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GB2270082A - Stains for decorating ceramics - Google Patents

Stains for decorating ceramics Download PDF

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Publication number
GB2270082A
GB2270082A GB9316798A GB9316798A GB2270082A GB 2270082 A GB2270082 A GB 2270082A GB 9316798 A GB9316798 A GB 9316798A GB 9316798 A GB9316798 A GB 9316798A GB 2270082 A GB2270082 A GB 2270082A
Authority
GB
United Kingdom
Prior art keywords
stain
item
sol
high temperature
firing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB9316798A
Other versions
GB9316798D0 (en
GB2270082B (en
Inventor
Philip John White
John Doorbar
Alan Atkinson
David Leslie Segal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson H & R Tiles Ltd
Portmeirion Potteries Ltd
UK Atomic Energy Authority
Original Assignee
Johnson H & R Tiles Ltd
Portmeirion Potteries Ltd
UK Atomic Energy Authority
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson H & R Tiles Ltd, Portmeirion Potteries Ltd, UK Atomic Energy Authority filed Critical Johnson H & R Tiles Ltd
Publication of GB9316798D0 publication Critical patent/GB9316798D0/en
Publication of GB2270082A publication Critical patent/GB2270082A/en
Application granted granted Critical
Publication of GB2270082B publication Critical patent/GB2270082B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00—Compounds of chromium
    • C01G37/02—Oxides or hydrates thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Surface Treatment Of Glass (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Glass Compositions (AREA)

Abstract

A stain comprising a sol of a metal compound which when fired produces a solid decoration of a required colour, the required colour developing during firing. The sol may comprise colloidal dispersions of titania, chromia and zirconia. The high reactivity between the components of the sols permits lower firing temperatures and may remove the calcination step in stain preparation if the stains are to be applied to items as a liquid.

Description

High Temperature Stains This invention concerns improvements in or relating to: high temperature stains; a method of forming a high temperature stain; methods of decorating an item; and particularly but not exclusively high temperature stains for decorating ceramic items.
The term "high temperature stain" when used in this specification is to be understood as referring to a material which when fired produces a solid coloured decoration. This material can be used on its own or when mixed with other materials. Such materials can be used to decorate e.g. ceramic items, enamelled steelwork or glass.
The conventional process for production of ceramic stains involves solid-state reactions between powder mixtures, a process often referred to as 'calcining', that utilizes high temperatures. For example, temperatures greater than 1300do are required for colour development in the chrome-alumina system and with other systems temperatures of around 18000C may be required.
After calcining the ceramic stain is ground and washed to produce a powder having the final decorative colour with a particle size which is greater than 1 micron. Stain powders are conventionally applied to ware by various methods, for example, stain powder is combined with a glaze slop (the glaze being a combination of a fused fritted glass suspension combined with clay which functions as a viscosity modifier) and applied to ceramic tiles e.g. by silk-screen printing.
Alternatively, ceramic decals which have been made from ceramic stains may be applied to tableware or tiles. A characteristic of these conventional stains is that the pigment compound, a ceramic oxide or silicate, is formed by a high temperature reaction in a separate process before the decoration is applied to the ceramic body.
The term "sol" when used hereinafter is to be understood as defining a liquid in which colloidal submicron particles are dispersed, the particles having a dimension of between 1 and -1000nm. These particles typically aggregate to form a solid-like gel on partial drying.
According to the present invention there is provided a high temperature stain, the stain comprising a sol of a metal compound which when fired produces a solid decoration of a required colour, the required colour developing during firing.
The metal of the compound is preferably trivalent or tetravalent.
The stain preferably comprises a mixture of sols of different metal compounds.
The or each sol may have been dried such that the stain is in the form of a gel.
The stain may comprise a flux and/or a modifier, and the flux and/or modifier may also be in the form of a sol.
The sol medium is preferably water.
Also according to the present invention there is provided a method of forming a high temperature stain, the method comprising mixing together a plurality of sols of different metal compounds to provide a mixture which when fired produces a solid decoration of a required colour, the required colour developing during firing.
The sol mixture may be dried to form a gel prior to firing.
A flux and/or modifier may be added to the sol mixture, and the flux and/or modifier may also be in the form of a sol.
The invention further provides a method of decorating an item, the method comprising applying onto the item a high temperature stain according to any of the preceding paragraphs or a high temperature stain made by a method according to any of the preceding paragraphs.
The stain may be dried prior to application onto the item, and applied as a gel powder, or a partially calcined gel powder.
A glaze may be mixed with the stain prior to application onto the item.
Still further according to the present invention there is provided a method of decorating an item, the method comprising applying a high temperature stain according to any of the preceding paragraphs onto the item and firing the item such that a solid decoration of a required colour is formed thereon, the required colour developing during firing.
The high temperature stain may be applied as a liquid by any of screen printing, ink jet printing, spraying or brushing.
Alternatively, a decal may be formed bearing the high temperature stain, the decal being subsequently applied to the item and fired. The stain on the decal may be dried into the form of a gel.
The stain may be applied to the decal by screen printing or ink jet printing.
The item may be decorated by trichromatic printing using variable proportions of stains which produce suitable component colours upon firing for trichromatic printing.
Glaze may be mixed with the stain prior to application onto the item to be decorated.
Embodiments of high temperature stains according to the present invention and methods of making such stains and applying them to items will now be described by way of example only.
EXAMPLE 1 117.09 of strontium acetate (Merck Ltd.) were dissolved in water and the solution added to a titania sol made by dispersing 43.59 of a flame-hydrolysed titania powder (Degussa) in water. The doped-sol contained 1349 dm 3 of total oxide and had the oxide composition of strontium titanate. Chromia sol made by deanionisation of chromic nitrate solution with the amine Primene JMT as described in U.K. Patent Application No. 2059933A was added to an aliquot of the doped-titania sol containing 109 of oxide so that the w chromia content in the sol was 5 /o (that is 0.59 of Cr203 for 109 of SrTiO3). The resulting sol was painted onto biscuit tiles that were fired at 8000C whereupon a pale lemon colour on the tile resulted.
EXAMPLE 2 Example 1 was repeated except that cobalt nitrate was added to the strontium acetate-doped titania sol instead of chromia sol; the cobalt oxide concentration in the sol was 5W/o. The resulting sol was painted onto biscuit tiles which exhibited a grey-blue colour after firing at 800 C.
EXAMPLE 3 A zirconia sol containing 5009 dim 3 of oxide was prepared by addition of zirconium carbonate (Magnesium Elektron) to nitric acid as described in U.K. Patent No.
1181794. 131.79 of calcium nitrate (Johnson Matthey) were dissolved in water and added to 137.4 cm3 of the zirconia sol so that the doped sol had a calcium zirconate composition and total oxide concentration of 1549 dm 3. An aliquot of doped-sol containing 109 of oxide was added to chromia sol whose preparation is described in U.K. Patent Application No. 2059933A to w give a chromia content of 5 /o. Sol was painted onto biscuit that exhibited a yellow-green colour after calcination at 800or.
EXAMPLE 4 Example 3 was repeated except that nickel chloride addition was substituted for the chromia sol. The nickel chloride-doped sol was painted onto biscuit tile that exhibited a pale pink colour after firing at 800 C.
EXAMPLE 5 An alumina sol was prepaced by dispersing a flame-hydrolysed alumina powder (Degussa) in water and doped with a nickel chloride solution so that the oxide composition in the sol was (NiO)o 25Al203; the oxide concentration was typically 2009 dim 3. The doped sol was painted onto two wall tile biscuits.
Tiles were oven-dried and one of them sprayed over with a commercial transparent glaze. Both tiles were fired in an industrial glost tunnel kiln. The biscuit tile was blue after firing as was the colour under the glaze of the other tile.
EXAMPLE 6 The doped sol described in Example 5 was painted onto:- (i) unglazed floor tile, (ii) glazed floor tile, and (iii) fully vitrified floor tile.
The glazed and unglazed floor tiles were fired through a production roller kiln with a peak temperature of 11600C and cycle of 60 minutes. The fully vitrified floor tile was fired through a production kiln with a peak temperature of 1200do and cycle of 66 minutes. The glazed floor tile and fully vitrified floor tile were blue after their respective heàt treatments, while the unglazed floor tile was yellow-grey in colour.
EXAMPLE 7 13.79 of zinc nitrate (Fluka) and 4.879 of chromic nitrate were dissolved in 13.0 cm3 of aluminium chlorohydrate (Albright and Wilson, 3139 dm 3 Awl203). 0.359 of boric acid (Unichem) dissolved in 3 30 cm of H20 were added to form a doped sol with a total oxide concentration of 2009 dim 3 and composition 40.48W/o Al203; 3.5woo B203; 37.45woo ZnO; 18.57W/o Cr203. The doped sol was painted onto biscuit ware which was heated in an electric enamel kiln. A bright pink decoration was obtained at 10200C.
EXAMPLE 8 The doped-sol described in Example 7 was painted onto biscuit ware which was heated in a gas-fired glost kiln. An orange-pink decoration formed at 1080 C.
EXAMPLE 9 A concentrated solution of zinc and chromium nitrates was prepared and split into two solutions in the proportion 1/3 to 2/3 by volume. Hydroxides of the two metals were precipitatEd from the larger volume by stirring in 2M sodium hydroxide until the pH had risen to 7. The precipitate was washed by stirring with demineralised water, allowed to settle and supernatant liquid was then decanted. The process was repeated three times. The washed precipitate was peptised with the remaining nitrate solution by mixing and heating to 800C. The resulting sol had a nitrate/metal mole ratio of 0.55. Boric acid was added with additional water to give an oxide content of ca. 10 ó by weight and alumina.
was introduced by dispersing a flame-hydrolysed powder (Degussa) into the peptised sol. The resulting sol had an oxide composition of 40.48W/o Al203; 3.5 woo B203; 37.45W/o ZnO; 18.57W/o Cr203.
70 cm3 of the resulting sol were added to 284 cm3 of a conventional base glaze suspension and then applied to biscuit tile. A pink colour was observed in the glaze coating on firing at 10000C.
There is thus described a wide range of high temperature stains and methods of forming and applying same. Using sols provides for greater reaction between the different components due to the large particle surface areas provided by sols. This high reactivity generally permits lower firing temperatures to be used.
In the examples where the stains are applied to items as a liquid, the steps of calcination and subsequent grinding and washing are alleviated. It is to be realised that the above stains are described by way of example only and the present invention can be used with a large number of stains producing a wide range of colours.
It is to be realised that the stains described above may also be applied to an item by any of screen printing, ink jet printing or spraying. Alternatively, the stains may be dried, or partially calcined, to a gel prior to application. Also the stains may be provided on a decal which is applied to an item. The stain may be dried, or partially calcined on, or prior to application onto, the decal to form a sol gel. When applied to the decal as a liquid the stain may be applied by screen printing or ink jet printing. The item is subsequently fired during which the colour of the stain develops.
Stains according to the invention can be applied to glazed or unglazed ware. The stains can be applied under, over, or in glaze. Firing conditions, such as temperature and time, can obviously be chosen for particular conditions and applications. Modifiers and/or fluxes can be added to the stains to vary the colour intensity and finish of the final decoration.
Stains according to the present invention are particularly suited for use in trichromatic printing, preferably using ink jet printing. Stains which produce suitable colours can be made along with a black. Again the colours will only fully develop after firing.

Claims (34)

Claims:
1. A high temperature stain, the stain comprising a sol of a metal compound which when fired produces a solid decoration of a required colour, the required colour developing during firing.
2. A stain according to claim 1, in which the metal of the compound is trivalent.
3. A stain according to claim 1, in which the metal of the compound is tetravalent.
4. A stain according to any of the preceding claims, in which the stain comprises a mixture of sols of different metal compounds.
5. A stain according to any' of the preceding claims, in which the or each sol has been dried such that the stain is in the form of a gel.
6. A stain according to any of the preceding claims, in which the stain comprises a flux.
7. A stain according to claim 6, in which the flux is in the form of a sol.
8. A stain according to any of the preceding claims, in which the stain comprises a modifier.
9. A stain according to claim 8, in which the modifier is in the form of a sol.
10. A stain according to any of the preceding claims, in which the sol medium is water.
11. A method of forming a high temperature stain, the method comprising mixing together a plurality of sols of different metal compounds to provide a mixture which when fired produces a solid decoration of a required colour, the required colour developing during firing.
12. A method according to claim 11, in which the sol mixture is dried to form a gel prior to firing.
13. A method according to claims 11 or 12, in which a flux is added to the sol mixture.
14. A method according to claim 13, in which the flux is in the form of a sol.
15. A method according to any of claims 11 to 14, in which a modifier is added to the sol mixture.
16. A method according to claim 15, in which the modifier is in the form of a sol.
17. A method of decorating an item, the method comprising applying onto the item a high temperature stain according to any of claims 1 to 10.
18. A method of decorating an item, the method comprising applying onto the item a high temperature stain made by a method according to any of claims 11 to 16.
19. A method of decorating an item, the method comprising applying a high temperature stain according to any of claims 1 to 10 onto the item and firing the item such that a solid decoration of a required colour is formed thereon, the required colour developing during firing.
20. A method of decorating an item, the method comprising applying a high temperature stain made by a method according to any of claims 11 to 16 onto the item and firing the item such that a solid decoration of a required colour is formed thereon, the required colour developing during firing.
21. A method according to any of claims 17 to 20, in. which the stain is dried prior to application onto the item.
22. A method according to claim 21, in which the stain is applied as a gel powder.
23. A method according to claim 21, in which the stain is applied as a partially calcined gel powder.
24. A method according to any of claims 17 to 23, in which a glaze is mixed with the stain prior to application onto the item.
25. A method according to any of claims 17 to 24, in which the high temperature stain is applied as a liquid by any of screen printing, ink jet printing, spraying or brushing.
26. A method according to any of claims 17 to 24, in which a decal is formed bearing the high temperature stain, the decal being subsequently applied to the item and fired.
27. A method according to claim 26, in which the stain on the decal is dried into the form of a gel.
28. A method according to claims 26 or 27, in which the stain is applied to the decal by screen printing or ink jet printing.
29. A method according to any of claims 17 to 24, in which the item is decorated by trichromatic printing using variable proportions of stains which produce suit able component colours upon firing for trichromatic printing.
30. A method according to any of claims 17 to 29, in which glaze is mixed with the stain prior to application onto the item to be decorated.
31. A high temperature stain substantially as hereinbefore described.
32. A method of forming a high temperature stain substantially as hereinbefore 'lescribed.
33. A method of decorating an item substantially as hereinbefore described.
34. Any novel subject matter or combination including novel subject matter disclosed in the foregoing specification or claims and/or shown in the drawings, whether or not within the scope of or relating to the same invention as any of the preceding claims.
GB9316798A 1992-08-13 1993-08-12 High temperature metal sol stains with colour development upon firing Expired - Fee Related GB2270082B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB929217204A GB9217204D0 (en) 1992-08-13 1992-08-13 High temperature stains

Publications (3)

Publication Number Publication Date
GB9316798D0 GB9316798D0 (en) 1993-09-29
GB2270082A true GB2270082A (en) 1994-03-02
GB2270082B GB2270082B (en) 1996-08-07

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GB929217204A Pending GB9217204D0 (en) 1992-08-13 1992-08-13 High temperature stains
GB9316798A Expired - Fee Related GB2270082B (en) 1992-08-13 1993-08-12 High temperature metal sol stains with colour development upon firing

Family Applications Before (1)

Application Number Title Priority Date Filing Date
GB929217204A Pending GB9217204D0 (en) 1992-08-13 1992-08-13 High temperature stains

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4047970A (en) * 1975-01-27 1977-09-13 Keeling And Walker, Limited Production of calcined ceramic pigments
GB2011366A (en) * 1977-11-01 1979-07-11 Atomic Energy Authority Uk Materials Containing Zirconium, Silicon and Oxygen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4047970A (en) * 1975-01-27 1977-09-13 Keeling And Walker, Limited Production of calcined ceramic pigments
GB2011366A (en) * 1977-11-01 1979-07-11 Atomic Energy Authority Uk Materials Containing Zirconium, Silicon and Oxygen

Also Published As

Publication number Publication date
GB9316798D0 (en) 1993-09-29
GB9217204D0 (en) 1992-09-23
GB2270082B (en) 1996-08-07

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Legal Events

Date Code Title Description
732E Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977)
PCNP Patent ceased through non-payment of renewal fee

Effective date: 19990812