WO2005058766A1 - Glass and glass-ceramic materials, articles and method of preparing the same - Google Patents
Glass and glass-ceramic materials, articles and method of preparing the same Download PDFInfo
- Publication number
- WO2005058766A1 WO2005058766A1 PCT/EP2004/014463 EP2004014463W WO2005058766A1 WO 2005058766 A1 WO2005058766 A1 WO 2005058766A1 EP 2004014463 W EP2004014463 W EP 2004014463W WO 2005058766 A1 WO2005058766 A1 WO 2005058766A1
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- WO
- WIPO (PCT)
- Prior art keywords
- glass
- ceramic material
- ceramic
- ceramics
- spodumene
- Prior art date
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- 239000006112 glass ceramic composition Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 53
- 239000011521 glass Substances 0.000 claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000006104 solid solution Substances 0.000 claims abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006025 fining agent Substances 0.000 claims abstract description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 238000002468 ceramisation Methods 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052642 spodumene Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 7
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003086 colorant Substances 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 238000010411 cooking Methods 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 3
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- -1 Fe O3 Chemical compound 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 33
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 7
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052644 β-spodumene Inorganic materials 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- 229910000500 β-quartz Inorganic materials 0.000 abstract description 2
- 241000252067 Megalops atlanticus Species 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 230000005540 biological transmission Effects 0.000 description 13
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 239000006064 precursor glass Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 238000003279 ceramming Methods 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
-
- 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
- C03C10/0009—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 silica as main constituent
-
- 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
-
- 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
- C03C10/0018—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 SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—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 SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
Definitions
- the present invention relates to glass and glass-ceramic materials, articles and method of making the same.
- the present invention relates to glass-ceramic materials having ?-quartz or ?-spodumene as the predominant crystalline phase having a high ⁇ -OH level.
- the present invention is useful, for example, in the production of glass- ceramic articles such as cooktops, cook utensils, stove windows, and the like.
- BACKGROUND OF THE INVENTION [0002]
- numerous glass-ceramic materials and articles have been described, for use such as cooktops, cooking utensils, stove windows and the like. [0003] In United States Patent No.
- the glass-ceramic mateiral is obtained by heat treatment of the glass precursor, which comprises a step of crystallization at a temperature on the order of 1,070°C to 1,090°C. The higher the temperature of this crystallization step is, the more the opacity of the material.
- the glass precursor of the glass-ceramics of the invention are also suitable for obtaining efficient glass-ceramics of main crystalline phase of ⁇ -quaxtz. It therefore enables the manufacture of various transparent or opaque products from the same glass precursor composition. This flexibility of the method in question is highly desirable in the art.
- a transparent, translucent or opaque glass-ceramic material containing, as main crystalline phase, solid solution of ?-quartz or /?-spodumene, characterized in that: (i) it essentially has the following composition, expressed as percentages by weight of oxides: 65 to 70% of SiO 2 18 to 23% ofAl 2 O 3 > 4 to 5% of Li 2 O 0 to ⁇ l% ofMgO 1 to 3% of ZnO 0 to 2% of BaO 1.8 to 4% ofTiO 2 1 to 2.5% of ZrO 2 0.4 to 1% of K 2 O and or Na 2 O; with, advantageously, an effective and non-excess amount of at least one fining agent; and (ii) it has a ?-OH value of higher than 0.2 mm "1 , preferably higher than 0.4 mm "1 .
- the composition of the glass-ceramic contains As O 3 and/or Sb 2 O 3 , as fining agent, in the following percentages by weight: As 2 O 3 0 - 1.5 Sb 2 O 3 0 - 1.5 with As 2 O 3 + Sb 2 O 3 0.5 - 1.5.
- the composition of the glass-ceramic material further comprises an effective amount of at least one colorant, advantageously selected from CoO, Cr 2 O 3 , Fe 2 O , MnO 2 , NiO, V 2 O 5) CeO 2 and their mixtures.
- an article made from a glass-ceramic material of the present invention described above which is preferably selected from the group consisting of a cook-top, a cooking utensil, a microwave oven plate, a fireplace window, a fire-door or fire-window, a pyrolysis oven window and a catalysis oven window.
- a third aspect of the present invention involves an inorganic glass, which is a precursor of a glass-ceramic material according to the present invention, characterized in that: (i) it essentially has the following composition, expressed as percentages by weight of oxides: 65 to 70% of SiO 2 18 to 23% ofAl 2 O 3 > 4 to 5% ofLi 2 O 0 to ⁇ l% ofMgO 1 to 3% of ZnO 0 to 2% of BaO 1.8 to 4% ofTiO 2 1 to 2.5% of ZrO 2 0.4 to 1% of K 2 O and/or Na 2 O; with, advantageously, an effective and non-excess amount of at least one fining agent; and (ii) it has a ⁇ - R value of higher than 0.2 mm "1 , preferably higher than 0.4 mm "1 .
- a fourth aspect of the present invention is a method of preparing a glass- ceramic material or article of the present invention described above, characterized in that it comprises heat-treating a crystallizable inorganic glass precursor of the glass-ceramic described above under conditions which ensure its ceramization.
- the heat treatment comprises a step of crystallization at a temperature of between 1,050 and 1,200°C.
- the heat treatment comprises a step of crystallization at a temperature of between 840 and 900°C.
- the present invention has the surprising benefit that, because of the choice of composition, notwithstanding the high water content of at least 0.2 mm "1 , preferably at least 0.4 mm "1 in the precursor glass, the glass-ceramic composition comprising ⁇ - spodumene solid solution as the main crystalline phase can be obtained at a high ceramming temperature without cracking and reduction in mechanical strength. Further, the cerammed material and/or articles have a low thermal expansion. In addition, effective glass-ceramic materials and/or articles comprising ?-quartz solid solution as the main crystalline phase can be produced as well from the precursor glass of the present invention.
- FIG. 1 is a diagram showing the transmission curves of the glass-ceramic materials in the Examples of the present invention and Comparative Examples.
- the glass-ceramic materials of the present invention which can exist in transparent, translucent (opalescent) or opaque form, i.e., which contain ?-quartz or ⁇ - spodumene as main crystalline phase, are characterized in that they essentially have the following composition, expressed in percentages by weight of oxides: 65 to 70% of SiO 2 18 to 23% ofAl 2 O 3 > 4 to 5% ofLi 2 O 0 to ⁇ l% ofMgO 1 to 3% of ZnO 0 to 2% of BaO 1.8 to 4% ofTiO 2 1 to 2.5% ofZrO 2 0.4 to 1% of K 2 O and or Na 2 O; with, advantageously, an effective and non-excess amount of at least one fining agent, and in that it comprises a ⁇ -O ⁇ .
- MgO over 1% of MgO and the thermal expansion is not acceptable
- ZnO ZnO enables, with Li 2 O, the coefficient of thermal expansion of the glass-ceramics to be adjusted. Thus, it must be incorporated at less than 1%. At too high a content (> 3%), a risk is taken of crystallizing other crystalline phases, such as spinels, which have a high thermal expansion
- BaO BaO is an optional element which enables the viscosity of the glass precursor to be adjusted. It remains in the amorphous phase of the glass-ceramic. If it is incorporated in an amount which is greater than 2%, it is difficult to keep a low thermal expansion;
- TiO 2 and ZrO 2 are incorporated as nucleation agents. If they are incorporated in too low an amount, the precursor glass does not crystallize; if they are incorporated in too high an amount, the devitrification, upon cooling, can be difficult to control;
- Na 2 O and K O enable the problems of mechanical strength and surface cracking to be limited. These constituents remain in the amorphous phase of the glass- ceramic. If they are incorporated in too great an amount, they have a harmful effect upon the thermal expansion. [0031] Within the composition set forth, it was possible, in a non-obvious manner, to take advantage of the beneficial action, of Al 2 O and/or K 2 O and/or Na 2 O, on the mechanical properties (also on the absence of cracks) while at the same time limiting, even compensating for, mainly by virtue of Li 2 O, their harmful action on the thermal expansion. [0032] The optional constituents, MgO and BaO, when they are present, are generally present at at least 0.1% by weight.
- composition specified above advantageously contains an effective and non-excess amount of at least one fining agent.
- the person skilled in the art knows well how to manage the incorporation of this type of compounds within the glass precursor. In general, it is incorporated at less than 3% by weight, rather at less than 2% by weight of this type of compounds.
- As 2 O 3 and/or Sb 2 O 3 are in general incorporated as fining agent in the following amounts: As 2 O 3 0 - 1.5 Sb 2 O 3 0 - 1.5 with As 2 O 3 + Sb 2 O 3 0,5 - 1.5 (% by weight).
- the glass-ceramic of the invention may be colored or not. In order for it to have a real coloration, it contains, in addition to its constituent elements listed above, an effective amount, which does not in general exceed 2% by weight, of at least one colorant.
- Said colorant(s) is(are) advantageously selected from CoO, Cr 2 O 3 , Fe 2 O 3 , MnO , NiO,
- As colored glass-ceramics (black, transparent) of the invention those which have the composition by weight indicated above are more particularly preferred with, in addition, 0.03 (advantageously 0.05) to 1% by weight of V O 5 and the following condition:
- the glass-ceramic materials of the invention which are efficient in terms of transmission, of mechanical strength and of thermal expansion, can contain relatively high water contents ( ⁇ -OH > 0.2 mm "1 , even /?-OH > 0.4 mm "1 ), which do not notably impose any constraint, during their preparation process. No particular precautions are required. These affirmations are confirmed by the Examples below.
- the glass-ceramic materials of the invention can exist with a predominant crystalline phase of ⁇ -quartz or 7-spodumene solid solution.
- the glass-ceramics of the invention are glass-ceramics having a predominant crystalline phase of ?-spodumene solid solution.
- Such glass- ceramics when they contain an effective amount of at least one colorant selected from CeO 2 , MnO 2 and Fe 2 O 3 , have a beige color.
- the present invention relates to crystallizable inorganic glasses which are precursors of the glass-ceramics described above.
- Said inorganic glasses, which are crystallizable and are precursors of the glass-ceramics above essentially have the following composition, expressed in percentages by weight of oxides: 65 to 70% of SiO 2 18 to 23% ofAl 2 O 3 > 4 to 5% of Li 2 O 0 to ⁇ l% ofMgO 1 to 3% of ZnO 0 to 2% of BaO 1.8 to 4% ofTiO 2 l to 2.5% ofZrO 2 0.4 to 1% of K 2 O and/or Na 2 O; with, advantageously, an effective and non-excess amount of at least one fining agent.
- the glass has advantageously a ⁇ -OH value higher than 0.2 mm "1 , preferably higher than 0.4 mm "1 .
- Said inorganic glasses are optionally colored. According to what has been seen above, they can notably contain an effective amount of at least one of the following colorants: CoO, Cr 2 O 3 , Fe 2 O 3 , MnO 2 , NiO, V 2 O 5 and CeO 2 .
- the present invention relates to articles made from a glass-ceramic materials as described above.
- the articles in question can notably be selected from the group consisting of a cook-top, a cooking utensil, a microwave oven plate, a fireplace window (fireguard plate), a fire-door or fire-window or a pyro lysis oven window or catalysis-oven window. They advantageously are cook-tops.
- the present invention relates to the methods of preparation of glass-ceramic materials and articles.
- Said methods constitute analogous methods, which are implemented characteristically with crystallizable inorganic glasses having the weight composition set forth above.
- the glass-ceramic materials and articles of the invention are obtained by heat treating a crystallizable inorganic glass precursor, as characterized above, this heat treatment being implemented under conditions which ensure the ceramization of said glass precursor.
- the glass-ceramic articles of the invention are obtained by such a heat treatment after shaping the crystallizable inorganic glass precursor in question.
- the shaping is a classical step. It can notably be pressing or rolling. It can notably be a shaping which is intended to confer the shape of a plate.
- the heat treatment in question classically comprises a rise in temperature, which is generally in stages, up to the crystallization temperature maintained over an adequate period of time. Said heat treatment of the invention generally lasts less than 2 hours. This is another advantageous point of the present invention.
- said heat treatment In order to obtain a glass-ceramic the main crystalline phase of which isf5-spodumene solid solution, said heat treatment generally comprises the crystallization step at a temperature of between 1,050 and 1,200°C. [0052] In order to obtain a glass-ceramic of the invention, the main crystalline phase of which is /J-quartz solid solution, said heat treatment generally comprises the crystallization step at a temperature of between 840 and 900°C.
- Example I the importance of which more particularly emerges upon consideration of Comparative Examples 1 and 2
- Examples II and III the importance of which more particularly emerges upon consideration of Comparative Example 3.
- Example I the present invention
- Comparative Examples 1 and 2 [0056] Said Comparative Examples 1 and 2 illustrate the prior art.
- the MOR values were measured according to ASTM standard
- MOR values 144 MPa and 124 MPa, respectively.
- Example 1 except that its OH content is much lower. Consequently, the glass-ceramics obtained from said glass - glass-ceramics comprising ?-spodumene as the main crystalline phase, white in color and slightly translucent (that obtained after the Ceramization
- Schedule 2 is a little more opaque than that obtained after the Ceramization Schedule 1) - have higher MOR values: 209 MPa and 294 MPa, respectively.
- the glass of Example I is a glass precursor of the invention. Despite a significant OH content (almost identical to that of the glass of Comparative Example 1), it does enable efficient glass-ceramics to be obtained, with regard to both: - their low thermal expansion values, and - their high MOR values (191 MPa and 195 MPa).
- the glass-ceramics of the invention obtained by the Ceramization Schedules 1 and 2 are glass-ceramics of ⁇ -spodumene, white in color and slightly translucent.
- the glass-ceramic of the invention obtained by the Ceramization Schedule 3 is a glass-ceramic of ⁇ -quartz. It is transparent.
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The present invention relates to novel glass and glass-ceramic materials, articles made from said novel glass-ceramic and to methods of preparing said novel glass-ceramics and articles. Said novel, transparent, translucent or opaque glass-ceramics, which contain, as main crystalline phase, a solid solution of β-quartz or of β-spodumene, essentially have the following composition, expressed as percentages by weight of oxides: 65 to 70% of SiO2; 18 to 23% of Al2O3;>4 to 5% of Li2O; 0 to <1% of MgO; 1 to 3% of ZnO; 0 to 2% of BaO; 1.8 to 4% of TiO2; 1 to 2.5% of ZrO2; 0.4 to 1% of K2O and/or Na2O; with, advantageously, an effective and non-excess amount of at least one fining agent. The glass-ceramic material is alse characterized by a water content of β-OH higher than 0.2 mm-1, preferably higher than 0.4 mm-1.
Description
GLASS AND GLASS-CERAMIC MATERIALS, ARTICLES AND METHOD OF PREPARING THE SAME
FIELD OF THE INVENTION [0001] The present invention relates to glass and glass-ceramic materials, articles and method of making the same. In particular, the present invention relates to glass-ceramic materials having ?-quartz or ?-spodumene as the predominant crystalline phase having a high β-OH level. The present invention is useful, for example, in the production of glass- ceramic articles such as cooktops, cook utensils, stove windows, and the like. BACKGROUND OF THE INVENTION [0002] In the prior art, numerous glass-ceramic materials and articles have been described, for use such as cooktops, cooking utensils, stove windows and the like. [0003] In United States Patent No. 5,446,008, glass-ceramics are described having improved transmission. With reference to this technical problem of transmission, it is taught that the water content of the glass-ceramic must be controlled. Said water content must in fact be less than 0.03 mol/1. Moreover, in this reference, the technical problems of mechanical strength and thermal expansion were not tackled.
[0004] In United States Patent No. 4,461,839, other glass-ceramics are described. Their composition, which is almost free from MgO, is not optimized with reference to said technical problems of mechanical strength and of thermal expansion.
[0005] In European patent application publication No. EP-A-1 170 264, the problem of surface cracking of the glass-ceramics is discussed and, with reference to said problem, novel glass-ceramics are proposed which are original through their composition and their state of crystallization. [0006] United States Patent No. 5,070,045 describes glass-ceramic materials having β- spodumene or ?-quartz solid solution as the predominant crystalline phase. The glass- ceramic materials comprising ?-spodumene solid solution as the predominant crystalline phase have an opaque, white or colored, appearance. They are opaque in the visible, in order to prevent the users of plates from being dazzled by heating elements which are placed under such plates, but they keep a high transmission in the infrared, so as to improve the heating of the cooking utensils which are placed on said plates. Said utensils are heated not only by conduction but also by radiation. The glass-ceramic mateiral is obtained by heat treatment of the glass precursor, which comprises a step of crystallization
at a temperature on the order of 1,070°C to 1,090°C. The higher the temperature of this crystallization step is, the more the opacity of the material. [0007] These glass-ceramics and the method of obtaining them are described more specifically in the patent application WO-A-99 06334. [0008] Though the materials have been used in widely commercialized glass-ceramic products, there is still room for improvement: a) said plates of ?-spodumene are less efficient than their /?-quartz counterparts, which are also described in US patent US-A-5,070,045, in terms of mechanical strength and thermal expansion; and b) where more opaque products are desired (e.g., for use in a context of heating by induction), it is suitable to ceramize the glass precursor at a higher temperature (> +20°C). As a result, cracks can be generated in the structure of the glass-ceramic. In the past, it was observed that a lower mechanical strength and the presence of cracks, when the ceramization temperature is increased, were linked to the presence of water content in the glass precursor. It is known that the water can be incorporated in said glass precursor during its melting. The water content of said glass does in fact depend upon the state of the starting materials used and upon the means of melting used. Thus, if the precursor glasses of the glass-ceramics are melted from starting materials which contain little water in an electric oven, the resulting glass-ceramics tend to have a high mechanical strength and do not have a tendency to crack, even if the ceramization is carried out at high temperature. Glasses having low water content can similarly be used by adding halogens into their basic composition. This is described in United States Patent No. 5,446,008. Industrially however, it is highly desired to not have to be concerned about controlling the water content of the glass. It is notably desired to be able to implement methods of melting employing burners of air-natural gas type or oxygen-natural gas type. The person skilled in the art cannot ignore that the use of such means of melting lead to significant contents of water in the glasses. It is the water contents which limit the ceramization temperatures. [0009] Thus, in accordance with the invention, the improvement sought after to said β- spodumene glass-ceramic materials has been along two lines. It was desired both to increase the mechanical strength and to avoid the appearance of cracks (in the case of glasses which contain much water and/or for ceramizations at high temperature) and to decrease the thermal expansion.
[0010] Furthermore, the glass precursor of the glass-ceramics of the invention are also suitable for obtaining efficient glass-ceramics of main crystalline phase of β-quaxtz. It therefore enables the manufacture of various transparent or opaque products from the same glass precursor composition. This flexibility of the method in question is highly desirable in the art. [0011] Said person skilled in the art has therefore already understood the interest of the present invention, the main subject of which consists of novel glass-ceramic compositions which are suitable for efficient ?-quartz and / -spodumene glass-ceramics, more particularly ?-spodumene glass-ceramics which are more efficient than those of the prior art (US-A-5,070,045 and WO-A-99 06334). SUMMARY OF THE INVENTION [0012] According to a first aspect of the present invention, it is provided a transparent, translucent or opaque glass-ceramic material containing, as main crystalline phase, solid solution of ?-quartz or /?-spodumene, characterized in that: (i) it essentially has the following composition, expressed as percentages by weight of oxides: 65 to 70% of SiO2 18 to 23% ofAl2O3 > 4 to 5% of Li2O 0 to < l% ofMgO 1 to 3% of ZnO 0 to 2% of BaO 1.8 to 4% ofTiO2 1 to 2.5% of ZrO2 0.4 to 1% of K2O and or Na2O; with, advantageously, an effective and non-excess amount of at least one fining agent; and (ii) it has a ?-OH value of higher than 0.2 mm"1, preferably higher than 0.4 mm"1. Preferably, the glass-ceramic material of the present invention comprises y^spodumene solid solution as the main crystalline phase.
[0013] In a preferred embodiment of the glass-ceramic material of the present invention, the composition of the glass-ceramic contains As O3 and/or Sb2O3, as fining agent, in the following percentages by weight: As2O3 0 - 1.5 Sb2O3 0 - 1.5
with As2O3 + Sb2O3 0.5 - 1.5. [0014] According to another preferred embodiment of the glass-ceramic material of the present invention, the composition of the glass-ceramic material further comprises an effective amount of at least one colorant, advantageously selected from CoO, Cr2O3, Fe2O , MnO2, NiO, V2O5) CeO2 and their mixtures. [0015] According to a second aspect of the present invention, it is provided an article made from a glass-ceramic material of the present invention described above, which is preferably selected from the group consisting of a cook-top, a cooking utensil, a microwave oven plate, a fireplace window, a fire-door or fire-window, a pyrolysis oven window and a catalysis oven window. [0016] A third aspect of the present invention involves an inorganic glass, which is a precursor of a glass-ceramic material according to the present invention, characterized in that: (i) it essentially has the following composition, expressed as percentages by weight of oxides: 65 to 70% of SiO2 18 to 23% ofAl2O3 > 4 to 5% ofLi2O 0 to < l% ofMgO 1 to 3% of ZnO 0 to 2% of BaO 1.8 to 4% ofTiO2 1 to 2.5% of ZrO2 0.4 to 1% of K2O and/or Na2O; with, advantageously, an effective and non-excess amount of at least one fining agent; and (ii) it has a β- R value of higher than 0.2 mm"1, preferably higher than 0.4 mm"1.
[0017] A fourth aspect of the present invention is a method of preparing a glass- ceramic material or article of the present invention described above, characterized in that it comprises heat-treating a crystallizable inorganic glass precursor of the glass-ceramic described above under conditions which ensure its ceramization. Preferably, in order to prepare a glass-ceramic material and/or article containing ?-spodumene solid solution as the main crystalline phase, the heat treatment comprises a step of crystallization at a temperature of between 1,050 and 1,200°C. Preferably, in order to produce glass-ceramic materials and/or articles having ^-quartz solid solution as the main crystalline phase, the
heat treatment comprises a step of crystallization at a temperature of between 840 and 900°C.
[0018] The present invention has the surprising benefit that, because of the choice of composition, notwithstanding the high water content of at least 0.2 mm"1, preferably at least 0.4 mm"1 in the precursor glass, the glass-ceramic composition comprising β- spodumene solid solution as the main crystalline phase can be obtained at a high ceramming temperature without cracking and reduction in mechanical strength. Further, the cerammed material and/or articles have a low thermal expansion. In addition, effective glass-ceramic materials and/or articles comprising ?-quartz solid solution as the main crystalline phase can be produced as well from the precursor glass of the present invention. [0019] Additional features and advantages of the invention will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from the description or recognized by practicing the invention as described in the written description and claims hereof as well as the appended drawing. [0020] It is to be understood that the foregoing general description and the following detailed description are merely exemplary of the invention, and are intended to provide an overview or framework to understanding the nature and character of the invention as it is claimed. BRIEF DESCRIPTION OF THE DRAWINGS [0021] The drawing, FIG. 1, is a diagram showing the transmission curves of the glass-ceramic materials in the Examples of the present invention and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION [0022] The glass-ceramic materials of the present invention, which can exist in transparent, translucent (opalescent) or opaque form, i.e., which contain ?-quartz or β- spodumene as main crystalline phase, are characterized in that they essentially have the following composition, expressed in percentages by weight of oxides: 65 to 70% of SiO2 18 to 23% ofAl2O3 > 4 to 5% ofLi2O 0 to < l% ofMgO 1 to 3% of ZnO 0 to 2% of BaO
1.8 to 4% ofTiO2 1 to 2.5% ofZrO2 0.4 to 1% of K2O and or Na2O; with, advantageously, an effective and non-excess amount of at least one fining agent, and in that it comprises a β-OΗ. value of over 0.2 mm"1 , and preferably over 0.4 mm"1. [0023] The relative contents of each one of the constituent oxides are relatively critical. Thus: [0024] Al O : it was observed that an increase in the content of Al2O3 is favorable to an improvement of the mechanical properties. Too high a content of said Al O3 does however unacceptably increase the thermal expansion of the glass-ceramic material; [0025] Li2O: characteristically, it is incorporated at more than 4%, advantageously more than 4.1% by weight of this oxide in order to obtain a low thermal expansion. Over 5% of Li2O and the crystallization becomes difficult to control; [0026] MgO: over 1% of MgO and the thermal expansion is not acceptable; [0027] ZnO: ZnO enables, with Li2O, the coefficient of thermal expansion of the glass-ceramics to be adjusted. Thus, it must be incorporated at less than 1%. At too high a content (> 3%), a risk is taken of crystallizing other crystalline phases, such as spinels, which have a high thermal expansion; [0028] BaO: BaO is an optional element which enables the viscosity of the glass precursor to be adjusted. It remains in the amorphous phase of the glass-ceramic. If it is incorporated in an amount which is greater than 2%, it is difficult to keep a low thermal expansion;
[0029] TiO2 and ZrO2 are incorporated as nucleation agents. If they are incorporated in too low an amount, the precursor glass does not crystallize; if they are incorporated in too high an amount, the devitrification, upon cooling, can be difficult to control;
[0030] Na2O and K O enable the problems of mechanical strength and surface cracking to be limited. These constituents remain in the amorphous phase of the glass- ceramic. If they are incorporated in too great an amount, they have a harmful effect upon the thermal expansion. [0031] Within the composition set forth, it was possible, in a non-obvious manner, to take advantage of the beneficial action, of Al2O and/or K2O and/or Na2O, on the mechanical properties (also on the absence of cracks) while at the same time limiting, even compensating for, mainly by virtue of Li2O, their harmful action on the thermal expansion.
[0032] The optional constituents, MgO and BaO, when they are present, are generally present at at least 0.1% by weight. [0033] The composition specified above advantageously contains an effective and non-excess amount of at least one fining agent. The person skilled in the art knows well how to manage the incorporation of this type of compounds within the glass precursor. In general, it is incorporated at less than 3% by weight, rather at less than 2% by weight of this type of compounds. [0034] As indicated in US patent US-A-5,070,045, As2O3 and/or Sb2O3 are in general incorporated as fining agent in the following amounts: As2O3 0 - 1.5 Sb2O3 0 - 1.5 with As2O3 + Sb2O3 0,5 - 1.5 (% by weight).
[0035] Similarly, other fining agents, such as SnO2, CeO2, fluorides or sulfates, alone or in a mixture, can be incorporated. [0036] The glass-ceramic of the invention may be colored or not. In order for it to have a real coloration, it contains, in addition to its constituent elements listed above, an effective amount, which does not in general exceed 2% by weight, of at least one colorant.
Said colorant(s) is(are) advantageously selected from CoO, Cr2O3, Fe2O3, MnO , NiO,
V2O5, CeO (and their mixtures). [0037] As colored glass-ceramics (black, transparent) of the invention, those which have the composition by weight indicated above are more particularly preferred with, in addition, 0.03 (advantageously 0.05) to 1% by weight of V O5 and the following condition:
3.8% < TiO2 + ZrO2 + 5V O5 < 6%; as well as a main crystalline phase of ?-quartz.
[0038] It has been surprisingly found that water content, expressed in terms of β-OH value in the glass and glass-ceramic materials, higher than 0.2 mm"1, even higher than
0.4 mm"1, does not negatively affect the transmission, mechanical strength and thermal expansion of the glass-ceramic materials of the present invention, contrary to the teachings regarding water content in the prior art discussed above. Since such water level is not incompatible with conventional glass-melting technology, especially those using oxygen- fuel or air-fuel burners, the glass and glass-ceramic materials of the present invention are particularly advantageous and preferred for industrial production.
[0039] According to the teaching of United States Patent No. 5,446,008, particularly with reference to the problem of transmission, the maximum water content acceptable was
fixed at less than 0.03 mol/1. It has furthermore been seen that this parameter had an influence upon the appearance of cracks, during ceramizations at high temperature. [0040] The water content, within the composition of the glass and glass-ceramic of the present invention, was expressed by the β-OΗ value, which can be calculated directly from transmission curves. It was not expressed by the concentration, in mol/1, as in United States Patent No. 5,446,008. The person skilled in the art cannot in fact ignore that it is difficult to convert the β-OH to water content expressed in mol/1, since this obliges having to know the index of the material at 2,800 nm and the coefficient of extinction of water in said material. These two parameters are difficult to measure. [0041] In any case, the glass-ceramic materials of the invention, which are efficient in terms of transmission, of mechanical strength and of thermal expansion, can contain relatively high water contents (β-OH > 0.2 mm"1, even /?-OH > 0.4 mm"1), which do not notably impose any constraint, during their preparation process. No particular precautions are required. These affirmations are confirmed by the Examples below. [0042] It has been seen above that the glass-ceramic materials of the invention can exist with a predominant crystalline phase of ^-quartz or 7-spodumene solid solution. According to a preferred variant, the glass-ceramics of the invention are glass-ceramics having a predominant crystalline phase of ?-spodumene solid solution. Such glass- ceramics, when they contain an effective amount of at least one colorant selected from CeO2, MnO2 and Fe2O3, have a beige color.
[0043] According to a second aspect, the present invention relates to crystallizable inorganic glasses which are precursors of the glass-ceramics described above. Said inorganic glasses, which are crystallizable and are precursors of the glass-ceramics above, essentially have the following composition, expressed in percentages by weight of oxides: 65 to 70% of SiO2 18 to 23% ofAl2O3 > 4 to 5% of Li2O 0 to < l% ofMgO 1 to 3% of ZnO 0 to 2% of BaO 1.8 to 4% ofTiO2 l to 2.5% ofZrO2 0.4 to 1% of K2O and/or Na2O;
with, advantageously, an effective and non-excess amount of at least one fining agent. The glass has advantageously a β-OH value higher than 0.2 mm"1, preferably higher than 0.4 mm"1.
[0044] Said inorganic glasses are optionally colored. According to what has been seen above, they can notably contain an effective amount of at least one of the following colorants: CoO, Cr2O3, Fe2O3, MnO2, NiO, V2O5 and CeO2.
[0045] According to a third aspect, the present invention relates to articles made from a glass-ceramic materials as described above. The articles in question can notably be selected from the group consisting of a cook-top, a cooking utensil, a microwave oven plate, a fireplace window (fireguard plate), a fire-door or fire-window or a pyro lysis oven window or catalysis-oven window. They advantageously are cook-tops.
[0046] According to a fourth aspect, the present invention relates to the methods of preparation of glass-ceramic materials and articles.
[0047] Said methods constitute analogous methods, which are implemented characteristically with crystallizable inorganic glasses having the weight composition set forth above.
[0048] The glass-ceramic materials and articles of the invention are obtained by heat treating a crystallizable inorganic glass precursor, as characterized above, this heat treatment being implemented under conditions which ensure the ceramization of said glass precursor.
[0049] The glass-ceramic articles of the invention are obtained by such a heat treatment after shaping the crystallizable inorganic glass precursor in question. The shaping is a classical step. It can notably be pressing or rolling. It can notably be a shaping which is intended to confer the shape of a plate. [0050] The heat treatment in question classically comprises a rise in temperature, which is generally in stages, up to the crystallization temperature maintained over an adequate period of time. Said heat treatment of the invention generally lasts less than 2 hours. This is another advantageous point of the present invention.
[0051] In order to obtain a glass-ceramic the main crystalline phase of which isf5-spodumene solid solution, said heat treatment generally comprises the crystallization step at a temperature of between 1,050 and 1,200°C.
[0052] In order to obtain a glass-ceramic of the invention, the main crystalline phase of which is /J-quartz solid solution, said heat treatment generally comprises the crystallization step at a temperature of between 840 and 900°C.
[0053] The invention is further illustrated by the following non-limiting Examples. EXAMPLES
[0054] More specifically, the invention is illustrated, respectively: - by Example I, the importance of which more particularly emerges upon consideration of Comparative Examples 1 and 2; and - by Examples II and III, the importance of which more particularly emerges upon consideration of Comparative Example 3.
[0055] Example I (the present invention) and Comparative Examples 1 and 2: [0056] Said Comparative Examples 1 and 2 illustrate the prior art.
[0057] They differ from each other by the water content of the glass precursors of the glass-ceramics in question. [0058] Table 1 below indicates: - in its first part, the compositions by weight of the precursor glasses in question, as well as their water content (β-OH); - in its second part, the characteristics of three glass-ceramics obtained from said glasses, after three different Ceramization Schedules. [0059] The glasses were prepared in a usual manner from oxides and/or from compounds which are easily decomposable, such as nitrates or carbonates. The starting materials were mixed in order to obtain a homogeneous mixture. 1,000 g of starting materials, which were placed in a platinum crucible, were melted in an electric oven for 12 hours at 1,650°C. [0060] After melting, the glasses were shaped into plates of 6 mm thickness, which were annealed at 650°C. For the glasses which contain the most water (Example I and Comparative Example 1), hydrated alumina was used as starting material (anhydrous alumina was used in Comparative Example 2). The water contents of the glasses prepared (before ceramization) were compared. [0061] In FIG. 1, transmission curves are given for the glasses according to said Example I of the present invention and Comparative Examples 1 and 2 of the prior art. The absorption peaks of the OHs, around 2,800 nm, are clearly visible. The fact that the glasses according to Comparative Example 1 and Example I of the present invention have almost
identical water contents is thus easily seen (the curves merge around 2,800 nm). Said water contents are very much greater than that of the glass of Comparative Example 2. [0062] The annealed plates were ceramised according to one or the other of the following ceramming schedules: [0063] Ceramization Schedule 1 : 26 minutes from ambient temperature to 660°C 40 minutes from 660°C to 830°C 11 minutes from 830°C to 1,000°C 9 minutes from 1,000°C to 1,070°C 15 minutes at 1070°C rapid cooling to ambient temperature. [0064] Ceramization Schedule 2: 26 minutes from ambient temperature to 660°C 40 minutes from 660°C to 830°C 11 minutes from 830°C to 1,000°C 11 minutes from 1,000°C to 1,090°C 15 minutes at 1,090°C rapid cooling to ambient temperature. [0065] Ceramization Schedule 3: 26 minutes from ambient temperature to 660°C 51 minutes from 660°C to 860°C 15 minutes at 860°C rapid cooling to ambient temperature.
Table 1
F394-78. Numbers in parentheses are standard deviation. [0067] After ceramization, the thermal expansion, the transmissions at 800 and 2,000 nm, as well as the modulus of rupture of the glass-ceramics obtained, were therefore evaluated. [0068] The glass of Comparative Example 1 contains a significant amount of OH.
The glass-ceramics obtained from said glass - glass-ceramics comprising /?-spodumene solid solution as the main crystalline phase, white in color and slightly translucent (that obtained after the Ceramization Schedule 2 is a little more opaque than that obtained after the Ceramization Schedule 1) - are not cracked. However, said glass-ceramics have low
MOR values: 144 MPa and 124 MPa, respectively.
[0069] The glass of Comparative Example 2 is identical to that of Comparative
Example 1, except that its OH content is much lower. Consequently, the glass-ceramics obtained from said glass - glass-ceramics comprising ?-spodumene as the main crystalline phase, white in color and slightly translucent (that obtained after the Ceramization
Schedule 2 is a little more opaque than that obtained after the Ceramization Schedule 1) - have higher MOR values: 209 MPa and 294 MPa, respectively.
[0070] The glass of Example I is a glass precursor of the invention. Despite a significant OH content (almost identical to that of the glass of Comparative Example 1), it does enable efficient glass-ceramics to be obtained, with regard to both: - their low thermal expansion values, and - their high MOR values (191 MPa and 195 MPa).
[0071] The glass-ceramics of the invention obtained by the Ceramization Schedules 1 and 2 are glass-ceramics of β-spodumene, white in color and slightly translucent. The glass-ceramic of the invention obtained by the Ceramization Schedule 3 is a glass-ceramic of β-quartz. It is transparent.
[0072] Examples II and III, and Comparative Example 3:
[0073] Said Examples were carried out under more stringent conditions with reference to the water content of the precursor glasses.
[0074] The process for obtaining said glasses was comparable to that carried out in the preceding Examples (melting). However, throughout the whole melting, the surface of the
glass was flushed with a current of water vapor. Consequently, the contents of water in the glasses were very high, higher than those in the glasses of Examples I, 1 or 2. [0075] Table 2 is proposed below, which is of the same type as Table 1 above. Table 2
Claims
1. A transparent, translucent or opaque glass-ceramic material containing, as main crystalline phase, solid solution of ?-quartz or /?-spodumene, characterized in that: (i) it essentially has the following composition, expressed as percentages by weight of oxides: 65 to 70% of SiO2 18 to 23% ofAl2O3 > 4 to 5% ofLi2O 0 to < l% ofMgO 1 to 3% of ZnO 0 to 2% of BaO 1.8 to 4% ofTiO2 1 to 2.5% of ZrO2 0.4 to 1 % of K2O and/or Na2O; with, advantageously, an effective and non-excess amount of at least one fining agent; and (ii) it has a β-OR value of higher than 0.2 mm"1, preferably higher than 0.4 mm'1.
2. The glass-ceramic material according to claim 1, the composition of which contains As2O3 and/or Sb2O3, as fining agent, in the following percentages by weight: As2O3 0 - 1.5 Sb2O3 0 - 1.5 with As2O3 + Sb2O3 0.5 - 1.5.
3. The glass-ceramic material according to claim 1 or claim 2, the composition of which further contains an effective amount of at least one colorant, advantageously selected from CoO, Cr2O3, Fe O3, MnO2, NiO, V O5) CeO2 and their mixtures.
4. The glass-ceramic material according to any one of claims 1 to 3, which contains, as main crystalline phase, a solid solution of ?-spodumene.
5. An article made from a glass-ceramic material according to any one of claims 1 to 4, which is preferably selected from the group consisting of a cook-top, a cooking utensil, a microwave oven plate, a fireplace window, a fire-door or fire-window, a pyrolysis oven window and a catalysis oven window.
6. A crystallizable inorganic glass, which is a precursor of a glass-ceramic material according to any one of claims 1 to 4, characterized in that: (i) it essentially has the following composition, expressed as percentages by weight of oxides: 65 to 70% of SiO2 18 to 23% ofAl2O3 > 4 to 5% ofLi2O 0 to < 1% of MgO 1 to 3% of ZnO 0 to 2% of BaO 1.8 to 4% ofTiO2 1 to 2.5% of ZrO2 0.4 to 1 % of K2O and/or Na2O; with, advantageously, an effective and non-excess amount of at least one fining agent; and (ii) it has a β-OU. value of higher than 0.2 mm"1, preferably higher than 0.4 mm'1.
7. A method of preparing a glass-ceramic material or article according to any one of claims 1 to 4, characterized in that it comprises heat-treating a crystallizable inorganic glass precursor of the glass-ceramic according to claim 6 under conditions which ensure its ceramization.
8. The method according to claim 7, characterized in that said heat treatment comprises a step of crystallization at a temperature of between 1,050 and 1,200°C.
9. The method according to claim 7, characterized in that said heat treatment comprises a step of crystallization at a temperature of between 840 and 900°C.
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| JP2006544372A JP4925187B2 (en) | 2003-12-17 | 2004-12-17 | Glass and glass ceramic materials, products and methods for their preparation |
| EP04804063.8A EP1704125B8 (en) | 2003-12-17 | 2004-12-17 | Glass and glass-ceramic materials, articles and method of preparing the same |
| KR1020067014276A KR101050281B1 (en) | 2003-12-17 | 2004-12-17 | Glass and Glass-Ceramic Materials, Products, and Methods for Making the Same |
| CN2004800381046A CN1898170B (en) | 2003-12-17 | 2004-12-17 | Glass and glass-ceramic material, article and method of preparing the same |
| ES04804063T ES2404281T3 (en) | 2003-12-17 | 2004-12-17 | Glass and glass ceramic materials, articles and corresponding preparation procedure |
| HK07104966.5A HK1098452A1 (en) | 2003-12-17 | 2007-05-10 | Glass and glass-ceramic materials, articles and method of preparing the same |
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| FR0314834 | 2003-12-17 | ||
| FR0314834A FR2864071A1 (en) | 2003-12-17 | 2003-12-17 | Improved vitroceramic from a glass precursor with transparent, translucent or opaque aspects for cooking plates and other fire resistant applications |
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| WO2005058766A1 true WO2005058766A1 (en) | 2005-06-30 |
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| US (1) | US7153795B2 (en) |
| EP (1) | EP1704125B8 (en) |
| JP (1) | JP4925187B2 (en) |
| KR (1) | KR101050281B1 (en) |
| CN (1) | CN1898170B (en) |
| ES (1) | ES2404281T3 (en) |
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- 2004-12-17 CN CN2004800381046A patent/CN1898170B/en active Active
- 2004-12-17 ES ES04804063T patent/ES2404281T3/en active Active
- 2004-12-17 WO PCT/EP2004/014463 patent/WO2005058766A1/en active Application Filing
- 2004-12-17 EP EP04804063.8A patent/EP1704125B8/en active Active
- 2004-12-17 KR KR1020067014276A patent/KR101050281B1/en active IP Right Grant
- 2004-12-17 JP JP2006544372A patent/JP4925187B2/en active Active
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| EP2094879A1 (en) * | 2006-11-27 | 2009-09-02 | Momentive Performance Materials Inc. | Quartz encapsulated heater assembly |
| EP3018107A1 (en) | 2014-11-06 | 2016-05-11 | Schott AG | Highly crystalline lithium aluminium silicate glass ceramic material and use of same |
| DE102014222645A1 (en) | 2014-11-06 | 2016-05-12 | Schott Ag | Highly crystalline lithium aluminum silicate glass-ceramic and its use |
| US10562808B2 (en) | 2014-11-06 | 2020-02-18 | Schott Ag | Highly crystalline lithium aluminium silicate glass-ceramic and its use |
| WO2016193171A1 (en) | 2015-05-29 | 2016-12-08 | Eurokera | Transparent, essentially colorless, tin-fined las glass-ceramics with improved microstructure and thermal expansion properties |
| DE202016007247U1 (en) | 2015-05-29 | 2016-12-21 | Eurokera S.N.C. | Transparent, substantially colorless, tin-refined Las glass-ceramic with improved microstructure and thermal expansion properties |
| US10961146B2 (en) | 2015-05-29 | 2021-03-30 | Eurokera | Transparent, essentially colorless, tin-fined las glass-ceramics with improved microstructure and thermal expansion properties |
| CN111908793A (en) * | 2020-06-29 | 2020-11-10 | 成都光明光电股份有限公司 | Glass-ceramic and glass-ceramic article with spinel crystal phase |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101050281B1 (en) | 2011-07-19 |
| EP1704125B1 (en) | 2013-02-13 |
| HK1098452A1 (en) | 2007-07-20 |
| ES2404281T3 (en) | 2013-05-27 |
| EP1704125B8 (en) | 2013-04-24 |
| JP4925187B2 (en) | 2012-04-25 |
| JP2007518657A (en) | 2007-07-12 |
| CN1898170B (en) | 2011-12-07 |
| US7153795B2 (en) | 2006-12-26 |
| EP1704125A1 (en) | 2006-09-27 |
| FR2864071A1 (en) | 2005-06-24 |
| CN1898170A (en) | 2007-01-17 |
| KR20060117992A (en) | 2006-11-17 |
| US20050143246A1 (en) | 2005-06-30 |
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