WO1995009131A1 - Cobalt glass compositions for coatings - Google Patents
Cobalt glass compositions for coatings Download PDFInfo
- Publication number
- WO1995009131A1 WO1995009131A1 PCT/GB1994/002105 GB9402105W WO9509131A1 WO 1995009131 A1 WO1995009131 A1 WO 1995009131A1 GB 9402105 W GB9402105 W GB 9402105W WO 9509131 A1 WO9509131 A1 WO 9509131A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass composition
- composition
- glass
- zno
- coo
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
Definitions
- the present invention relates to glass
- a coloured glass to be used for on-glaze enamel decoration must simultaneously satisfy a number of key requirements.
- the softening point of the glass should be such as to allow maturation within the temperature range of from 750° to
- the coloured glass should be compatible with a wide variety of glazes.
- the coloured glass should display good resistance to pronounced opacity or mattness during a conventional enamel firing schedule in order to promote good colour development with a glossy finish.
- the linear coefficient of thermal expansion (CTE) of the coloured glass should be compatible, or made compatible through additions of filler materials, with that of the glaze coated thereon to prevent crazing and/or spalling.
- the durability of the coloured glass should be such as to enable the fired colours to withstand attack by acidic foodstuffs and alkali detergents. With controls on permissable levels of metal release into acidic and alkali solutions becoming more stringent, more exacting demands are being placed on the durability requirements of decorated pieces.
- the present invention provides a glass composition which is essentially free from lead and cadmium and which comprises the following
- TiO 2 0-1 optionally one or more of SnO 2 , WO 3 , MoO 3 or
- 0-5 optionally one or more of Y 2 O 3 , La 2 O 3 or
- the glass of the present invention relies on the presence of Co 2+ i.n the glass network to provide a blue colour.
- the glasses of the present invention may be non-crystallizing or "stable". However, the intensity of the blue colour of the glass may be further increased by altering the glass chemistry to promote precipitation of the (Co,Zn) 2 SiO 4 phase either during enamel firing or by a prior thermal treatment of the glass.
- a nucleating agent such as ZrO 2 , P 2 O 5 or other agents known to those
- ZnO is preferably included in an amount of from 1 to 5 wt%, more preferably 1 to 3 wt% , and the preferred range for CoO is 10 to 20 wt%, more preferably 10 to 15 wt%.
- the preferred range for CoO is 10 to 20 wt%, more preferably 10 to 15 wt%.
- ZnO is 5 to 15 wt%, more preferably 7 to 12 wt%
- CoO is 5 to 15 wt%, more preferably 5 to 12 wt%.
- the presence of Bi 2 O 3 is generally required in order to provide a glossy fired appearance.
- the preferred range is 5-25 wt%., the more preferred range is 3-15 wt%.
- composition of the present invention contains ZrO 2 in order to improve the resistance of the composition of the present invention
- compositions to attack by alkali detergent solutions compositions to attack by alkali detergent solutions.
- the glasses of the invention can be prepared from natural (benificated) rocks and minerals e.g.
- inventions are usually in the form of fine powders.
- Precursors of these oxides can also be useful,
- Suitable "fine chemical" precursors are the nitrites, nitrates, carbonates, metal organic salts, for example citrates, acetates, etc.
- the glass of the present invention may be any glass of the present invention.
- the frit may be ground into a powder by conventional grinding techniques.
- the glasses of the present invention are identical to The glasses of the present invention.
- fluxes which are used in combination with one or more pigments as a colour on ceramic substrates or glass.
- the glass compositions will melt at a temperature of below 1350 C, preferably at a temperature in the range of from 1150°C to 1300°C.
- the present invention thus includes within its scope a composition for the decoration of ceramic substrates and/or glasses which comprise a blue glass frit as hereinbefore described on its own or in admixture with one or more pigments, or other
- the compositon for the decoration of ceramic materials and/or glass may additionally contain a plastic binder therein.
- the glasses of the present invention may be made into decoration printing inks or pastes and applied to ceramic or glass substrates using standard
- decalomania transfers to the substrates.
- a dry powder of the glass is dispersed in an oil-, water-, solvent- or wax-based medium with the aid of shear mixers and triple roll mills.
- oil-based media are generally used, whilst for pad printing, wax-based inks are more commonly used because of their thermoplastic nature.
- the ink or paste is applied to the substrate by using a sharply-edged rubber squeegee to press the ink through the open areas of a fine mesh stretched on a frame.
- the mesh is generally no longer made of silk but is more commonly made of either metal or polyester.
- the substrate is positioned below the screen and as the two contact, the ink adheres in a precise pattern relating to the open area of the design of the screen. Precise control over the thickness of the ink or paste is achieved through adjustment of the ink or paste rheology, the diameter of the mesh filament or pores, the distance of the screen from the substrate and the pressure on the squeegee.
- Pad printing involves transferring an ink design from a metal or plastic engraved cliche (plate) or from a screen printed image (an image deposited on to a flat silicone plate), to a substrate by means, for example, of a pliable silicone pad.
- a cliche depending on the machine type the first step in the process involves pouring the ink into or directly on to the etched plate. The cliche is flooded with ink and then cleaned off with a doctor blade, leaving the ink only in the etched impression of the image. Using appropriate pressures and cycle times, the pad is pressed on to the etched portion of the plate, where it picks up the ink. The pad then rises up and travels laterally towards the substrate. It is lowered (with appropriate pressure and cycle time) on to the substrate to deposit the image. Pad printing has the advantage over
- the decoration or design containing the glass enamel is formed independent of the surface to be decorated, usually on a transfer paper or other carrier. Subsequently, as and when required, the decal is transferred on to the substrate surface.
- the organic components of the printing inks or pastes either evaporate or burn away during thermal fusion of the decoration to the substrate during the firing cycle.
- the glasses of the present invention are identical to The glasses of the present invention.
- the glasses of the present invention give good colour development, i.e. the fired colour is bright and "wet".
- filler material such as fused silica or /3-spodumene may be added to the glass such that the net thermal expansion of the fired mixture is similar to that of the tableware piece.
- the softening point (S.P.) of the glass should be in the region glass 450-600 C, while for enamel firing at 950°C, it may be as high as 700°C.
- the CTE's of the enamels should lie ideally in the range 7.0 - 9.5 X 10 - 6 /oC for use on bone china and in the range 4.5 - 5.6 X 10 - 6 /oC for use on porcelain.
- the thermal expansion mismatch with the substrate can be greater.
- the glass compositions of the present invention may also be used in vitreous enamel coating
- compositions for application to metallic substrates with the particular glass composition being chosen with a thermal expansion which is compatible with that of the metallic substrate.
- the crystallizing glasses may be thermally treated, for example, at a temperature in the range of from 750° to 950 C, and subsequently ground to the
- the particulate pigments may be dispersed in paints, polymers, ceramic bodies or glazes to provide colour in a manner analogous to conventional pigments, the particle size of the pigment being chosen having regard to the desired application.
- glass frits were prepared by fusing together raw materials of the listed oxides in the amounts as stated in parts by weight at 1200 C, and fritting the glasses
- the coarse frits were ground to give a particle size distribution of 90% less than 16
- the fired enamels were assessed in terms of colour development and acid and alkaline durability.
- the developed colour was assessed using an ICS
- the glasses of Examples 1 to 5 and 29 to 51 are stable glasses, whilst the glasses of Examples 6 to 28 are crystallizing glasses in which the blue colour is intensified by the formation of (Co,Zn) 2 SiO 4 crystallites during the enamel firing cycle.
- Examples 15 and 17 in powder form having a particle size of 90% less than 14 micrometres were heated separately at 13 C/minute to 850°C, held at this temperature for 10 minutes and cooled down to room temperature at 13°C/min. The resulting fused materials were pulverised and passed through a 100 micrometre sieve. The intensity of the blue colour was increased in each case by the thermal treatment, with X-ray diffraction analysis confirming the presence of (Co,Zn) 2 SiO 4 in each case.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU77036/94A AU7703694A (en) | 1993-09-28 | 1994-09-28 | Cobalt glass compositions for coatings |
DE69419928T DE69419928T2 (en) | 1993-09-28 | 1994-09-28 | COBALT GLASS COMPOSITIONS FOR COATINGS |
EP94927732A EP0721430B1 (en) | 1993-09-28 | 1994-09-28 | Cobalt glass compositions for coatings |
US08/619,558 US5747395A (en) | 1993-09-28 | 1994-09-28 | Cobalt glass compositions for coatings |
TW083109241A TW340834B (en) | 1994-09-28 | 1994-10-05 | Cobalt glass compositions for coatings |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB939319971A GB9319971D0 (en) | 1993-09-28 | 1993-09-28 | Cobalt glass compositions for coatings |
GB9319971.9 | 1993-09-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995009131A1 true WO1995009131A1 (en) | 1995-04-06 |
Family
ID=10742636
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1994/002105 WO1995009131A1 (en) | 1993-09-28 | 1994-09-28 | Cobalt glass compositions for coatings |
Country Status (6)
Country | Link |
---|---|
US (1) | US5747395A (en) |
EP (1) | EP0721430B1 (en) |
AU (1) | AU7703694A (en) |
DE (1) | DE69419928T2 (en) |
GB (1) | GB9319971D0 (en) |
WO (1) | WO1995009131A1 (en) |
Cited By (21)
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DE19744803C1 (en) * | 1997-10-10 | 1999-01-28 | Heraeus Gmbh W C | New decorative cobalt blue ceramic colour |
EP1302939A2 (en) * | 1997-06-09 | 2003-04-16 | Hitachi, Ltd. | Optical information recording medium |
US7144633B2 (en) | 2002-07-29 | 2006-12-05 | Evanite Fiber Corporation | Glass compositions |
US7160824B2 (en) | 2002-07-29 | 2007-01-09 | Evanite Fiber Corporation | Glass compositions |
US8357515B2 (en) | 2007-12-17 | 2013-01-22 | Queen Mary & Westfield College | Latency associated protein construct with aggrecanase sensitive cleavage site |
US8651203B2 (en) | 2011-02-17 | 2014-02-18 | Baker Hughes Incorporated | Polycrystalline compacts including metallic alloy compositions in interstitial spaces between grains of hard material, cutting elements and earth-boring tools including such polycrystalline compacts, and related methods |
US9034062B2 (en) | 2010-04-27 | 2015-05-19 | Baker Hughes Incorporated | Methods of forming polycrystalline compacts |
CN104973784A (en) * | 2015-07-10 | 2015-10-14 | 山东省淄博市博山长虹陶瓷装饰材料厂 | Over-glaze lead-cadmium-free low-temperature ceramic pigment flux |
US9198842B2 (en) | 2009-06-30 | 2015-12-01 | Repregen Limited | Multicomponent glasses for use in personal care products |
EP2963090A1 (en) * | 2014-06-30 | 2016-01-06 | Instytut Elektrotechniki | Method of manufacturing an anticorrosive pigment, the anticorrosive pigment and its application |
CN106396413A (en) * | 2016-09-08 | 2017-02-15 | 长春理工大学 | Erbium-ytterbium co-doped up-conversion luminescent glass ceramic containing barium tungstate crystalline phase and preparation method thereof |
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EP3650414A1 (en) * | 2018-11-09 | 2020-05-13 | LG Electronics Inc. | Enamel composition, method of preparing same, and cooking appliance |
US11261124B2 (en) | 2018-10-31 | 2022-03-01 | Lg Electronics Inc. | Enamel composition and method of preparing the same |
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US11773007B2 (en) | 2019-02-22 | 2023-10-03 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
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JP3067580B2 (en) * | 1995-04-04 | 2000-07-17 | 株式会社村田製作所 | Insulating paste and thick-film printed multilayer circuit using the same |
US6221147B1 (en) * | 1998-12-18 | 2001-04-24 | Cerdec Aktiengesellschaft Keramischre Farben | Bismuth manganese oxide pigments |
US6105394A (en) * | 1999-01-12 | 2000-08-22 | Ferro Corporation | Glass enamel for automotive applications |
US6346493B1 (en) * | 1999-10-27 | 2002-02-12 | Ferro Corporation | Decorative glass enamels |
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JP7029727B2 (en) * | 2018-04-19 | 2022-03-04 | 佐賀県 | Enamel glass material, enamel product, manufacturing method of enamel product |
CA3117892A1 (en) | 2018-11-26 | 2020-06-04 | Owens Corning Intellectual Capital, Llc | High performance fiberglass composition with improved elastic modulus |
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1993
- 1993-09-28 GB GB939319971A patent/GB9319971D0/en active Pending
-
1994
- 1994-09-28 AU AU77036/94A patent/AU7703694A/en not_active Abandoned
- 1994-09-28 WO PCT/GB1994/002105 patent/WO1995009131A1/en active IP Right Grant
- 1994-09-28 US US08/619,558 patent/US5747395A/en not_active Expired - Fee Related
- 1994-09-28 DE DE69419928T patent/DE69419928T2/en not_active Expired - Fee Related
- 1994-09-28 EP EP94927732A patent/EP0721430B1/en not_active Expired - Lifetime
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Cited By (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1302939A2 (en) * | 1997-06-09 | 2003-04-16 | Hitachi, Ltd. | Optical information recording medium |
EP1302939A3 (en) * | 1997-06-09 | 2003-06-04 | Hitachi, Ltd. | Optical information recording medium |
DE19744803C1 (en) * | 1997-10-10 | 1999-01-28 | Heraeus Gmbh W C | New decorative cobalt blue ceramic colour |
EP0908420A1 (en) * | 1997-10-10 | 1999-04-14 | W.C. Heraeus GmbH | Cobalt containing ceramic decoration paint and its use |
US8211575B2 (en) | 2002-07-29 | 2012-07-03 | Hollingsworth & Vose Company | Batteries containing bismuth glass compositions |
US8012629B2 (en) | 2002-07-29 | 2011-09-06 | Hollingsworth & Vose Company | Batteries containing bismuth glass compositions |
US7144633B2 (en) | 2002-07-29 | 2006-12-05 | Evanite Fiber Corporation | Glass compositions |
US7160824B2 (en) | 2002-07-29 | 2007-01-09 | Evanite Fiber Corporation | Glass compositions |
US7939166B2 (en) | 2004-07-21 | 2011-05-10 | Hollingsworth & Vose Company | Glass compositions |
US8357515B2 (en) | 2007-12-17 | 2013-01-22 | Queen Mary & Westfield College | Latency associated protein construct with aggrecanase sensitive cleavage site |
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Also Published As
Publication number | Publication date |
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EP0721430A1 (en) | 1996-07-17 |
GB9319971D0 (en) | 1993-11-17 |
US5747395A (en) | 1998-05-05 |
DE69419928D1 (en) | 1999-09-09 |
EP0721430B1 (en) | 1999-08-04 |
AU7703694A (en) | 1995-04-18 |
DE69419928T2 (en) | 1999-12-23 |
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