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USO05614448A
United States Patent 1191

1111 Patent Number:

Kreiner

[45]

Date of Patent:

5,614,448
Mar. 25, 1997

[54]

METHOD FOR THE MANUFACTURE OF
PORCELAIN

2,776,899
2,898,217

1/1957 Donahey ............................... .. 501/144
8/1959 Selsing ..
501/144

[75]

Inventor;

3,431,126
3,501,321
3,674,519

3/1969 Fukui
3/1970 Margola ...... ..
7/1972 1-I1guch1 6131,

[73]

Ass1gnee. Rosenthal Aktlengesellschaft, Germany

[211

-

.

-

Appl- N914101871
.

[22]

Roswitha Kreiner, 561b, Germany

3,846,098

3,8918 4 1

'

_

Flled-

Mar-27,1995
_

_

Related 145- APPllcatlon Data

[62]

11/1974

Nakashima 61111..

7/1975 Nijhawan et a1.

4,183,760

1/1980 Funk eta].

501/144

4,219,360

8/1980 Thompson

501/142

4,337,317

6/1982 Beard ...... ..

501/142

6/1989

501/143

4,983,556

1/1991 Seike et 11, ........................... .. 501/143

Oda ..... ..

Prim’? Examiner—Mark L- B611

Int C16

[58]

501,70; Sol/141; Sol/142; Sol/143; 501,144
Field Of Search .............................. .. 501/5, 141, 142,

[56]
2,635,058

,

C04B 33/24

. ........... .. 501132; 501/5; 501/63;

501/144

4,843,047

Assistant Examiner—Michael Marcheschi

US. Cl.

501,123

1/1979 IChikO 61111. ..

Division of Ser. N0. 157,634, Nov. 24, 1993, Pat. N0.

[52]

501/144

4,134,772

5,455,210.
[51]

501/143
501/144
501/143

Attorney, Agent, or Firm—Jones & Askew
[57]

ABSTRACT

The invention relates to a porcelain with a transparency and
strength properties of a hard porcelain, characterized by a

501/ 143’ 144’ 321 63’ 70

phosphate-containing glass phase as well as the predomi

,

nance of unreacted quartz bodies [sic; grains] in the matrix.

"

References Clted

The invention relates to a porcelain batch composition as

Us‘ PATENT DOCUMENTS

well as to a method for the manufacture of the porcelain.

4/1953 Wooldridge ........................... .. 501/144

9 Claims, 4 Drawing Sheets

614. 25.448 . 1997 Sheet 1 0f 4 5.US. Patent Mar.

448 . 1997 Sheet 2 of 4 v 5. 25.614.US. Patent Mar.

614. 1997 Sheet 3 0f 4 5. 25.448 .US. Patent Mar.

614.448 . 1997 Sheet 4 of 4 5. Patent Mar. 25.US.

it is characterized by a high mechanical strength. 1993. a porcelain batch composition and a method for the manufacture of the porcelain. 3 is a photograph of hard porcelain. pages 228-231). The hard porcelain is ?red primarily with oxidation at 20°-900° C. an increase in the 25 quartz portion can lead to an increase in mechanical compositions. Pat. . mica and a small Bone porcelains (bone china) are characterized by a high The invention relates to a porcelain. vitreous porcelain and bone porcelain. possibly. One advantage resulting from the lower ?ring temperatures is FIG.4 g/cm3 Pressure resistance irregular 450-550 MPa Impact bending resistance irregular 23 MPa . Primary components: mullitc quartz cristobalite traditional principle to change nothing or make only insig ni?cantly small changes to the operating conditions. quartz and glass phase.5.. Currently three tableware porcelain types are distin guished in Germany: hard porcelain. such as particular feldspar sands. FIG. For example attempts have been made and mixed with water. A minor omission or change in the selected batch compo sitions and/or a change in the particular ?ring conditions as a rule results in unusable products. particularly a table ware porcelain. of application Ser. ?led on Nov..3 wt. The 35 40 The following property values are required for hard known ‘batch composition has. The ?red body of hard porcelain. the transparency decreases. As a rule the batch composition consists of 20-45% bone ash.614. A decrease in the quartz portion results in an improve ment in resistance to temperature changes. 5. transparency. For this reason it is a porcelain: Water uptake 0 Raw density 2.210. Bone ash is prepared from defatted leached bones by calcining with addition of air. a broader range of colors for decorations or glazings is available. with oxidation at 900°-1000° C. by sharp ?ring.3-2. The composition for the manufacture of bone porcelain is di?icult to process particularly because of the low kaolin portion and it is more di?icult to ?re than other porcelain acts as a ?ux and it is usually used in the form of a potassium feldspar or as a potassium-sodium feldspar. FIG. Cornish stone is a partially kolin ized potassium and sodium feldspar-containing stone which contains besides feldspar quartz. a high degree of white ness and good mechanical strength. 08/157.5 x 10'6 K-1 Transparency with d = 1 mm 2-l0% Resistance to temperature change >165 K. 1 is a photograph of a disclosed embodiment of porcelain made in accordance with the present invention. (Silikattechnik 39 (1988).634.448 1 2 METHOD FOR THE MANUFACTURE OF PORCELAIN that. Accordingly. The problem is solved by the use of a batch composition with the following chemical composition: 18-27 wt. % SiO2 0.5% 2 i 0. and with have an effect on quartz dissolution. No.1-0. 55 FIG. but here too the batch compositions have been de?ned with narrow ranges and lead to certain properties of the products. good thermal and electrical properties and sui?cient resis 20 tance to corrosion.455. where the sharp ?re temperature is still relatively high at 13500 or 1380° C. such as ZnO and chalk reduction at 1000°-1450° C. The problem of the invention is to formulate a manufac turing process to produce a porcelain which has the prop erties of a hard porcelain but is more economical and tolerates greater variations of the ?ring conditions while 60 maintaining the relatively simple manufacturing technology and the usual ?ring equipment. in an oxidizing atmosphere. now US.5% Vitreous porcelain diifers from hard porcelain in its higher feldspar and quartz portions as well as. No. The ?ring occurs in an oxidizing atmosphere at 1200°-l300° C. resulting in lower ?ring tempera tures. The ?ring for glazing is conducted at l000°-l140° C. kaolin. which is ?red at 1350°-1450° C.) Degree of whiteness irregular 40-70 MPa 4. This is a division. No. exhibits a high transparency and a high degree of whiteness. The shaping step is followed by strength. Hard porcelain as a rule is made from a batch composi tion consisting of 50% clay material. attempts have been made to change the batch composition so that lower ?re sharp ?re temperatures can be used while still ture of hard porcelain. in comparison to hard porcelain. 2 is a photograph of vitreous porcelain. % A1203 50-65 wt.. In principle the clay material used is a light-burning ?ring kaolin. which consists essen tially of secondary mullite. Fur thermore. white-burning clays in the batch composition. the raw materials are ?nely divided 30 guaranteeing that the values of the properties of hard por celain are obtained. During the cooling the atmosphere is neutral or oxidizing. 4 is a photograph of bone china. If the kaolin portion is increased to the detriment of the quartz. It contains as essential mineral phase calcium phosphate. a creamy white color. 25% feldspar and 25% quartz. Deformations during ?ring are minimal. 20-45% comish stone and 20-35% kaolin. and the ?rst ?ring step is the glazing.. Vitreous porcelains are ?red primarily with oxi dation and as a result they often are the color of ivory. The highly transparent body of bone porcelain is however relatively brittle. The relatively low ?ring temperature results in glazings which are softer and less scratch resistant than the conventional porcelain glaz ings. The glazing is applied to the raw body to improve the sintering properties using mineralizers which or to a body which has been spoiled by too high annealing temperatures at 900°-1100° C.m Bending resistance irregular Average linear heat expansion coe?icient (20-500° C. been designed especially for raw materials which occur only regionally. During the ?ring the composition exhibits a very good preservation of shape. 7. In other countries. >70% 45 BRIEF DESCRIPTION OF THE DRAWING 50 glass phase 64-65% 27 i 1% 7 i 0. As a result. porcelains are classi?ed differently. however. The glaze is applied to the densely ?red body. 24. Because of the batch composition deformations occur relatively frequently during ?ring. Most of the high manufacturing costs of hard porcelain are the result of the sharp ?re temperatures. For the preparation of the composition for the manufac drying and glazing. Feldspar quantity of ?uorspar. in that it has a certain content of fatty. where the sharp ?re takes place in a reducing atmosphere. % Fe2O3 . the values of the properties of vitreous porcelain do not correspond to the high standard of hard porcelain.

5. with either oxidation or 65 reduction. mullite. The matrix of the porcelain according to the invention been regulated. and Water is admixed with the batch composition so that a whether there is any residual quartz at all. glass phase.1 wt. The product exhibits a high transparency. The composition presents only small deformation dur ing ?ring. The phases of bone china the compositions. A glass phase surrounds all of this. is a low—[temperature]~?red transparent porcelain with the mechanical properties of hard porcelain and a ?ring color which depends on the oven atmosphere which [color] has with only a few quartz particles which have not reacted completely because of their size. The ?red product 35 consist of anorthite. % Na2O 2.0 wt. % TiO2 tance. span of ?ring adjuvants. The matrix of hard porcelain (FIG.0 <2. The batch composition is suited for an oxidizing or a reducing ?ring atmosphere. The residual quartz portion. spe transparency. 2. the The matrix of vitreous porcelain (FIG. 10 composition. A body with low deformation during ?ring makes it possible to use. can be ?red either by rapid ?ring or by normal ?ring. as with hard porcelain. calcium orthophosphate and quartz. lain. Furthermore it is known that the melting process can be in?uenced. It is essential that as a function of the oven 6.00 <20. feldspar. This results in great advantages for design and production. % P20S Raw materials of high purity with a FezO3 and a TiO2 Ur content of less than 0. % MgO 0. impact resis ci?cally with colors ranging from a creamy white in an . selected advantageously as follows: pm prn prn pm pm pm pm 95~l00 wt % 82-97 wt % 67-80 wt % 50-65 wt % 36~55 wt % 24-35 wt % 15-25 wt % The purpose here was to be able to use the manufacturing 15 The particle size distribution of quartz should be as follows: <40.5 <l. suitability for microwave ovens. By means of appropriately regulated oven atmospheres it is possible to obtain intermediate white tints. a broad ?ring spectrum can be used. calcium orthophosphate and quartz..3 wt. The new composition has a carefully deter mined portion of flux. appearances which have never been obtained before. primary mullite is present which is formed from feldspar and kaolin.0 <l0.4 wt. glass and pores. hardness. 4) consists of anorthite. could be reached by a rational change of the ' The particle size distribution of the batch compositions is <40 <20 <10 <5 <2. Low ?ring temperature: This results in an economic advantage which permits a considerable energy saving and which multiplies the life size. However. 5. % are used for the batch composition which is made up of clay material. there is an increase in vitri?cation and thus in transparency so that it is possible to lower the ?ring temperature. mullite. depends on the processable composition is formed. quartz and bone ash. acid resistance. 3. The matrix structure of the body of the low-[temperature] ?red porcelain according to the invention is clearly distin guishable from that of hard porcelain and that of bone china. The invention thus contains a selected batch composition which.6—4. O. 3) consists of residual quartz. As a rule the phases of hard porcelain consist of 30 primary and secondary mullite. quartz and plastic raw materials. at relatively low temperatures. The values of the physical and chemical properties of atmosphere the color of the body can be in?uenced. for example. 1) consists of quartz. The conversion of primary mullite to secondary mullite is also in?uenced by the ?ring curve.0 wt.0 <0.0 <5. and there is also tricalcium phosphate and anorthite.5—6. bending-rupture resistance. In an oxidizing atmosphere one obtains a creamy white [color] corresponding to bone china and in a 40 (FIG.5 With the new batch composition an alternate product for either hard porcelain or bone china is created. and not to have to use the expensive and complicated manufacturing method of bone china.614. with only a few quartz particles which have not completely reacted because of their the following advantages: 1. and then dried and ?red.448 4 0. 2) consists of quartz. anorthite. The composition is suited for rapid ?ring (4—6 h) and normal ?ring (l0—l8 h). glass and reducing atmosphere the gray-speckled white hard porce pores. The batch composition according to the invention permits The matrix of bone china (FIG. 50 It is known that as the granular ?neness of the quartz and of the feldspar increases. to achieve approxi 55 mately the same melt phase portion in the body with rapid ?ring compositions as with normal ?ring compositions.5 <1 <0. remaining properties of the low-[temperaturel-?red porce lain in all cases correspond to those of hard porcelain.02-0. to prevent a strong deformation during ?ring.5-2. and it is responsible for the high transparency of the body and contains an enriched content of P205. The advantage of this product is that depending on the atmosphere the white color can be in?uenced and thus it is possible to produce 25 technologies which are conventionally used for hard porce lain. 4. the considerably less complicated glazing application onto the absorbing body. The ?ring occurs at a temperature between 1120°-l220° C. freedom from heavy metal [content] correspond to the properties of hard porcelain ?red at 1400° C. for example. Objects are formed from ?ring temperature and the time in the sharp ?re. and residual quartz in various ratios. washing-machine 5—8 wt. % K20 3. An important prereq uisite here is a good stability under load of the composition during ?ring. % CaO resistance.5 pm pm pm pm pm prn pm 88-100 wt % 55-86 wt % 30-55 wt % l8—30 wt % 8-15 wt % 3~9 wt % 1-6 wt % The targeted decrease in the ?ring temperature to 1200° C.l5—0. and use with oxidizing or reducing atmosphere is possible.0 wt. 60 In comparison the invention has taken another route and surprisingly it has attained a transparency and strength levels corresponding to those of nonnal hard porcelain with a relatively low quartz dissolution and a relatively low melt portion . glass and pores. mullite. Besides the completely unrcacted quartz.

l5-0. matt glazings. 8.1-0. preparing a porcelain batch composition from raw mate rials. glass 25 phase.0 wt. % P205. % FeZO3 0. said batch composition consisting essentially oft’ l8—29 wt. % A1203 50-65 wt. 6.5.02-0. Method according to claim 3. Furthermore. % K20 3.0 wt. the basic compo <40 <20 <10 <5 <2.0 <2.6-4. wherein the ?ring is conducted in an oxidizing atmosphere thereby producing a 5-8 wt.0 um <l0.4 wt. % SiO2 0.5 <1 <O. ?ring. .0 <0. transparent.l wt.5 pm um pm um 88-100 wr % 55-86 wt % 30-55 wt % 18-30 wt % 8-15 wt % 3-9 wt % l-6 wt %. covering. wherein the quartz in the batch composition has the following particle size distribu tion: known ?ring equipment..00 pm <20.5 sition can be covered to produce a white or colored cover with all the glazing variants conventionally used in ceram ics.5-2. % MgO 0. and all intermediate colors can be produced depending on the oven atmosphere used during the 3.3 wt. wherein the batch com position comprises clay material. wherein the ?ring takes from 10-18 hours in a conventional normal ?ring process. distribution of the raw materials of the batch composition is as follows: The composition can be colored by the addition of dissolved or pigment-like color additives and in that case the result is a colored transparent body.448 5 6 oxidizing atmosphere to a blue-gray speckled white in a reducing atmosphere. Method according to claim 1. feldspar.3 wt. wherein the particle size The relatively low ?ring temperature and the possibility of selecting the atmosphere also provide the possibility to extend the glazing palette of usable glazings considerably. Method according to claim 1.0 pm optimal.614. 9.5-6. % CaO 0. 7. wherein the sum of Fe2O3 and TiO2 in the batch composition is less than 0.0 wt. % TiO2 30 gray-specked white porcelain. crystal sepa rating.5 <1. for example. quartz and bone ash. wherein the ?ring takes from 4-6 hours in a conventional rapid ?ring process. quartz grains and pores comprising the steps of: <5. where the stability under load of the shaped body during the entire temperature treatment is <40. 4. Method according to claim 1. Method according to claim 1. opaque. It is surprising that in spite of the batch composition which is different compared to conventional porcelain and in spite of the resulting different matrix structure of the por celain according to the invention a very broad ?ring range is available and the ?ring can be conducted simply and with 5. wherein the ?ring is conducted in a reducing atmosphere thereby producing a 35 cream colored porcelain. Method according to claim 1. urn um um urn pm pm pm 95-100 wt ‘70 82-97 wt % 67-80 wt % 50-65 wt % 36-55 wt % 24-35 wt % 15-25 wt %. Method according to claim 1. Method according to claim 1. I claim: 1. and ?ring the batch composition 2. % Na2O 2.A method for the manufacture of porcelain having a porcelain matrix consisting essentially of mullite. %.

Signed and Sealed this Twenty-fourth Day of June‘.448 DATED : March 25. delete "29" and insert therefor ——27——.UNITED STATES PATENT AND TRADEMARK OFFICE.614. CERTIFICATE OF CORRECTION PATENTNO. : 5. 1997 Attest: 6M 2 BRUCE LEHMAN Arresting O?icer Commissioner of Parents and Tradenmrkx . 1997 INVENTUMS) ': Roswitha Kreiner It is certi?ed that error appears in the above-identi?ed patent and that said Letters Patent is hereby mnectedasahom below: ' In column 5. line 29.