2) is sreater than that ofthe china (comparative china 2) wherein the purified alumina is used. This is because the calcined luminous shale comprises mullite, tis thus believed that in 0 3s 10 the use of caleined aluminous shale resulis in an increase in the mullite content of the chine and accordingly, the thermal shock resistance thereat is improved ‘As has been discussed above, china for ceramic whitew= ave having high strength and exeellent thermal shock resis- tance can be prepared through the use of corundum aad ‘mullite-containing natural ore raw materials ‘The china 3 is one obtained using uncaleined aluminovs, ‘shale and itis slightly inferior in both strength and thermal shock resistance to the ehina wherein calcined aluminous sale is used. However, the china has a merit in cost since the calcining treatment of aluminous shale ean be omitted and may be used in applications whieh do not require ‘exicemely high strength and thermal shock resistance. ‘The chins 4 comprises silica sand for the purpose of further improvement of the theensl shock resistance thereof and accordingly, exhibits high strength and excellent ther mal shock resistance approximately identical to that ‘observed for the conventional china (comparative ebina 1) mainly comprising pottery stone, feldspar and clay. “The china 5-1 10 54 have a composition identical to that ‘of the china 4, but dilfer inthe particle size of calcined sluminous shale from the latter If the particle size of ‘calcined aluminous shale becomes large, the strength of the ‘china is not changed, but i it becomes too small, te stent is lowered. However, the lager the particle size of ealcined luminous shale, the longer the time required for pulverize ing. In the china 6 and 7, bauxite and ealeined bauxite are used as the corundum source material. When calcined bauxite is used, china exbibiting high singh can be obtained, but hea unealcined bauxite i used, the resulting china is not sintered and the strength thereof is almost identical to that ‘observed for the conventional chins for ceramic whiteware ‘The china 8 and 9 have compositions identical to that of the china It except that andilusite and calcined andalusite are used as the mullite source materials. The resulting china \were slightly inferior in the strength tothe china 1—1, but ‘exhibited excellent theemal shock resistance, EXAMPLE 2 ‘There were prepared, according 10 the method of the present inveation, two kinds of sanitary-wares, ie.,a wash bow as shown in FIG. 1 and a water eloset as shown in FIG. 2. Two kinds of china (comparative china 2 and the china 4 ‘oF Example 1) were used for the preparation ofthe snitary= ‘wares to thus confirm the effet of the present invention. The preparation of these sanitaryswares: was carried cut by ‘molding while using gypsum molds for Forming respective sanitary-wares instead of the gypsum molds for preparing the green test pioces used in Comparative Example 1 and Example 2, then drying and spraying a glaze, thereafter firing the molded article in a heavy oil combustion type ‘continuous tunnel kiln, in whieh a eyele comprising heating from room temperature up to a maximum temperature of| 1200° C- and eooling down to room temperature required 24 hours was used, in place of the electric Furnace. ‘The results thus obtained are summarized in the following. Table 4. In Table 4, the term “kiln crack” phenomenon micans that an article causes cracking by the heat shock ‘during cooling step of the tiring process and elatively ‘small-sized artiles such as wash bowls do not cause “kiln ‘crack phenomenon even when the comparative china 2 is used. However, lagessized articles such as water closet ‘eause the “kiln crack” phenomenon when using the com= parative china 2 having poor thermal shock resistance.6,107,223 u Moreover, its cleined in JIS (5207) thatthe sanitary-ware rus pase a desired quenching test and the articles prepared from the comparative china 2 cannot pass such a quenching ‘This quenching test comprises the steps of maintaining a fragment of a ceramic whiteware having a size of shout 100 ‘em and a thickness of not more than 15 mm in a heated furnace for one hour, then quenching in water and immers- ing it in red ink to inspect it forthe presence of eracks in the china andthe glaze layer. The fragment should not cause any crack at a temperate dilference between the heating 12 temperature and the temperature of the quenching water of| ‘aot more than 110° C. ‘AS has been discussed above in desi, the high strength ‘china for ceramie whitewares prepared by the conventional techniques in which alumina is substituted forthe quartz in the quartzifeldspariclay three component china for ceramic \whitewares exhibits poor thermal shock resistance. Coaetcy to this, the present invention permits, for the frst time, the preparation of a high strength china for ceramic whiteware having excellent thermal shock resistance ata low cost. The ‘china of the present invention ean be applied to sanitary= ‘TABLE 2 Tear Alumiacs Sle ‘acai ‘natn ‘atte Sil Sena Fedor Fuiag Tee. ((C) 1200 » is Campos oe) uate Mite ending Seng ours ‘Thermal Shook Resisuoce (C) 10 eat Alumiacs Sle ‘seine Shale ‘aunt ‘andl ‘atte Fedor Fring Ten. (°C) Miner a Compo oe) Ccorandin ‘one ‘md Pays Popes. reo Sie rt 0 ry 100 » » 100 8 a 1280 Re 1 190 Gem Cm i ym) (80am ©, “ seBI 0 36,107,223 13. TABLE 2-continued Chinn Pep hy the Mato of he Panwa nventon id Pail Properties Meteor 14 a3 na 7s ae (st) ° ° Temisie = — = = = = = Resanoe CC) ‘TABLE 3 ‘Companion of aa Ov Maes Cred a he atic sr Siac” “'She"_paucte ‘xe _Anabste Andee Gen Camp. G9) no, mm sw wD Se. a as Sa 383 TO, 27 4380 os O48: 60 ass das sts xo om <8 Dl a ttn KO o7 = or koa Composios (wt) Diapore 3 X XX x xX x Oise x xX ox © x 3 nase x XxX x ue x me Xk é ave 4 XxX x x Numerical values mean the quantitatively determined ones. ‘The symbols © and A represent that quantitative values ‘were not determined, ©! means principal components and A ‘means minor components. The symbol X means that each ‘corresponding component was not detected. TABLE 4 ” C2 Chins C2 Chim SS formceg mento) Xen Acre Ge: Comparative Chine What is claimed is 1. A method for preparing high strength and high ‘shockeresistant china for ceramie whiteware comprising the steps of: ‘molding a china-forming raw material mainly comprising an luminous shale which comprises 50% weight or more of ALO, and Si03; yey material; and flux, and then firing the molded chins-forming saw materia 2. A method for preparing high strength and high thermal shock-resistant china for ceramic whiteware comprising the steps of: ‘molding a china-forming raw material mainly comprising 4 material obtained by calcining an aluminous shale ‘which comprises 50% weight or mote of AIO, and 'Si0. to form corundum and mullite; a clayey material; and a flux, and then firing the molded chins-forming raw materia 3. The method of claim 1 or 2, wherein the china-forming, raw material includes pottery sfone comprising quartz 4. The method for claim Yor 2, wherein the china-forming, raw miaterial includes silica sand comprising quae 43. The method of claim I or 2, wherein the flux is at last ‘one member selected from the group consisting of feldspar, repheline and dolomite6,107,223 15 16 6. The method of claim 1 or2, wherein the overall average particles and 30 to 854 of a glass matrix mainly comprising particle size ofthe chins-forming raw material is controlled SiO, on the basis of the total weight of the china, sid between the range of 1 to 20 ga. crystalline particles comprising 10 to 65% of corundum. 7. The method of claim 1 or 2, wherein the china for 9. The method of claim 1, wherein the aluminous shale is ‘ceramic whiteware is china for sanitary-wace 5 not calcined before the firing sep. 8. The method of claim 1 or 2, wherein the china for ‘ceramic whiteware comprises. 15 10 70% of erysialline sees