AU2005248952A1 - Ceramic material, compostions and process for manufacture thereof - Google Patents

Description

S&FRef: 732737

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT Name and Address of Applicant Actual Inventor(s): Address for Service: Invention Title: Caroma Industries Limited, an Australian company, ACN 000 189 499, of 10 Market Street, Brisbane, Queensland, 4000, Australia Emile Saleh Spruson Ferguson St Martins Tower Level 31 Market Street Sydney NSW 2000 (CCN 3710000177) Ceramic material, compositions and process for manufacture thereof The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845 0 reae0oacrmcmtra aefo h iigo lypoutaca opsto adpoessfrmnfcue rpeaainteefTepesn neto lorltst anegb lycmoito o plcto n lybd eoeglzn n iig n apcERAMIC oftecrmmaterial, cOMOSTIN AopsiinD PRgOES Fy oRston Thsern inetin lteus o ceramic aetei a clad ompoitiand la roce sse anf a te rc paatiols the inks atclar, vth presn vento rlaes tc aemeo a ceramic material, maefrmteigoflyput, a cla y caeompoitions IDadpossfrmanufacture ofnrctlr paitrparithereo Then pirestinenionso reficltesinto ovanrenob ciaa copositn forin aplcaoncton roafr clay body fr lzn and firing Onfe applh rblmo sgiicatio ofgn drn the ceramicfthi material, cla copsiin engobe ca cop sitnand.

procsswesn appictieons therefo ise ins t manufate ol aitayze su asctoilae bowls, ihen botaols bath tubs ashrbsains then sinks, tofsase aiytl n theopeditron Boacground pofetes Invaenton vteu hn.Ti oldte lo ieag Cfsapdpocse iterbest inun of crmcsfhasrele i a wdemande fo sintrt l0 are sitaraeiessuhamoltbolkthnsnksassait.ol n h lewhcharmeomosicric aerqidal, Previ tous wcraich oypimaey ofitrou ciawsusuetone clykoits proflper ofd begipermeable to wtherac Hoeer thela manufaTuroe of triae large sanary wae iemsudsngvireou chinat ise difcltsince itrousinaa ul the fifaetetrin oatoae of afie clay body and alsdigabaelae o suffher onntation rpterti s ompred o vteu.hn.Ti oldte lo ie ag [RALIBZZJcartnaspcdoc:AWL 2 o A disadvantage with the known engobe composition is that the properties of thermal shock resistance, good glaze appearance and chemical resistance are poor for fired clay products and particularly for fired sanitary ware products.

0 Object of the Invention It is an object of at least the preferred embodiment(s) of the present invention to overcome or at least substantially ameliorate at least one of the above problems or N disadvantages or to provide a useful alternative to the prior art.

ON\ Throughout this specification, the term "clay" is intended to mean fine-grained 00 earthy materials that become plastic when mixed with water. Clays include hydrous to aluminum silicates which contain impurities, e.g. potassium, sodium, magnesium, or iron o in small amounts.

Throughout this specification, the term "fire clay" includes flint clay which is typically hard and nonplastic and which resembles flint in appearance. The term "fire clay" also includes plastic fire clay. The term "fire clay" includes hard and soft embedded clay rich in hydrated aluminum silicate or silica, low in alkalis and iron, and which can withstand high temperature without fusion.

Summary of the Invention In an embodiment of the present invention, there is provided a method of producing a ceramic material comprising the steps of: a) mixing silica, a silicate mineral and at least one first clay with a second clay which is different to the at least one first clay to form a silicalsilicate clay mixture; and a) firing the silica/silicate clay mixture clay to form a ceramic material.

In another embodiment of the present invention, there is provided a method of producing a ceramic material comprising the steps of: a) mixing silica, a silicate mineral and at least one first clay with water to form a silica/silicate clay slurry mixture; b) adding a second clay which is different from the at least one first clay to the silica/silicate clay slurry mixture; C) drying the resultant clay mixture from step and d) firing the dried clay mixture from step c) to form a ceramic material.

In a further embodiment of the present invention, there is provided a method of producing a ceramic material which further comprises the step of: a) casting the clay mixture to form a desired shape; b) drying the clay mixture; and [t:UBZjcrmrnflnuispec doc:AWL

I

3 c) and firing the shaped clay mixture to form a ceramic material.

Cl Step b) of casting the mixed clay composition may be in suitable moulds which are made 3of a suitable material such as metal, plastic or composite materials. In an embodiment, 0 the step of casting may be in one or more plastic moulds.

ec C, 5 The first clay composition may comprise one or more clay materials which may be selected from the group consisting of carbonaceous clays, ball clays, kaolin clays, c china clays, and other suitable clays. The particular clays may be selected from the group Sconsisting of bentonite, kyanite, kaolinite, halloysite, dickite, nacrite, illite, 00 C" montmorillonite, pyrophyllite and mixtures thereof.

The second clay which is different to the first clay may comprise one or more Cl clay materials. The one or more clay materials of the second clay may include fire clays such as flint clay, plastic fire clays or mixtures thereof. The one or more fire clay materials of the second clay may have a high degree of resistance to heat. The fire clay materials may have a fusion point higher than about 1000°C to about 1800°C, or higher is than about 1250 0 C to about 1750°C, or higher than about 1400°C to about 1700°C, or higher than about 1450°C to about 1650°C, or higher than about 1500 C to about 1600 0

C.

The one or more fire clay materials may contain high percentages of silica and alumina.

The one or more clay materials may contain as little as possible of such impurities such as lime, magnesia, soda, and potash, which lower the fusion point of the one or more clay materials. In an embodiment of the present invention, the second clay may also comprise flint clay. The second clay may also comprise a calcined flint clay composition.

The step a) of mixing at least one first clay comprising silica and a silicate mineral with a second clay and water to form a slurry may comprise mixing the first clay comprising silica and a silicate mineral with the second clay in ratios which may be as set out in the following Table I: [R;JBZZ)carcfinlpKccdm:AWL Table I First clay Second clay First clay Second clay (wt%) 10 62 38 89 11 61 39 88 12 60 87 13 59 41 86 14 58 42 15 57 43 84 16 56 44 83 17 55 82 18 54 46 81 19 53 47 20 52 48 79 21 51 49 78 22 50 77 23 49 51 76 24 48 52 25 47 53 74 26 46 54 73 27 45 72 28 44 56 71 29 43 57 30 42 58 69 31 41 59 68 32 40 67 33 39 61 66 34 38 62 35 37 63 64 36 36 64 63 37 35 [R:\LI BZZ]caromafinaspcc.docAWL First clay Second clay First clay Second clay (wt%) 34 66 22 78 33 67 21 79 32 68 20 31 69 19 81 70 18 82 29 71 17 83 28 72 16 84 27 73 15 26 74 14 86 75 13 87 24 76 12 88 23 77 11 89 Further, about 90 to about 98wt% of the first clay comprising silica and a silicate mineral may also be mixed with about 2 to about 10wt% of the second clay. In particular, about 92 to about 96wt% of the first clay comprising silica and a silicate mineral may be mixed with about 4 to about 8wt% of the second clay. Further, about 94 to about 96wt% of the first clay comprising silica and a silicate mineral may be mixed with about 4 to about 6wt% of the second clay. Further, about 95wt% of the first clay comprising silica and a silicate mineral may be mixed with about 5wt% of the second clay.

In an embodiment of the present invention, about 70 to about 85wt% of the first o0 clay comprising silica and a silicate mineral may be mixed with about 15 to about of the second clay. In another embodiment, about 75 to about 85wt% of the first clay comprising silica and a silicate mineral may be mixed with about 15 to about 25wt% of the second clay. In another embodiment, about 75 to about 80wt% of the first clay comprising silica and a silicate mineral is mixed with about 20 to about 25wt% of the second clay. In an example of the invention, about 77 to about 80wt% of the first clay comprising silica and a silicate mineral is mixed with about 20 to about 23wt% of the second clay.

In another embodiment of the present invention, a deflocculant agent may be added to the first and second clay. The deflocculant agent may be selected from the (R:\LIBZZ]caromfinalspoc. do:AWL O group consisting of soda ash, sodium silicate, sodium hydroxide, sodium poly CN acrylate (such as Dispex N40) and deflocculants formed by the alkali extraction of lignite such as Dolaflux (sodium humates). The deflocculant may be added in an amount of 0 about 0.01 to about 10.0wt%, about 0.01 to about 9.5wt%, about 0.01 to about S 5 about 0.01 to about 8.wt%, about 0.01 to about 8.0wt%, about 0.01 to about about 0.01 to about 7.0wt%, about 0.01 to about 6.5wt%, about 0.01 to about ci about 0.01 to about 5.5wt%, or about 0.01 to about 5.0wt% to the first and second clay Scomposition. The deflocculant may also be added in an amount of about 0.01 to about about 0.01 to about 4.wt%, about 0.01 to about 3.5wt%, about 0.01 to about 3.wt%, about 0.01 to about 2.5wt%, about 0.01 to about 2.5wt%, about 0.02 to about 0 1.5wt%, about 0.02 to about 1.5wt%, about 0.0 to about 1.25wt%, about 0.05 to about about 0.05 to about 0.5wt%, about 0.1 to about 0.25wt%, about 0.2 to about 0.0wt%, about 0.0 to about 0.75wt%, about 0.4 to about 0.7wt%, and about 0.5 to about 0.80wt%, about 0.3 to about 0.75wt%, about 0.4 to about 0.7wt%, and about 0.5 to about 0.6wt% to the first and second clay.

The silica may be selected from the group consisting of silica, silica sand, silica flour, quartz and flint. In an embodiment, the silica may be silica sand having a grade of up to about 30mesh, up to about 35 mesh, up to about 40mesh, up to about 45mesh, up to about 50mesh, up to about 55 mesh, up to about 60mesh, up to about 65mesh, up to about mesh, up to about 75mesh, up to about 80 mesh, up to about 85mesh, up to about mesh, up to about 95mesh or up to about 100 mesh.

In another embodiment, the silica may be silica flour having a grade of up to about 30mesh, up to about 35 mesh, up to about 40mesh, up to about 45mesh, up to about up to about 55 mesh, up to about 60mesh, up to about 65mesh, up to about mesh, up to about 75mesh, up to about 80 mesh, up to about 85mesh, up to about mesh, up to about 95mesh or up to about 100 mesh.

The silicate mineral(s) used in this invention may include neosilicate(s), inosilicate(s), cyclosilicate(s), phyllosilicate(s), and tectosilicate(s). The silicate mineral may include inosilicates and particularly single chain inosilicates. Some examples may include calcium silicate (CaSiO 3 magnesium silicate (MgSiO 3 and alpha dicalcium silicate (a-CaSiO 4 and steatite (3MgO.4SiO 2

.H

2 In particular, the silicate mineral may be calcium silicate and more particularly may be wollastonite and still more particularly may be acicular wollastonite. The initial particle size of the silicate mineral before milling may be 99% passing 120 mesh screen.

[RUIBZZl]carmnalwplcc dc.AWL O The silica and silicate mineral may be mixed and milled together before being 0 C added to the clay material. The silica and silicate mineral may also be intimately wet ()milled together. The intimate wet milling may be achieved in a ball mill.

0 The median particle size and the particle size distribution of the silica and silicate mineral mixture after mixing and milling were tested by the SEDIGRAPH 5100 machine method. However, the particle sizes referred to in this specification are measured and C expressed as "equivalent spherical diameter", or "ESD". The median particle size is the O value d 50 at which there is 50wt% of the particles present in the composition which have 00 oO l an ESD less than that value, as determined by the SEDIGRAPH 5100 machine method.

All particle size distribution (PSD) values which are measured and reported in the O specification were taken in a known manner with measurements made in water at the standard temperature of 34.9C.

A suitable median particle size of the silica and silicate mineral blend may be up to about 100 microns, up to about 95 microns, up to about 90 microns, up to about microns, up to about 80 microns, up to about 75microns, up to about 70 microns, up to about 65 microns, up to about 60 microns, up to about 55 microns, up to 50 microns, up to about 49 microns, up to about 48 microns, up to about 47 microns, up to about 46 microns, up to about 45 microns, up to about 44 microns, up to about 43 microns, up to about 42 microns, up to about 41 microns, up to about 40 microns, up to about 39 microns, up to about 38 microns, up to about 37 microns, up to about 36 microns, up to about 35 microns, up to about 34 microns, up to about 33 microns, up to about 32 microns, up to about 31 microns, up to about 30 microns, up to about 29 microns, up to about 28 microns, up to about 27 microns, up to about 26 microns, up to about microns, up to about 24.5 microns, up to about 24.0 microns, up to about 23.5 microns, up to about 23.0 microns, up to about 22.5 microns, up to about 22.0 microns, up to about 21.5 microns, up to about 21.0 microns, up to about 20.5 microns, up to about 20.0 microns, up to about 19.5 microns, up to about 19.0 microns, up to about 18.5 microns, up to about 18.0, up to about 17.5 microns, up to about 17.0 microns, up to about up to about 16.5 microns, up to about 16.0 microns, up to about 15.5 microns, up to about 15.0 microns, up to about 14.5 microns, up to up to about 14.0 microns, up to about 13.5 microns, up to about 13.0 microns, up to about 12.5 rhicrons, up to about 12.0 microns, up to about 11.5 microns, up to about 11.0 microns, up to about 10 microns, up to about microns, up to about 9.0 microns, up to about 8.5 microns, up to about 8.0 microns, up to about 7.5 microns, up to about 6.5 microns, up to about 6.0 microns, up to about microns, up to about 5.0 microns, up to about 4.5 microns, up to about 4.0 microns, up to [R:dJBZZ]crcmxalnalspec doc:AWL o about 3.5 microns, up to about 3.0 microns, up to about 2.5 microns, up to about C microns, up to about 1.5 microns, up to about 1.0 microns and up to about 0.5 microns.

The step of mixing the silica and silicate mineral may be fine milling such that 0the silicate mineral and silica are intimately milled together. The silicate mineral and C 5 silica may be milled together such that the median particle size distribution is up to about 15.0 microns, up to about 14.5 microns, up to about 14.0 microns, up to about 13.5 C microns, up to about 13.0 microns, up to about 12.5 microns, up to about 12.0 microns, up Oto about 11.5 microns, up to about 11.0 microns, up to about 10.5 microns, up to about 00 oO l 10.0 microns up to about 9.5 microns, up to about 9.0 microns, up to about 8.5 microns, 1o up to about 8.0 microns, up to about 7.5 microns, up to about 7.0 microns, up to about o microns, up to about 6.0 microns, up to about 6.5 microns, up to about 6.0microns, up to about 5.5 microns, up to about 5.0 microns, up to about 4.5 microns, up to about about 5.5 microns, up to about 5.0 microns, up to about 4.5 microns, up to about 4.02.0 microns, up to microns, up to about 3 microns, up to about 2.5 microns, up to about 2.0 microns, up to about 1.5 microns, up to about 1.0 microns and up to about 0.5 microns, up to about 0.25 microns. An example of a suitable range of the median particle size of the silica and silicate mineral is from about 2 to about 1 Omicrons.

An example of the silica and silicate mineral which may be used in this invention is silica and calcium silicate. In particular, the silica may be silica sand and the calcium silicate may be wollastonite. In a particular example, the silica sand and calcium silicate may be ground or milled and in particular may be wet milled to a median particle size of up to about 15 microns, up to about 14.5 microns, up to about 14.0 microns, up to about 13.5 microns, up to about 13.0 microns, up to about 12.5 microns, up to about 12.0 microns, up to about 11.5 microns, up to about 11.0 microns, up to about 10.5 microns, up to about 10.0 microns, up to about 9.5 microns, up to about 9.0 microns, up to about microns, up to about 8.0 microns, up to about 7.5 microns, up to about 6.5 microns, up to about 6.0 microns, up to about 5.5 microns, up to about 5.0 microns, up to about microns, up to about 4.0 microns, up to about 3.5 microns, up to about 3.0 microns, up to about 2.5. microns, up to about 2.0 microns, up to about 1.5 microns, up to about microns and up to about 0.5 microns.

The particle size distribution of the blend of silica and silicate mineral may be narrow. However, the silica and silicate mineral mixture may be controlled in size so that the median particle size measured by the SEDIGRAPH 5100 is about 2 to about microns, about 2.5 to about 9.5 microns, about 2.5 to about 9.0 microns, about 2.5 to about 8.5microns, about 2.5 to about 8.0 microns, about 2.5 to about 7.5 microns, about (RALJ BZZlcrmafinalspe .dcAWL o 3.0 to about 7.0 microns, about 3.5 to about 6.5 microns, about 3.5 to about 6.0 microns, Nl about 4.0 to about 5.5 microns, or about 4.5 to about 5 microns.

In another embodiment of the present invention, the silicate mineral and silica 0 may be mixed or milled together with water to form a slurry. The slurry may then be Cl 5 blended with a flint clay composition. In a particular example, the silicate mineral is wollastonite and the silica is silica sand. The flint clay composition may be calcined flint N clay.

ON\ In another embodiment of the present invention, a method for producing a slurry 00 Cl of the silicate and silica blend used in the methods of the invention comprises: milling the silicate together with silica and suitable amounts of water to form a o mixture having a median particle size from about 0.5 to about 15gm and having a narrow particle size distribution; and then blending the silicate and silica slurry with a clay material.

In another embodiment of the present invention, there is provided a method of producing a ceramic material comprising the steps: a) mixing a first composition comprising: i) a silica! wollastonite slurry mixture; 1i) a first clay material; iii) optionally a second clay material; and iv) optionally a third clay material; with b) a second composition comprising flint clay wherein the silica/wollastonite slurry in a)i) has a median particle size selected from the group consisting of about 0.5 to about 15 microns, and may be 0.5 to about 10 microns, 1.0 to about 10 microns, 1.5 to about 10 microns, about 2.0 to about 10 microns, about 2.0 to about 9.5 microns, about 2.0 to about 9.0 microns, about 2.0 to about 8.5 microns, about 2.0 to about 8.0 microns, about 2.0 to about 7.5 microns, about 2.0 to about 7.0 microns, about 2.0 to about microns, about 2.0 to about 6.0 microns, about 2.0 to about 5.5 microns, about 2.0 to about 5.0 microns, about 2.0 to about 4.5 microns, about 2.0 to about 4.0 microns, about to about 3.5 microns, about 2.0 to about 3.0 microns, about 2.0 to about 2.5 microns, and about 2.0 to about 2.2$ microns.

In another embodiment, the second clay material is added in step iii) above and the third clay material is added in step iv) above where the first, second and third clay material are selected from the goup consisting of ball clays, kaolin, china clays, and other suitable clays.

(RALIBZZ fcartmlspec doCCAWi.

0 In another embodiment of the present invention, there is provided a ceramic l material comprising: a) at least one first clay; Sb) a second clay comprising a fire clay; c) silica; and d) wollastonite.

Cl In another embodiment of the present invention, there is provided a ceramic material Scomprising: 00 a) at least one clay selected from the group consisting of carbonaceous clay, ball clay, china clay and kaolin clay; o b) a second clay comprising a fire clay; c) silica; and d) wollastonite.

The ceramic material which may be formed by the method of the present invention may comprise: carbonaceous clay; fired white plastic ball clay; fired white kaolin clay; silica sand, quartz or flint; calcined flint clay or mullite; and wollastonite.

The ceramic material which may be formed by the method of the present invention may comprise: about 5 to about 30wt% carbonaceous clay; about 5 to about 30wt% fired white plastic ball clay; about 10 to about 40wt% fired white kaolin clay; about 10 to about 40wt% silica sand, quartz or flint; about 10 to about 40wt% calcined flint clay or mullite; and about 1 to about 20wt% wollastonite.

The carbonaceous clay may be present in the ceramic material formed by method of the present invention in an amount of about 5 to about 30wt%, or about 6 to about 28wt%, or about 7 to about 26wt%, or about 8 to about 24wt%, or about 9 to about 22wt%, or about 10 to about 20wt%, or about 11 to about 18wt%, or about 12 to about 16wt%, or about 13 to about 15wt%, or about 14wt%.

[Ru BZcaruCxnflnzcpc.de:AWL O The fired white plastic ball clay may be present in the ceramic material 0 N formed by method of the present invention in an amount of about 5 to about 30wt%, or )about 6 to about 28wt%, or about 7 to about 26wt%, or about 8 to about 24wt%, or about 9 to about 22wt%, or about 10 to about 20wt%, or about 11 to about 19wt%, or about 12 C 5 to about 18wt%, or about 13 to about 18wt%, or about 14wt to about 18%, or about to about 18%, or about 16wt to about 18%, or about 17wt%.

C The fired white kaolin clay may be present in the ceramic material formed by Smethod of the present invention in an amount of about 10 to about 40wt%, or about 11 to 00 Sabout 38wt%, or about 12 to about 36wt%, or about 13 to about 34wt%, or about 14 to about 32wt%, or about 15 to about 30wt% or about 16 to about 28wt%, or about 17 to o about 26wt%, or about 18 to about 25wt%, or about 19wt to about 24%, or about 20wt to about 23%, or about 21wt% to about 23%, or about 22wt%.

The silica sand, quartz or flint may be present in the ceramic material formed by method of the present invention in an amount of about 10 to about 40wt%, or about 11 to about 38wt% or about 12 to about 36wt%, or about 13 to about 34wt%, or about 14 to about 32wt%, or about 15 to about 30wt% or about 16 to about 28wt%, or about 17 to about 26wt%, or about 18 to about 25wt%, or about 19wt to about 24%, or about 20wt to about 23%, or about 20wt% to about 22%, or about 21wt%.

The calcined flint clay or mullite may be present in the ceramic material formed by method of the present invention in an amount of about 10 to about 40wt%, or about 11 to about 38wt% or about 12 to about 36wt%, or about 13 to about 34wt%, or about 14 to about 32wt%, or about 15 to about 30wt% or about 16 to about 28wt%, or about 17 to about 26wt%, or about 18 to about 25wt%, or about 19wt to about 24%, or about to about 23%, or about 20wt% to about 22%, or about 21wt%.

The wollastonite may be present in the ceramic material formed by method of the present invention in an amount of about 1 to about 20wt%, or about 1 to about 19wt% or about 1 to about 18wt% or about 1 to about 17wt%, or about 1 to about 16wt%, or about 1 to about 15wt%, or about 1 to about 14wt%, or about 1 to about 13wt%, or about 1 to about 12wt%, or about 1 to about lwt%, or about 1 to about 10wt%, or about 1 to about 9wt% or about 1 to about 8wt%, or about 1 to about 7wt%, or about I to about 6wt%, or about 1 to about 5wt%, or about 2wt% to about or about 3wt% to about or about 4wt% to about 5wt%, or about Swt%.

The ceramic material formed by method of the present invention may also comprise a deflocculant in the final ceramic material product. The deflocculant may be present in an amount of from about 0.lwt% to about 10wt%, or about 0.lwt% to about RCLIBZZ)cuaromanalspec.doc:AWL 12 0 9.5wt%, or about O.lwt% to about 9.0wt%, or about O.lwt% to about 8.5wt%, or about CN 0.1wt% to about 8.0wt%, or about 0.lwt% to about 7.5wt%, or about 0.lwt% to about or about 0.lwt% to about 6.5wt%, or about O.lwt% to about 6.0wt%, or about 00.lwt% to about 5.5wt%, or about 0.lwt% to about 5.0wt%, or about 0.lwt% to about C 5 4.5wt%, or about 0.lwt% to about 4.0wt%, or about 0.lwt% to about 3.5wt%, or about 0.2wt% to about 3.0wt%, or about 0.3wt% to about 2.5wt%, or about 0.3wt% to about C wt%, or about 0.3wt% to about 1.5wt%, or about 0.3wt% to about 1.0wt%, or about N 0.3wt% to about 0.75wt%, or about 0.3wt% to about 0.6wt%, or about 0.lwt% to about oO Cl 0.5wt%, or about 0.1wt% to about 0.4.5wt%.

The deflocculant may be selected from the group consisting of sodium silicate, C soda ash, sodium silicate, sodium hydroxide, sodium poly acrylate (such as Dispex) and deflocculants formed by the alkali extraction of lignite such as Dolaflux (sodium humates).

In a particular embodiment, the deflocculant present in the ceramic material is formed by method of the present invention may be a mixture of sodium silicate, soda ash, sodium polyacrylate (Dispex) and sodium humates (Dolaflux). In particular, the deflocculant may comprise: about 0.1 to about 1.0wt% sodium silicate; about 0.1 to about 0.5wt% soda ash; about 0.01 to about 0.05wt% Dispex; and about 0.01 to about 0.05wt% Dolaflux SP NUE.

The composition of the ceramic material body components of the present invention may also be 52 to 75wt% SiO 2 16 to 30wt% A1 2 0 3 1.5 tol0wt% CaO, 0.1 to MgO, 0.1 to0.8wt% Na20 and 0.8 to 1.1wt% K 2 0.

The carbonaceous clay may be Morwell clay. The fired white plastic ball clay may be Axedale clay. The fired white kaolin clay may be Oakland clay.

In another embodiment of the present invention, there is provided an engobe clay composition comprising one or more clays and a silicate mineral. The engobe composition may also include one or more additional components selected from the group consisting of one or more fluxes, silica, lithium containing minerals and opacifiers.

In another embodiment of the present invention, there is provided an engobe clay composition comprising: a) one or more clays; b) a silicate mineral; c) optionally, an opacifier; [R:\LUBZZjcaromafin&alsc do AWL 0 d) silica; Cl e) one or more fluxes.

C)

SThe engobe clay composition may further comprise a lithium containing mineral.

ec S 5 In a further embodiment, there is provided an engobe clay composition comprising: N a) one or more clays; Sb) a silicate mineral; 00 Sc) optionally, an opacifier; S 10 d) silica; o e) one or more fluxes; and f) a lithium containing mineral comprising spodumene or petalite.

The one or more clays of component a) may be selected from the group consisting of ball clays, kaolin, china clays, and other suitable clays. The particular clays may be selected from the group consisting of bentonite, kyanite, kaolinite, halloysite, dickite, nacrite, illite, montmorillonite, pyrophyllite and mixtures thereof. In one embodiment, component a) of the engobe clay composition may include a mixture of clays and may include one or more members selected from the group consisting of Sanblend 75® clay and Remblend® Clay. Sanblend 75® is fine grained, plastic clay, which is normally a carbonaceous clays comprising mainly of disordered to ordered kaolinite with mica and quartz minerals. Remblend® Clay is white burning kaolin having the approximate composition Al 2 0 3 .2SiO 2 2H 2 0.

The silicate mineral used in the engobe composition may include neosilicate(s), inosilicate(s), cyclosilicate(s), phyllosilicate(s), and tectosilicate(s). The silicate mineral may include inosilicates and particularly single chain ihosilicates. Some examples may include calcium silicate (CaSiO 3 magnesium silicate (MgSiO 3 and alpha dicalcium silicate (a-CaSiO 4 zirconium silicate and steatite (3MgO.4SiO 2

.H

2 In particular, the silicate mineral may be calcium silicate and more particularly may be wollastonite and still more particularly may be acicular wollastonite. The initial particle size of wollastonite may be 99% passing 120 mesh screen. The engobe composition of the present invention may further comprise wollastonite. Wollastonite may be added to the engobe composition in the form of acicular wollastonite (calcium metasilicate, CaSiO 3 [RILIBZZcaronafnulspcc.doc:AWL 14 O The initial particle size of the starting raw wollastonite is pulverized 0 Cl using a ball mill and the resultant slurry mix may be adjusted to comprise a median q particle size of about 2 to about 10 pm.

0 Wollastonite may be added to the engobe composition in an amount ranging C, 5 from about 0.5 to about 20wt%, or about 1.0 to about 19wt%, about 1.5 to about 18wt%, about 2.0 to about 17wt%, about 2.5 to about 16wt%, about 3.0 to about 15wt%, about C to about 14wt%, about 4.0 to about 13wt%, about 4.5 to about 12wt%, 5.0 to about N 1 lwt%, about 5.5 to about 10wt%, about 5.5 to about 9wt%, about 6 to about 8wt%, and oO Sabout 7wt%. Wollastonite may be in the form of acicular wollastonite. The presence of wollastonite may provide improved dimensional stability green strength and may reduce Sthe cracking and chipping of the engobe composition. Also, the addition of wollastonite in the engobe composition may substantially eliminate or at least reduce the spangling defect and provides the fire clay ware with excellent glaze appearance.

The opacifier c) may be selected from the group consisting of zirconium silicate, rutile (TiOz), zinc borate, zirconium oxide, zinc oxide, titanium dioxide, tin oxide, cassiterite or any other agent which is able to make the engobe composition opaque.

The opacifier may be contained in the engobe composition in an amount ranging from about 0.5wt% to about 20wt%, or about 0.6wt% to about 19wt%, or about 0.7wt% to about 18wt%, or about 0.8wt% to about 18wt%, or about 0.9wt% to about 17wt%, or about 1.0wt% to about 16wt%, or about 1.25 to about 15wt%, or about 1.5 to about 14wt%, or about 1.75 to about 13wt%, or about 2.0 to about 12.5wt%, or about 2.5 to about 12wt%, or about 3.0 to about 11.5wt%, or about 3.5 to about I lwt%, or about to about 1 lwt%, or about 4.5 to about 1 lwt%, or about 5.0 to about I lwt%, or about to about 1 lwt%, and about The engobe composition of the present invention may comprise zirconium silicate (ZrSiO 4 or tin oxide. The presence of zirconium silicate (zircon) or tin oxide provides the engobe composition with the desired whiteness and improves the abrasion and mechanical resistance.

The silica may be selected from the group consisting of silica, silica sand, silica flour, quartz and flint. In an embodiment, the silica may be silica sand, silica quartz or silica flour having a grade of up to about 30mesh, up to about 35 mesh, up to about 40mesh, up to about 45mesh, up to about 50mesh, up to about 55 mesh, up to about 60mesh, up to about 65mesh, up to about 70 mesh, up to about 75mesh, up to about 80 mesh, up to about 85mesh, up to about 90 mesh, up to about 95mesh or up to about 100 mesh.

[R:\IBZZ]caraintlarilspe.doc:AWL 0 The one or more fluxes in the engobe composition may comprise one or 0 CI more of nepheline syenite, potash and soda feldspar, rhyolite minerals, and mesolite S(Na20.A1 2 0 3 .3SiO 2 .2H 2 The one or more fluxes may be present in an amount of about to about 30wt%, about 7.5wt% to about 27.5wt%, about 10wt% to about 25wt%, about C 5 10wt% to about 22.5wt%, or about 12.5wt% to about 22.5wt%, about 15wt% to about about 17.5Wt% to about 20wt%, and about 19wt%.

r Nepheline syenite is a medium to coarse-grained, light to medium-gray, igneous.

Srock that is composed predominantly of a silicate mineral called orthoclase (KAISi0Os) 00 and has a granite-like appearance. It may be distinguished from granite by little or no S 10 quartz content (free SiO 2 Nepheline syenite is sometimes referred to as "blue granite" O and "gray granite" varieties.

In a particular embodiment, nepheline syenite and a lithium containing mineral may be mixed together in a ratio of about 1:10, 1.5:10, 2:10, 2.5:10, 3:10; 3.5:10, 4:10, 4.5:10, 5:10, 5.5:10, 6:10, 6.5:10, 7:10, 7.5:10, 8:10, 8.5:10, 9:10, 9.5;10, 1:1, 1.1:1, 1.2:1, is 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:12, 1.8:1, 1.9:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6.0:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, and 10:1. However, other fluxes such as potash, feldspar, rhyolite minerals and mesolite may also be mixed in the aforementioned ratios (instead of nepheline syenite) with the lithium containing mineral.

In the engobe clay composition of the present invention, the lithium-containing mineral may also contain aluminum. The lithium containing mineral may be selected from spodumene, petalite, lepidolite or mixtures thereof. The lithium containing mineral may be contained in the engobe composition in the range of about 0.1 to about about 0.2 to about 22.5wt%, about 0.3 to about 20wt%, about 0.4 to about 17.5wt%, or about 0.5 to about 15wt%, about 0.75 to about 12.5wt%, about 1.0 to about 10wt%, about 1.5 to about 7.5wt%, about 1.5 to about 5wt%, and about 2.0 to about 5.0wt%, and about to about In one example of the engobe composition, the lithium-containing mineral is spodumene which may be selected from one or both of the two varieties called Kunzite and Hiddenite. The presence of lithium-containing mineral aluminum silicate (spodumene) may provide the engobe composition of the present invention with an excellent thermal shock resistance and may lessen the incident of cooling cracks (dunts).

In a further embodiment of the invention, the engobe composition may further comprise a deflocculant.

The deflocculant may be selected from sodium silicate (grade vitrosol Dolaflux (grade SP NEW) and Dispex (grade N40) solutions. These chemicals provide [kUJBZZ]carnmfnapacc.d=cAWL O the casting slip with a long term stability and consistency. Dispex N40 is a 0 CN deflocculant and dispersant material based on a lower molecular weight of sodium q polyacrylate. Dispex N40 has 44 to 46% active sodium polyacrylate. Dolaflux is a 0 sodium humate base deflocculant that has the following composition; silicic acid H 2 SiO 3 ec C s disodium salt silicic acid H 6 Si20 7 hexasodium salt>10%and sodium hydroxide C In a further embodiment of the invention, there is provided an engobe clay Scomposition comprising: 00 Sa) about 3 to about 43wt% of a first clay material; b) about 3 to about 43wt% of a second clay material; o c) about 0.5 to about 20wt% wollastonite; d) about 0.5 to about 20wt% of an opacifier; e) about 5 to about 65wt% silica; f) about 3 to about 45wt% of one or more fluxes; and g) about 0.1 to about 25wt% of a lithium containing mineral.

In particular, the first clay material may be present in the engobe composition in an amount of about 3 to about 43wt%, about 4 to about 41wt%, about 5 to about 39wt%, about 6 to about 37wt%, about 7 to about 35wt%, about 8 to about 33wt%, about 9 to about 31wt%, about 10 to about 29wt%, about 11 to about 27wt%, about 12 to about 25wt%, about 13 to about 23wt%, about 14 to about 21wt%, about 15 to about about 15 to about 19wt%, about 15 to about 18wt%, about 15 to about 17wt%, and about 16wt%.

In particular, the second clay material may be present in the engobe composition in an amount of about 3 to about 43wt%, about 4 to about 41wt%, about 5 to about 39wt%, about 6 to about 37wt%, about 7 to about 35wt%, about 8 to about 33wt%, about 9 to about 31wt%, about 10 to about 29wt%, about 11 to about 27wt%, about 12 to about about 13 to about 23wt%, about 14 to about 21wt%, about 14 to about about 14 to about 19wt%, about 14 to about 18wt%, about 14 to about 17wt%, about 14 to about 16wt%, and about In particular, the second clay material may be present in the engobe composition in an amount of about 0.5 to about 20wt%, or about 1.0 to about 19wt%, about 1.5 to about 18wt%, about 2.0 to about 17wt%, about 2.5 to about 16wt%, about 3.0 to about about 3.5 to about 14wt%, about 4.0 to about 13wt%, about 4.5 to about 12wt%, to about 1 wt%, about 5.5 to about 10wt%, about 5.5 to about 9wt%, about 5.5 to [R:\UJBZ]fcarninallspc doc:AWL 0 about 8wt%, about 5.5 to about 7.5wt%, about 5.5 to about 7wt%, about 5.5 to 0 CN about 6.5wt%, and about 6wt%.

The opacifier may be contained in the engobe composition in an amount ranging Sfrom about 0.5wt% to about 20wt%, or about 0.6wt% to about 19wt%, or about 0.7wt% C 5 to about 18wt%, or about 0.8wt% to about 18wt%, or about 0.9wt% to about 17wt%, or about 1.0wt% to about 16wt%, or about 1.25 to about 15wt%, or about 1.5 to about C 14wt%, or about 1.75 to about 13wt%, or about 2.0 to about 12.5wt%, or about 2.5 to ON about 12wt%, or about 3.0 to about 11.5wt%, or about 3.5 to about 1 lwt%, or about 00 to about 1 lwt%, or about 4.5 to about 1 lwt%, or about 5.0 to about 1 lwt%, or about 0 n io to about 1 lwt%, and about 1Owt%.

o The silica may be contained in the engobe composition in an amount ranging from about 5 to about 65wt%, or about 7.5wt% to about 62.5wt%, or about 10 to about or about 12.5wvt% to about 57.5wt%, or about 15 to about 55wt%, or about 17.5wt% to about 52.5wt%, or about 20 to about 50wt%, or about 22.5 to about or about 25 to about 40wt%, or about 27.5 to about 37.5wt%, or about 27.5 to about 32.5wt%, or about 27.5 to about 30wt%, or about The one or more fluxes may be present in the engobe composition in an amount of about 3 to about 45wt%, about 3 to about 40wt%, about 4 to about 35wt%, about 5 to about 30wt%, about 7.5wt% to about 27.5wt%, about 10wt% to about 25wt%, about 10wt% to about 22.5wt%, or about 12.5wt% to about 22.5wt%, about 15wt% to about about 17.5Wt% to about 20wt%, and about 19wt%.

The lithium containing mineral may be contained in the engobe composition in the range of about 0.1 to about 25wt%, about 0.2 to about 22.5wt%, about 0.3 to about about 0.4 to about 17.5wt%, or about 0.5 to about 15wt%, about 0.75 to about 12.5wt%, about 1.0 to about 10wt%, about 1.5 to about 7.5wt%, about 1.5 to about and about 2.0 to about 5.0wt%, about 3.0 to about 5.0wt%, and about 4wt%.

In particular, the first clay material may be a carbonaceous or ball clay. An example of a carbonaceous clay is Sanblend 75 clay.

In particular, the second clay material may be a pure kaolin clay which fires white at a high casting rate. An example of a pure kaolin clay is Remblend clay.

In particular, the silicate mineral may be wollastonite.

In particular, the silicate mineral may be wollastonite.

In particular, the opacifier may be zirconium silicate or tin oxide.

In particular, the silica may be silica flour.

In particular, the lithium-containing mineral may be spodumene or petalite.

[R:\UBZZcaromafinalspc doc:AWL O In particular, the one or more fluxes may be nepheline syenite, potash feldspars, soda 0 CN feldspars, and mixtures thereof.

.)The first clay material may be a clay comprising kaolinite with mica and quartz Sminerals. In a particular example, the first clay may be a ball clay composition. In particular, the ball clay composition may be Sanblend 75® clay.

cI 00 cI 0 00 Raw SiO, A1zO 3 Fe 2

O

3 CaO MgO Na z O K 2 0 TiO 2 Ignition Materials loss Sanblend 52.4 30.5 1.00 0.200 0.300 0.300 2.200 1.200 11.90 75® clay Caroso FC 56.1 29.1 0.9 0.1 0.3 0.3 2.3 1.3 9.6 Sanblend 57.6 26.8 1 0.2 0.3 0.3 2.2 1.3 The second clay material may be a clay comprising kaolin. In a particular example, the second clay may be Remblend® clay.

Raw SiO 2 A1 2 0 3 FezO 3 CaO NazO K 2 0 TiO 2 Ignition materials Loss Kaolin 47.8 36.7 0.8 0.1 0.1 2.1 0.1 12.2

HPC

The opacifier may be zirconium silicate or tin oxide. The one or more fluxes may comprise nepheline syenite. The lithium containing mineral may be spodumene.

In another embodiment, there is provided a method for producing an engobe composition comprising: Is a) adding water and silica to a mill; b) adding optionally an opacifier, one or more fluxes and a silicate mineral to at least one clay; and c) grinding the components in a) and b) to a suitable median particle size.

In a further embodiment of the method for producing an engobe composition, a lithium containing mineral may be added in step b).

The step of grinding in step c) may result in a median particle size selected from the group consisting of about 0.5 to about 15 microns, and may be 0.5 to about microns, 1.0 to about 10 microns, 1.5 to about 10 microns, about 2.0 to about 10 microns, about 2.0 to about 9.5 microns, about 2.0 to about 9.0 microns, about 2.0 to about IRI\UBZZljarnfinalipc doc:AWL O microns, about 2.0 to about 8.0 microns, about 2.0 to about 7.5 microns, about 2.0 to Sabout 7.0 microns, about 2.0 to about 6.5 microns, about 2.0 to about 6.0 microns, about to about 7.0 microns, about 2.0 to about 6.5 microns, about 2.0 to about 6.0 m icrons, about to about 5.5 microns, about 2.0 to about 5.0 microns, about 2.0 to about 4.5 microns, Sabout 2.0 to about 4.0 microns, about 2.0 to about 3.5 microns, about 2.0 to about microns, about 2.0 to about 2.5 microns, and about 2.0 to about 2.25 microns.

The engobe composition, may range in color (for example from red to buff) may C be applied between the ceramic body and the glaze layer. The engobe composition is Stypically classified between a glaze and a clay. Although the engobe composition fires 00 Smore vitreous than the ceramic body it covers, the engobe composition does not become S0o glassy like a glaze during firing. One of the benefits of using an engobe is that it can be o applied over a wet or dry clay body, and then fired to the clay's specified temperature.

Engobes can be painted, brushed, sprayed and layered. An engobe in a stiffer form can be used to add texture, and after the piece is fired, a stain wash can be applied to highlight the surface.

In another embodiment, the ceramic material of the present invention may comprise one ore more layers of the engobe composition of the present invention.

Detailed Description of the Preferred Embodiments At least one preferred embodiment of the present invention will now be described, by way of example only, which is not intended to limit the scope and generality of the invention as defined in the claims of the present invention.

Examples of the Invention In the following examples of the present invention, reference is made to one or more of the following clay materials, the chemical composition of which are set out in Table II below.

Table II Raw SIO A 2 sO 3 Fe 2

O

3 CaO MgO NazO K 1 0 ZrO 2 Li 2 0 TiO, Igniti Materials 2 on loss Oakland 48.4 34.4 0.99 0.12 0.25 0.15 2.85 1.6 10.9 Clay Morwell 62.4 21.6 0.85 0.12 0.14 0.04 0.26 3.01 11.2 clay BZZ)crumafinHpec docAWL Axedaleclay 59.4 26.0 1.02 0.03 0.83 0.3 3.19 1.58 7.37 Calcined 50.6 46.5 0.8 0.2 0.1 0.1 0.1 0.8 0.1 flint clay Zirconium 32.1 1.33 0.07 65.6 0.12 0.53 silicate Spodumene 66.3 26.8 0.07 0.01 0.00 0.17 0.11 7.65 0.01 0.52 Wollastonite 51.0 0.2 0.4 47.5 0.1 0.02 0.68 Silica Sand 99.8 0.09 0.04 0.0 0.0 0.0 0.0 0.0 0.03 Nepheline 60.1 23.5 0.09 0.41 0.02 10.4 5.0 0.44 Syenite Remblend 48.0 37.0 1.0 0.07 0.30 0.1 2.0 0.05 12.5 clay Sanblend 75 52.4 30.5 1.0 0.2 0.3 0.3 2.2 1.2 11.9 The ignition loss (LOI) summarizes the components within a raw material that burn away or products of decomposition that are lost as gases during firing. Some companies separate the different components of weight lost during firing as C, H 2 0, SO 3 etc. A formula weight of zero should be used in each oxide of this type so there is no impact on fired formula calculations.

Example 1.

In a first example of the present invention, there is shown a method of producing a ceramic material in accordance with the present invention.

A first step of the method is producing a silica sand/wollastonite slurry mixture.

This is achieved by a wet milling step ofwollastonite and silica sand as follows.

Wet milling is used to grind silica sand (30 mesh grade) and wollastonite (common grade) together. High density Alubit grinding media is used. Silica and wollastonite are milled together for 12 hours or less to give a specified median particle size. In particular examples, the silica sand and calcium silicate (wollastonite) may be ground or milled to achieve a median particle size of up to 10 microns.

In this example of the invention, a silica /wollastonite slurry is formed by mixing 3500 kg of silica sand with 1500 kg of wollastonite and water to form a slurry like consistency. The wollastonite may be selected from commercially available common grades of wollastonite including acicular wollastonite. Some examples of wollastonite are Kemolite A60 and FW 70 C. The starting particle size of the common grade wollastonite raw material is 99% passing 120 mesh screen. The silica is available as R :L BZZ]cirosinldspec.doc:AWL O silica sand which is commercially available as silica sand grade 30 to 40 mesh.

Cl Suitable addition of water is added to the silica/wollastonite mixture in order to arrive at the desired slip density for the desired mixing blunger. In one example of the invention, 0 26dry wt% of the silica/wollastonite mixture slurry is added to the mixing blunger.

ec C 5 Thereafter, a further step of the method is adding 14wt% of dry Morwell clay (carbonaceous ball clay grade) to the silica/wollastonite slurry mixture.

C Thereafter, a further step is adding 0.1% of soda ash solution (light soda ash Sgrade Na 2

CO

3 by way of incremental amounts using a special dosing pump.

SThereafter, a further step is adding 17-19wt% of Axedale clay (High plastic white fired ball clay).

SThereafter, a further step is adding approximately half of a mixture of 0.2wt% sodium silicate (grade vitrosol A60), Dolaflux (grade SP NEW) and Dispex (grade solutions. These chemicals were selected to provide the casting slip with a long term stability and consistency. Dispex N40 is a deflocculant and dispersant material based on is a lower molecular weight of sodium polyacrylate. Dispex N40 has 44 to 46% active sodium polyacrylate.

Dolaflux is a sodium humate base deflocculant that has the following composition; silicic acid H 2 SiO 3 disodium salt silicic acid H 6 Si20 7 hexasodium salt>10%and sodium hydroxide Thereafter, a further step of the present invention is adding 22wt% of Oakland clay (Low plasticity Kaolin grade The method of the present invention then comprises mixing the composition comprising the clays and other components mentioned above for approximately minutes or longer in order to enable a good balance of the desired particle size distribution in the final clay composition. The mixing is achieved by a high speed blunger.

Thereafter, calcined flint clay (grade 120 mesh) is then added to the composition from the high-speed blunger together with the remaining portion of the mixture of sodium silicate, Dolaflux and Dispex solutions. The resulting composition is then mixed for approximately another 45 minutes or longer to ensure proper control of the particle size distribution of the final mixture.

The resultant prepared slip composition is then aged for approximately 72 hours or longer. The aging of the slip composition is required to achieve the slip stability before casting into desired shapes.

IR \LBZZ]caronialispec do: AWL 22 O In the casting process, the slip slurry is poured into plaster moulds and 0 Ci allowed to cast for a specified time period. The casting time of the clay body of this Sexample is in the range of 55 to 65 minutes to achieve 12 mm thickness in the hollow cast 0 areas. The green ware is then removed from the moulds, dried over one night in the open CI 5 cast shop. Then the ware is completely dried in the chamber drier for 12 hours. Then two layers of engobe are applied onto the dried ware. Immediately 4 layers of first fire glaze N are applied on the top of the engobe. The spayed ware is placed onto the kiln car and fired O at 1195° C for 15 hours.

00 The resulting fire clay ceramic clay body comprises: to 14wt% Morwell clay; o 17 wt% Axedale clay; 22 wt% Oakland clay; 26wt% silica/wollastonite; and 21 wt% calcined flint clay.

Is It should be noted that the main constituents of the fire clay body comprise Morwell clay, Axedale clay, Oakland clay, silica/wollastonite and calcined flint clay represent 100wt%. Sodium Silicate, Dispex, Dolaflux and soda ash deflocculants act as modifiers to the casting slip rheology and usually are not considered as main constituents.

They are present in addition in the fire clay body in the following amounts: 0.2wt% sodium silicate, Dispex and Dolaflux; and 0. wt% soda ash.

The preferable content of the body components are 52 to 75wt% SiO 2 16 to A1 2 0 3 1.5 tol0wt% CaO, 0.1 to 5wt% MgO, 0.1 to0.8wt% Na20 and 0.8 to 1.lwt% The ceramic body resulting from the method of the present invention achieved the following advantages: 1. Dunting (cooling cracks) tendency was reduced; 2. Excellent thermal shock resistance; 3. Improvement in the re-firing process; 4. Unfired and fired strength were increased by almost The differential moisture content between the hollow and solid section within the cast was reduced; and 6. Significant improvement of the glaze appearance.

[R-itUBZZ]aManT inlspccdoc AWL 23 0 Engobe composition CN Before glazing of the ceramic body of the present invention, an engobe )composition is applied to the surface of the ceramic body. The engobe composition is a 0 mixture of clays, fluxes, silica zirconium silicate and wollastonite which is applied on the cn C s fire clay body to form a homogenous thin coating, usually applied to smoothly cover all surface defects. It should be noted that the engobe composition of the present invention should not be restricted to the clay bodies described in the present invention but can be Sused on any suitable clay surface or other substrate. The engobe composition of the present invention is as follows: O 0 o 16wt% Sanblend 75 clay (or other carbonaceous clay) Remblend clay (or other pure kaolin which fires white at high casting rate) 6wt% wollastonite zirconium silicate 30wt% silica flour 4wt% spodumene or petalite; 19wt% nepheline syenite, potash feldspars and soda feldspars.

In the above example, Sanblend 75 clay in another example can be substituted by any other carbonaceous clay that has high dry and fired strength. The Remblend clay in another example can be substituted by any other pure kaolin that fires white with a high casting rate. In another example, spodumene can be substituted by Petalite minerals. In another example, nepheline syenite can be replaced by a mixture of potash and soda feldspars.

Process of production of Engobe Composition The engobe composition is prepared by milling the components: o Sanblend 75 clay o Remblend clay o wollastonite o zirconium silicate o silica flour o spodumene; and o nepheline syenite; in a 1500 kg capacity ball mill as follows.

First preparation: a) Add 800 litres of water to the ball mill; (R:Ul BZZ]caronainulspec.dc:AWL 24 b) Add 450 kg silica flour (fineness 55% <10 microns); c) Add 150 kg zirconium silicate (fineness 90% <5 microns); d) Add 285 kg nepheline syenite (fineness 50% 10 microns); and e) Add 60 kg spodumene (fineness 55% 10 microns).

f) Add 90 kg wollastonite (120 mesh) Firstly grind the above components for 4.5 hours.

Second Preparation: In the same mill and after the 4.5 hours are completed, add the rest of the components as follows: Add 240 kg Sanblend 75 ball clay, and.

Add 225 kg Remblend kaolin.

Secondly, after the addition of the clays grind for extra 1.5 hours.

Engobe slurry must have a particle size distribution of up to 10 microns size in the range of 79 -86%.

The advantages of the Engobe composition of the present invention are as follows: 1. Improved thermal shock resistance of the fired ware.

2. Improved fired mechanical strength of the ware.

3. Reduced cooling cracks (dunt) faults.

4. Greatly improved glaze surface appearance.

Modifications and variations such as would be apparent to a skilled addressee are deemed to be within the scope of the present invention. It is to be understood that the invention should not be restricted to the particular embodiment(s) as described above.

(R'LUBZZci]anmafiapmx doC:AWL

Claims (18)

1. 3. A method according to claim 1 or 2, wherein the silica is selected from the group consisting of silica sand, silica flour, quartz and flint.
2. 4. A method according to any one of claims 1 to 3, wherein the silicate mineral is selected from the group consisting of calcium silicate, magnesium silicate, sodium titanium silicate, sodium aluminum silicate, sodium calcium silicate hydroxide, hydrated calcium silicate hydroxide, calcium iron silicate, magnesium iron silicate, calcium magnesium silicate and calcium aluminum silicate. A method according to any one of claims 1 to 4, wherein the silicate mineral is calcium silicate or wollastonite.
3. 6. A method according to any one of claims I to 5, wherein the silica is silica sand and the silicate mineral is wollastonite.
4. 7. A method according to any one of the preceding claims, wherein the silica and the silicate mineral blend is wet milled to a median particle size of from about 2 to about
5. 8. A method according to any one of the preceding claims, wherein the second clay composition comprises flint clay.
6. 9. A method according to any one of the preceding claims, further comprising IR: U ZZcronflnu1pec. doc:AWL 26 O adding a deflocculant selected from the group consisting of soda ash, 0 Cl sodium silicate, sodium polyacrylate, sodium humate and mixtures thereof 0) 0 10. A method according to claim 8, wherein the flint clay is calcined flint clay. C(
7. 11. A ceramic material produced by the method of any one of claims 1 to In N 12. A ceramic material comprising: 00 Se) at least one first clay; n 10 f) a second clay comprising a fire clay; Sg) silica; and h) wollastonite.
8. 13. An engobe clay composition comprising: Is a) one or more clays; b) a silicate mineral; c) optionally, an opacifier; d) silica; and e) one or more fluxes.
9. 14. An engobe clay composition according to claim 13, further comprising a lithium containing mineral. An engobe clay composition according to claim 14, wherein the lithium containing mineral is selected from the group consisting of spodumene, petalite, lepidolite and mixtures thereof.
10. 16. An engobe clay composition according to claim 13, wherein the at least one clay is selected from the group consisting of Sanblend clay and Remblend clay.
11. 17. An engobe clay composition according to any one of claims 13 to 16, wherein the opacifier is selected from the group consisting of zirconium silicate, tin oxide, titanium dioxide, zinc borate, zirconium oxide, zinc oxide, rutile, cassiterite and mixtures thereof. [RALI BZZlcarmulralspc dc:AWL O 18. An engobe clay composition according to any one of claims 13 to 17 0 C wherein the silicate mineral is wollastonite. C) 0 19. An engobe clay composition according to any one of claims 13 to 18 wherein the C 5 one or more fluxes is selected from the group consisting of nepheline syenite, potash feldspars, soda feldspars, rhyolite minerals and mesolite. In O 20. An engobe clay composition according to claim 13, wherein the silica is selected 00 from the group consisting of silica, silica flour or silica quartz and mixtures S 10 thereof.
12. 21. An engobe composition according to claim 13, comprising: a) 5 to 30wt% carbonaceous clay; b) 5 to 30wt% white ball clay; c) 5 to 20wt% of an opacifier; d) 0.5 to 10wt% wollastonite; e) 5 to 50wt% silica flour; f) 0.1 to 15wt% spodumene; and g) 5 to 30wt% nepheline syenite.
13. 22. An engobe composition according to claim 13, comprising: a) 10 to 20wt% Sanblend clay; b) 10 to 20wt% Remblend clay; c) 0.5 to 10wt% wollastonite; d) 5 to 10wt% zirconium silicate; e) 20 to 40wt% silica flour; f) 0.1 to 5wt% spodumene; and g) 10 to 20wt% nepheline syenite.
14. 23. A ceramic material of claim 12 comprising one ore more layers of the engobe composition of any one of claims 13 to 22.
15. 24. A method for producing an engobe composition comprising: d) adding water and silica to a mill; [R:VLIBZZZIc mafinalspec doc:AWL O e) adding optionally an opacifier, one or more 0 CI fluxes and a silicate mineral to at least one clay; and f) grinding the components in a) and b) to a suitable median particle size. Ci 5 25. A method according to claim 24, wherein the median particle size is below microns. C 26. A method according to claim 24, wherein a lithium-containing mineral is added Sin step b). 00oO
16. 27. A method of manufacturing sanitary ware comprising S 10o a) mixing a first composition comprising: O i) a silica/ wollastonite slurry mixture having a median particle size of from 0.5 to about 10 microns; with ii) a first clay and a second clay; b) mixing the first clay in step a) with a fire clay; c) shaping the resulting composition; drying and firing the composition.
17. 28. A method according to claim 27, wherein a deflocculant selected from the group consisting of sodium silicate, Dolaflux and Dispex solutions and mixtures thereof is added to the first clay composition.
18. 29. Sanitary ware produced by the method of claim 27 or 28. Dated 23 December, 2005 Caroma Industries Limited Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON [RALIBZZ]carofmfinalspec do:AWL