WO2010090208A1 - 結晶化ガラスおよびそれを用いた調理器用トッププレート - Google Patents
結晶化ガラスおよびそれを用いた調理器用トッププレート Download PDFInfo
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- WO2010090208A1 WO2010090208A1 PCT/JP2010/051490 JP2010051490W WO2010090208A1 WO 2010090208 A1 WO2010090208 A1 WO 2010090208A1 JP 2010051490 W JP2010051490 W JP 2010051490W WO 2010090208 A1 WO2010090208 A1 WO 2010090208A1
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- Prior art keywords
- glass
- crystallized glass
- less
- transmittance
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- 239000011521 glass Substances 0.000 title claims abstract description 146
- 238000010411 cooking Methods 0.000 title claims description 9
- 239000013078 crystal Substances 0.000 claims description 66
- 238000002834 transmittance Methods 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 29
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 27
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 26
- 230000008859 change Effects 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- 238000002835 absorbance Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 11
- 239000006064 precursor glass Substances 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 abstract description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract description 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 26
- 238000002425 crystallisation Methods 0.000 description 23
- 230000008025 crystallization Effects 0.000 description 23
- 238000000034 method Methods 0.000 description 19
- 230000007423 decrease Effects 0.000 description 16
- 238000000465 moulding Methods 0.000 description 16
- 229910000500 β-quartz Inorganic materials 0.000 description 16
- 238000004040 coloring Methods 0.000 description 15
- 238000004031 devitrification Methods 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 12
- 230000007774 longterm Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 230000001133 acceleration Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- 239000003086 colorant Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 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 description 4
- 239000006103 coloring component Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 229910052644 β-spodumene Inorganic materials 0.000 description 4
- 238000006124 Pilkington process Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000156 glass melt Substances 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000007372 rollout process Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000004017 vitrification Methods 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
- 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
- C03C10/0036—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 a divalent metal oxide 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
- 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
- C03C10/0036—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 a divalent metal oxide as main constituents
- C03C10/0045—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 a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
Definitions
- This invention relates to the crystallized glass used for the top plate of the cooking appliance which uses IH (electromagnetic heating apparatus), a halogen heater, etc. as a heat source.
- IH electromagnettic heating apparatus
- a halogen heater etc.
- the top plate used in cooking devices that use IH, halogen heaters, etc. as the heat source is not easily damaged (high mechanical strength and thermal shock resistance), beautiful in appearance, and hardly corroded (high chemical durability) ) And high transmittance of infrared rays, which are heat rays.
- As a material satisfying such characteristics there is a low-expansion transparent crystallized glass whose main crystal is ⁇ -quartz solid solution (Li 2 O—Al 2 O 3 —nSiO 2 (n ⁇ 2)). It is used.
- Low-expansion transparent crystallized glass is a compounding process in which various glass raw materials are mixed at a predetermined ratio, a melting process in which glass raw materials are melted at a high temperature of 1600 to 1900 ° C. to obtain a homogenized fluid, and various shapes are obtained by various methods It is manufactured through a molding process for molding, an annealing process for removing strain, and a crystallization process for precipitating fine crystals.
- the crystallization step includes a nucleation step for precipitating microcrystals serving as crystal nuclei and a crystal growth step for growing crystals.
- the low-expansion transparent crystallized glass produced in this way is generally transparent to visible light, when it is used as it is as a top plate, the internal structure of the cooker arranged below the top plate can be directly seen. It is inferior in appearance. Therefore, the crystallized glass itself is colored with a colorant such as V 2 O 5 (for example, see Patent Document 1), or a light shielding film is formed on the surface of the crystallized glass (for example, see Patent Document 2). Used in a state where the visible light is sufficiently shielded.
- a colorant such as V 2 O 5
- a light shielding film is formed on the surface of the crystallized glass
- the crystallized glass described in Patent Document 3 has excellent infrared transmittance at the start of use, but has a problem that the infrared transmittance decreases as it is used for a long time.
- the ability to maintain high infrared transmittance even after long-term use is important from the viewpoint of energy saving as well as cooking performance.
- the present invention provides a crystallized glass having a sufficient visible light shielding performance, a high infrared transmittance, and whose properties are not impaired even after long-term use, and a top plate for a cooker using the same. It is a technical subject to do.
- the present invention relates to a crystallized glass characterized by substantially not containing 2 O 3 and Sb 2 O 3 .
- V 2 O 5 has a function as a colorant, and also has an effect of reducing infrared transmittance.
- the content of V 2 O 5 is suppressed as low as 0.02 to 0.1% and the mixing ratio of SnO 2 and V 2 O 5 is V 2 O 5 / (SnO 2 + V 2 O 5 ). Is adjusted to be 0.2 to 0.4, and the content of TiO 2 is adjusted to be relatively high as 4 to 5.5%. It has become possible to increase the coloring efficiency of V 2 O 5 so that the internal structure of the cooking device can be shielded.
- the crystallized glass of the present invention preferably has a Na 2 O content of 0.5% or less.
- the crystallized glass of the present invention preferably further contains 0 to 2.3% of ZrO 2 .
- the total amount of TiO 2 and ZrO 2 is preferably 4 to 6.5%.
- the crystallized glass of the present invention preferably has a transmittance at a thickness of 3 mm of 35% or less at a wavelength of 700 nm and 85% or more at a wavelength of 1150 nm.
- the transmittance of crystallized glass is measured using a sample whose surface is mirror-polished.
- the inventors of the present invention have a decrease in visible light and infrared transmission performance due to long-term use, because crystallization has not progressed sufficiently, and crystallization further proceeds by further heating. It was determined that the cause was the change in the composition of the matrix glass phase. Then, it discovers that the said subject can be solved by performing heat processing so that crystallization fully advances, and proposes as 2nd this invention.
- the method for producing crystallized glass of the present invention preferably further includes (4) a step of growing the crystal by heat-treating the precursor glass having crystal nuclei formed in a temperature range of 800 to 930 ° C. for at least 10 minutes. .
- a step of growing the crystal by heat-treating the precursor glass having crystal nuclei formed in a temperature range of 800 to 930 ° C. for at least 10 minutes.
- the crystallized glass produced by the method for producing crystallized glass of the present invention has an absorbance change rate of, for example, 20% or less at a wavelength of 700 nm after heat treatment at 900 ° C. for 50 hours.
- the coloring mechanism of crystallized glass is as follows.
- V ions are mainly present in a trivalent to pentavalent state, but it is estimated that coloring of the crystallized glass is caused by tetravalent V ions present in the matrix glass phase. Furthermore, it is known that when the tetravalent V ions are combined with TiO 2 present in the matrix glass phase, the degree of coloring is further increased (visible light transmittance is reduced). Thus, the coloring of crystallized glass is greatly influenced by the amount of tetravalent V ions and TiO 2 in the matrix glass phase.
- V 2 O 5 and SnO 2 affects the degree of coloring.
- crystallized glass of the present invention when used as a top plate for a cooker for a long period of time, crystallization further proceeds by heating during use.
- the matrix glass composition changes, and in the matrix glass phase, the concentrations of tetravalent V ions and TiO 2 that do not contribute to the crystal composition are relatively increased.
- the binding state of tetravalent V ions and TiO 2 changes, and the transmittance in the visible region and the infrared region changes.
- the bond between tetravalent V ions and TiO 2 can be obtained even when the matrix glass composition changes due to long-term use.
- the state hardly changes and the visible light transmittance hardly changes.
- the crystallized glass of the present invention is a crystallized glass containing a ⁇ -quartz solid solution as a main crystal.
- the ⁇ -quartz solid solution Li 2 O—Al 2 O 3
- the ⁇ -quartz solid solution can be transformed from a ⁇ -quartz solid solution by heating due to long-term use. It has the property of causing crystal transition to -nSiO 2 (n ⁇ 4) and causing white turbidity.
- nSiO 2 nSiO 2
- white turbidity When white turbidity occurs in the crystallized glass, the appearance changes and the infrared transmittance decreases due to scattering.
- 2 O 3 and Sb 2 O 3 are known to be components having a large effect of promoting crystal transition.
- the crystallized glass of the present invention does not substantially contain As 2 O 3 and Sb 2 O 3 , the crystallized glass is characterized in that it hardly undergoes crystal transition and has a small change in transmittance in the visible region and infrared region due to long-term use.
- V 2 O 5 is also known to have an effect of promoting crystal transition, and by limiting the content of V 2 O 5 to be small as in the first aspect of the present invention, The effect can be enhanced.
- crystallized glass of the present invention does not substantially contain these components, it can reduce the environmental burden at the time of disposal.
- “substantially does not contain” refers to a level in which these components are not intentionally added as raw materials but mixed as impurities contained in various glass raw materials. Specifically, the content is It means 0.1% or less.
- SiO 2 forms a glass skeleton and is a component constituting a ⁇ -quartz solid solution.
- the content of SiO 2 is 55 to 73%, preferably 60 to 71%, more preferably 63 to 70%.
- the thermal expansion coefficient tends to increase, and it becomes difficult to obtain crystallized glass having excellent thermal shock resistance.
- chemical durability tends to decrease.
- the content of SiO 2 is increased, the meltability of the glass is lowered, or the viscosity of the glass melt is increased, so that it is difficult to form the glass.
- Al 2 O 3 forms a glass skeleton and is a component constituting a ⁇ -quartz solid solution.
- the content of Al 2 O 3 is 17 to 25%, preferably 17.5 to 24%, more preferably 18 to 22%.
- the content of Al 2 O 3 decreases, the thermal expansion coefficient tends to increase, and it becomes difficult to obtain crystallized glass excellent in thermal shock resistance. In addition, chemical durability tends to decrease.
- the content of Al 2 O 3 increases, the meltability of the glass decreases, the viscosity of the glass melt increases, and it tends to be difficult to form the glass. Further, the glass tends to be devitrified due to the precipitation of mullite crystals, and cracks are likely to occur in the glass from the devitrified portion, so that molding becomes difficult.
- Li 2 O is a component that constitutes a ⁇ -quartz solid solution, has a great influence on crystallinity, and lowers the viscosity of the glass to improve the meltability and moldability.
- the content of Li 2 O is 2 to 5%, preferably 2.3 to 4.7%, more preferably 2.5 to 4.5%.
- the glass tends to be devitrified by mullite crystals, and cracks are likely to be generated in the glass from the devitrified portion, so that molding becomes difficult.
- ⁇ -quartz solid solution crystals are difficult to precipitate, making it difficult to obtain crystallized glass having excellent thermal shock resistance.
- the meltability of the glass tends to decrease or the viscosity of the glass melt tends to increase, making it difficult to mold the glass.
- the content of Li 2 O increases, the crystallinity becomes too strong and coarse crystals are likely to precipitate in the crystallization process. As a result, it becomes cloudy and a transparent crystallized glass cannot be obtained or is easily damaged. It becomes difficult to form.
- TiO 2 is a component constituting a crystal nucleus for precipitating a crystal in the crystallization step, and has an action of enhancing the coloration of tetravalent V ions.
- the content of TiO 2 is 4 to 5.5%, preferably 4.1 to 5.3%, more preferably 4.2 to 5.1%.
- the concentration of tetravalent V ions and TiO 2 in the glass matrix increases, and the bonding state of the two changes. (Especially, the color becomes darker).
- SnO 2 is a component that enhances color development by increasing tetravalent V ions, which are coloring components.
- the SnO 2 content is 0.05 to less than 0.2%, preferably 0.06 to 0.18%, more preferably 0.07 to 0.15%.
- tetravalent V ions are not efficiently generated, so that the coloring effect is hardly increased.
- the content of SnO 2 is increased, the glass tends to be devitrified when it is melted and molded, so that the molding becomes difficult.
- the content of SnO 2 increases, the color tone tends to easily change due to slight differences in melting conditions and crystallization conditions even if the composition is the same.
- V 2 O 5 is a coloring component.
- the content of V 2 O 5 is 0.02 to 0.1%, preferably 0.02 to 0.05%.
- the coloring becomes thin and the visible light cannot be sufficiently shielded.
- the infrared transmittance tends to decrease.
- the crystal transition from ⁇ -quartz solid solution to ⁇ -spodumene solid solution is likely to cause white turbidity.
- the mixing ratio of V 2 O 5 and SnO 2 2 is such that V 2 O 5 / (SnO 2 + V 2 O 5 ) is 0.2 to 0.4, preferably 0.25 to 0.35, in terms of mass ratio. Even if the mixing ratio of V 2 O 5 and SnO 2 is larger or smaller than the above range, the amount of tetravalent V ions is reduced, so that it is difficult to obtain a high coloring effect.
- MgO is a component that dissolves in ⁇ -quartz solid solution crystals instead of Li 2 O.
- the content of MgO is 0 to 1.5%, preferably 0 to 1.4%, more preferably 0.1 to 1.2%.
- the content of MgO is increased, the crystallinity becomes too strong and tends to devitrify, and as a result, the glass is easily broken and molding becomes difficult.
- ZnO is a component that dissolves in ⁇ -quartz solid solution crystal in the same manner as MgO.
- the content of ZnO is 0 to 1.5%, preferably 0 to 1.4%, more preferably 0.1 to 1.2%.
- the crystallinity tends to be too strong. For this reason, if the glass is molded while being slowly cooled, the glass tends to devitrify and break, and thus, for example, it is not suitable for molding by the float process.
- ZrO 2 is a component constituting a crystal nucleus for precipitating crystals in the crystallization step, like TiO 2 .
- the content of ZrO 2 is 0 to 2.3%, preferably 0 to 2.1%, more preferably 0.1 to 1.8%.
- the glass tends to be devitrified in the melting and forming process of the glass, making it difficult to form the glass.
- P 2 O 5 is a component that promotes phase separation of glass. Since crystal nuclei are likely to be generated at the place where the glass is phase-separated, P 2 O 5 serves to assist the formation of crystal nuclei.
- the content of P 2 O 5 is 0 to 2%, preferably 0.1 to 1%. When the content of P 2 O 5 increases, phase separation occurs in the melting step, so that it becomes difficult to obtain a glass having a desired composition and tends to be opaque.
- the total amount of TiO 2 and ZrO 2 is 4 to 6.5%, preferably 4.5 to 6%.
- the glass tends to be devitrified in the melting and forming process, and it becomes difficult to form the glass.
- the total amount of these components is too small, crystal nuclei are not sufficiently formed, and the crystal is likely to be coarsened. As a result, it becomes difficult to obtain a crystallized glass that is cloudy and transparent.
- Na 2 O is a component that lowers the viscosity of the glass and improves glass meltability and moldability.
- the content of Na 2 O is 0.5% or less, preferably 0.3% or less, more preferably 0.2% or less.
- the thermal expansion coefficient tends to be high, and it becomes difficult to obtain crystallized glass excellent in thermal shock resistance.
- CaO, SrO, and BaO are components that cause devitrification when the glass is melted. Therefore, the total amount of these components is preferably 2% or less. Further, since CaO has an action of promoting crystal transition from ⁇ -quartz solid solution to ⁇ -spodumene solid solution, it is better to refrain from using it as much as possible.
- SO 2 and Cl may be added alone or in combination as necessary.
- the total amount of these components is desirably 0.5% or less.
- 2 O 3 and Sb 2 O 3 are also clarifying components, but are components that are considered to have a large environmental load, and it is important that they are not substantially contained.
- Colored transition metal elements not described above absorb infrared rays or lose the ability to reduce Sn ions. Since it may react with Sn ions and, as a result, the reaction between V ions and Sn ions may be hindered), it is preferably not contained as much as possible.
- the crystallized glass of the present invention preferably has a transmittance at a wavelength of 700 nm of 35% or less, more preferably 30% or less at a thickness of 3 mm, thereby sufficiently shielding the internal structure of the cooker.
- permeability in wavelength 700nm is 15% or more, 18% or more, and also 20% or more in 3 mm thickness.
- the crystallized glass of the present invention preferably has a change rate of absorbance of 10% or less at a wavelength of 700 nm after heat treatment at 900 ° C. for 50 hours.
- the rate of change in absorbance is calculated as follows.
- Absorbance log 10 (transmittance (%) / 100)
- Absorbance change rate (Absorbance after heat treatment ⁇ Absorbance before heat treatment) / Absorbance before heat treatment ⁇ 100 (%)
- the crystallized glass of the present invention is preferably 3% thick and has a transmittance of 85% at a wavelength of 1150 nm, more preferably 86% or more, because it can efficiently transmit heat rays (infrared rays).
- the amount of change in transmittance at a wavelength of 1150 nm after heat treatment at 900 ° C. for 50 hours as an accelerated test is 5% or less, 3% or less, 2% or less, 1.5%
- the change in transmittance at a wavelength of 700 nm is preferably 5% or less, 3% or less, 2% or less, 1.5% or less, particularly preferably 1% or less.
- the thermal expansion coefficient of the crystallized glass of the present invention in the temperature range of 30 to 750 ° C. is preferably ⁇ 10 to 30 ⁇ 10 ⁇ 7 / ° C., more preferably ⁇ 10 to 20 ⁇ 10 ⁇ 7 / ° C.
- the thermal expansion coefficient is a value measured with a dilatometer.
- the crystallized glass of the present invention can be produced as follows.
- various glass raw materials are prepared so as to have the above composition. If necessary, MgO and ZnO solid solution in the crystal by replacing a part of Li 2 O, components for improving the melting property and formability of the glass, may be added to fining agent.
- the prepared glass raw material is melted at a temperature of 1600 to 1900 ° C. and then molded to obtain crystalline glass.
- various molding methods such as a blow method, a press method, a roll-out method, and a float method can be applied.
- heat treatment is performed at 700 to 800 ° C. for 10 minutes to 10 hours to form crystal nuclei, followed by heat treatment at 800 to 900 ° C. for 10 minutes to 10 hours to grow ⁇ -quartz solid solution crystals. To obtain crystallized glass.
- the crystallized glass produced in this way may be subjected to post-processing such as cutting, polishing, bending, reheat pressing, etc., and the surface may be painted or filmed.
- Tables 1 to 3 show Examples (Sample Nos. 1 to 7 and 12) and Comparative Examples (Sample Nos. 8 to 11, 13, and 14) of the first present invention.
- Glass raw materials were prepared so as to have the compositions shown in Tables 1 to 3, and were melted at 1600 ° C. for 20 hours and further at 1700 ° C. for 4 hours using a platinum crucible. Two spacers having a thickness of 5 mm were placed on the carbon plate, and molten glass was poured out between the spacers, and leveled with a roller to form a plate shape.
- the obtained plate-like sample was put into an electric furnace maintained at 700 ° C., held for 30 minutes, then turned off, and cooled to room temperature in the furnace over 10 hours.
- the cooled sample was crystallized with an electric furnace to obtain crystallized glass.
- the profile was such that nucleation was 770 ° C. for 3 hours and crystal growth was 880 ° C. for 1 hour.
- Each crystallized glass was evaluated for transmittance and devitrification in the visible and infrared regions.
- the transmittance was measured for 700 nm and 1150 nm using a spectrophotometer (V-760, manufactured by JASCO Corporation) by processing each crystallized glass into a 3 mm thick sample whose surfaces were mirror-polished.
- the measurement conditions were a measurement range of 1500 to 380 nm and a scan speed of 200 nm / min.
- permeability was similarly measured about the sample which performed the heat processing (acceleration test) for 50 hours at 900 degreeC.
- Devitrification was evaluated by determining whether or not devitrification occurs in an electric furnace set at 1350 ° C. while holding each sample on a platinum foil for 24 hours. If no devitrification was confirmed, “ ⁇ ” was indicated. If devitrification was confirmed, “x” was indicated.
- the sample No. Nos. 1 to 7 and 12 can sufficiently block light in the visible region and have high infrared transmittance, and it is understood that the transmittance change in the visible and infrared regions is small even in an acceleration test assuming long-term use. .
- sample No. which is a comparative example. No. 8 had a large change width of transmittance in the visible and infrared regions after the acceleration test.
- Sample No. which is a comparative example. 9 and 11 were not sufficiently low in transmittance in the visible region after crystallization.
- sample No. In No. 9 devitrification was confirmed.
- No. which is a comparative example. No. 10 was not sufficiently high in transmittance in the infrared region after crystallization, and devitrification was confirmed.
- sample No. In 13 and 14 the change in transmittance (absorbance) before and after the heat treatment was large.
- the raw material powder is prepared so as to have a composition containing 0.01 to 0.3%, V 2 O 5 0.02 to 0.2%, and substantially free of As 2 O 3 and Sb 2 O 3. .
- the reason for limiting to the composition in this way will be described below.
- TiO 2 is a component constituting a crystal nucleus for precipitating a crystal in the crystallization step, and has an action of enhancing the coloration of tetravalent V ions.
- the content of TiO 2 is 2.6 to 5.5%, preferably 2.6 to 5%, more preferably 2.8 to 4.8%, and further preferably 3 to 4.5%. When the content of TiO 2 decreases, the amount remaining in the matrix glass phase without being used as crystal nuclei decreases, so that it is difficult to combine with tetravalent V ions, and the color development efficiency tends to be low.
- SnO 2 is a component that enhances color development by increasing tetravalent V ions, which are coloring components.
- the SnO 2 content is 0.01-0.3%, preferably 0.03-0.25%, more preferably 0.05-0.23%.
- tetravalent V ions are not efficiently generated, so that the coloring effect is hardly increased.
- the content of SnO 2 is increased, the glass tends to be devitrified when it is melted and molded, so that the molding becomes difficult. Further, even with the same composition, the color tone tends to change easily due to slight differences in melting conditions and crystallization conditions.
- V 2 O 5 is a coloring component.
- the content of V 2 O 5 is 0.02 to 0.2%, preferably 0.03 to 0.15%.
- the coloring becomes thin and the visible light cannot be sufficiently shielded.
- the infrared transmittance tends to decrease.
- the crystal transition from ⁇ -quartz solid solution to ⁇ -spodumene solid solution is likely to cause white turbidity.
- various components can be added as long as the required properties are not impaired.
- MgO, ZnO, ZrO 2 , P 2 O 5 , Na 2 O, K 2 O, CaO, SrO, BaO, SO 2 , Cl are also the same for the same reason described in relation to the first invention described above. You may add in the range of content.
- ZrO 2 is added, the total amount of TiO 2 and ZrO 2 is 3.8 to 6.5%, preferably 4.2 to 6%.
- the glass tends to be devitrified in the melting and forming process, and it becomes difficult to form the glass.
- the raw material powder prepared as described above is melted to obtain a crystalline precursor glass.
- the melting temperature is not particularly limited, but is preferably 1600 to 1900 ° C., for example, in order to sufficiently promote vitrification.
- molding methods such as a blow method, a press method, a rollout method, and a float method, are applicable.
- the formed precursor glass is subjected to annealing as necessary.
- the precursor glass is heat-treated at a temperature range of 765 to 785 ° C. for at least 10 minutes.
- Crystal nuclei can be precipitated in the heat treatment step.
- the temperature range of 765 to 785 ° C. is the range where nucleation is most likely to occur, and crystal nuclei can be sufficiently formed.
- the heat treatment time is shorter than 10 minutes, the color immediately after crystallization is light and tends to cause white turbidity.
- the upper limit of the heat treatment time is preferably 10 hours or less, 3 hours or less, particularly 2 hours or less.
- the precursor glass on which crystal nuclei are formed is further subjected to heat treatment to cause crystal growth to obtain a desired crystallized glass.
- the heat treatment is preferably performed at 800 to 930 ° C., preferably 850 to 920 ° C., more preferably 870 to 890 ° C. for at least 10 minutes in order to sufficiently promote crystallization.
- the heat treatment time is shorter than 10 minutes, the color immediately after crystallization is light and tends to cause white turbidity.
- the upper limit of the heat treatment time is preferably 10 hours or less, 3 hours or less, particularly 2 hours or less.
- the crystallized glass obtained by the production method of the present invention has a thickness of 3 mm and a transmittance at a wavelength of 700 nm of 35% or less, more preferably 30% or less, thereby sufficiently shielding the internal structure of the cooker. It becomes possible.
- the transmittance at a wavelength of 700 nm is 15% or more, and further 18% or more at a thickness of 3 mm. Thereby, when it uses for the top plate of a cooking appliance, it becomes possible to fully recognize the display by LED etc. through crystallized glass.
- the crystallized glass of the present invention is preferably 3% thick and having a transmittance at a wavelength of 1150 nm of 85% or more, and more preferably 86% or more because it can efficiently transmit heat rays (infrared rays).
- the crystallized glass of the present invention is 3 mm thick, and the change in transmittance at a wavelength of 1150 nm after heat treatment at 900 ° C. for 50 hours as an accelerated test is 5% or less, 3% or less, particularly 2% or less. Preferably there is.
- the change in transmittance at a wavelength of 700 nm is preferably 5% or less, 3% or less, particularly 2% or less.
- the crystallized glass of the present invention preferably has an absorbance change rate (calculated by the above-described calculation formula) at a wavelength of 700 nm after heat treatment at 900 ° C. for 50 hours of 20% or less, particularly preferably 10% or less.
- the thermal expansion coefficient of the crystallized glass of the present invention in the temperature range of 30 to 750 ° C. is preferably ⁇ 10 to 30 ⁇ 10 ⁇ 7 / ° C., more preferably ⁇ 10 to 20 ⁇ 10 ⁇ 7 / ° C. When the thermal expansion coefficient is in this range, the glass has excellent thermal shock resistance.
- the crystallized glass obtained by the production method of the present invention may be subjected to post-processing such as cutting, polishing, bending, reheat press or the like, and the surface may be painted or filmed.
- the crystallized glass thus produced can be used as a top plate for IH cookers equipped with IH heaters, halogen heater cookers equipped with halogen heaters, gas cookers equipped with gas burners, and the like.
- Tables 4 and 5 show Examples of the second invention (Sample Nos. 15 to 19) and Comparative Examples (Sample Nos. 20 to 23).
- Glass raw materials were prepared so as to have the compositions shown in Tables 4 and 5, and melted at 1600 ° C. for 20 hours and further at 1700 ° C. for 4 hours using a platinum crucible. Two spacers having a thickness of 5 mm were placed on the carbon plate, molten glass was poured out between the spacers, and the plate was formed into a uniform thickness with a roller.
- the obtained plate-like sample was put into an electric furnace maintained at 700 ° C., held for 30 minutes, then turned off, and cooled (annealed) to room temperature in the furnace over 10 hours.
- Tables 4 and 5 show the heat treatment profile of each sample.
- the rate of temperature increase from room temperature to the nucleation temperature is 15 ° C./min
- the rate of temperature increase from the nucleation temperature to the crystal growth temperature is 10 ° C./min
- the temperature decrease from the crystal growth temperature to room temperature is 80 ° C./min. did.
- Each crystallized glass was evaluated for transmittance and devitrification in the visible and infrared regions.
- the transmittance was measured for 700 nm and 1150 nm using a spectrophotometer (V-760, manufactured by JASCO Corporation) by processing each crystallized glass into a 3 mm thick sample whose surfaces were mirror-polished.
- the measurement conditions were a measurement range of 1500 to 380 nm and a scan speed of 200 nm / min.
- permeability was similarly measured about the sample which performed the heat processing (acceleration test) for 50 hours at 900 degreeC.
- the rate of change in absorbance after the acceleration test was calculated according to the above formula.
- Devitrification was evaluated by determining whether or not devitrification occurs in an electric furnace set at 1350 ° C. while holding each sample on a platinum foil for 24 hours. If no devitrification was confirmed, “ ⁇ ” was indicated. If devitrification was confirmed, “x” was indicated.
- sample No. which is a comparative example The crystallized glass of 21 to 23 had a large absorbance change rate in the visible region after the acceleration test.
- sample No. which is a comparative example The appearance of 20 crystallized glass was cloudy in appearance.
- the crystallized glass of the present invention is suitable as a top plate for cooking appliances such as gas, IH and halogen heaters. It can also be used for observation windows and fireproof windows for observation in high-temperature furnaces where low-expansion crystallized glass with ⁇ -quartz solid solution as the main crystal has been used.
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- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
Description
吸光度変化率=(熱処理後の吸光度-熱処理前の吸光度)/熱処理前の吸光度×100(%)
Claims (11)
- 質量%で、SiO2 55~73%、Al2O3 17~25%、Li2O 2~5%、TiO2 4~5.5%、SnO2 0.05~0.2%未満、V2O5 0.02~0.1%、V2O5/(SnO2+V2O5)が0.2~0.4である組成を含有し、As2O3およびSb2O3を実質的に含有しないことを特徴とする結晶化ガラス。
- Na2Oの含有量が0.5%以下であることを特徴とする請求項1に記載の結晶化ガラス。
- さらに、ZrO2を0~2.3%含有することを特徴とする請求項1または2に記載の結晶化ガラス。
- TiO2とZrO2の合量が4~6.5%であることを特徴とする請求項3に記載の結晶化ガラス。
- 3mm厚での透過率が、波長700nmにおいて35%以下、かつ波長1150nmにおいて85%以上であることを特徴とする請求項1~4のいずれかに記載の結晶化ガラス。
- 請求項1~5のいずれかに記載の結晶化ガラスを用いてなる調理器用トッププレート。
- (1)質量%で、SiO2 55~73%、Al2O3 17~25%、Li2O 2~5%、TiO2 2.6~5.5%、SnO2 0.01~0.3%、V2O5 0.02~0.2%を含有し、As2O3およびSb2O3を実質的に含有しない組成となるように原料粉末を調合する工程、(2)原料粉末を溶融して前駆体ガラスを作製する工程、(3)前駆体ガラスを765~785℃の温度域で少なくとも10分間熱処理し結晶核を形成する工程、を含むことを特徴とする結晶化ガラスの製造方法。
- さらに、(4)結晶核が形成された前駆体ガラスを800~930℃の温度域で少なくとも10分間熱処理して結晶を成長させる工程を含むことを特徴とする請求項7に記載の結晶化ガラスの製造方法。
- 請求項7または8に記載の製造方法により作製されたことを特徴とする結晶化ガラス。
- 900℃で50時間熱処理した後の波長700nmにおける吸光度変化率が20%以下であることを特徴とする請求項9に記載の結晶化ガラス。
- 請求項9または10に記載の結晶化ガラスを用いてなる調理器用トッププレート。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/147,400 US20110283738A1 (en) | 2009-02-05 | 2010-02-03 | Crystallized glass and top plate for cooking device comprising same |
CN2010800056401A CN102300824A (zh) | 2009-02-05 | 2010-02-03 | 结晶化玻璃及使用该结晶化玻璃的烹调装置用顶板 |
EP10738539.5A EP2394970A4 (en) | 2009-02-05 | 2010-02-03 | CRYSTALLIZED GLASS AND TOP PLATE FOR COOKING DEVICE COMPRISING SUCH A GLASS |
Applications Claiming Priority (6)
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JP2009025398 | 2009-02-05 | ||
JP2009-025398 | 2009-02-05 | ||
JP2010-002761 | 2010-01-08 | ||
JP2010-002757 | 2010-01-08 | ||
JP2010002761 | 2010-01-08 | ||
JP2010002757A JP5645101B2 (ja) | 2009-02-05 | 2010-01-08 | 調理器用トッププレート |
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WO2010090208A1 true WO2010090208A1 (ja) | 2010-08-12 |
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Family Applications (1)
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PCT/JP2010/051490 WO2010090208A1 (ja) | 2009-02-05 | 2010-02-03 | 結晶化ガラスおよびそれを用いた調理器用トッププレート |
Country Status (4)
Country | Link |
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US (1) | US20110283738A1 (ja) |
EP (1) | EP2394970A4 (ja) |
CN (1) | CN102300824A (ja) |
WO (1) | WO2010090208A1 (ja) |
Cited By (3)
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US20130085058A1 (en) * | 2010-05-31 | 2013-04-04 | Nippon Electric Glass Co., Ltd. | Li2O-Al2O3-SiO2 BASED CRYSTALLIZED GLASS AND PRODUCTION METHOD FOR THE SAME |
WO2014027274A3 (de) * | 2012-08-14 | 2014-07-24 | BSH Bosch und Siemens Hausgeräte GmbH | Deckplatte mit integriertem topfträger für eine gaskochstelle, gaskochstelle und gaskochfeld |
WO2014027270A3 (de) * | 2012-08-14 | 2014-07-24 | BSH Bosch und Siemens Hausgeräte GmbH | Brennerdeckel und topfträger für eine gaskochstelle, gaskochstelle und gaskochfeld |
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JP2013249221A (ja) * | 2012-05-31 | 2013-12-12 | Nippon Electric Glass Co Ltd | Li2O−Al2O3−SiO2系結晶化ガラス及びその製造方法 |
US20140309099A1 (en) | 2013-04-15 | 2014-10-16 | Ppg Industries Ohio, Inc. | Low iron, high redox ratio, and high iron, high redox ratio, soda-lime-silica glasses and methods of making same |
US11261122B2 (en) * | 2013-04-15 | 2022-03-01 | Vitro Flat Glass Llc | Low iron, high redox ratio, and high iron, high redox ratio, soda-lime-silica glasses and methods of making same |
US20220081348A1 (en) * | 2019-04-23 | 2022-03-17 | Nippon Electric Glass Co., Ltd. | Li2O-Al2O3-SiO2-BASED CRYSTALLIZED GLASS |
DE102020202602A1 (de) * | 2020-02-28 | 2021-09-02 | Schott Ag | Kristallisierbares Lithiumaluminiumsilikat-Glas und daraus hergestellte Glaskeramik sowie Verfahren zur Herstellung des Glases und der Glaskeramik und Verwendung der Glaskeramik |
CN111517640B (zh) * | 2020-06-30 | 2021-03-02 | 成都光明光电股份有限公司 | 环保玻璃材料 |
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US7456121B2 (en) * | 2006-06-23 | 2008-11-25 | Eurokera | Glass-ceramic materials, precursor glass thereof and process-for making the same |
FR2946041B1 (fr) * | 2009-05-29 | 2012-12-21 | Eurokera | Vitroceramiques et articles en vitroceramique, notamment plaques de cuisson, colores |
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2010
- 2010-02-03 EP EP10738539.5A patent/EP2394970A4/en not_active Withdrawn
- 2010-02-03 US US13/147,400 patent/US20110283738A1/en not_active Abandoned
- 2010-02-03 WO PCT/JP2010/051490 patent/WO2010090208A1/ja active Application Filing
- 2010-02-03 CN CN2010800056401A patent/CN102300824A/zh active Pending
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US20130085058A1 (en) * | 2010-05-31 | 2013-04-04 | Nippon Electric Glass Co., Ltd. | Li2O-Al2O3-SiO2 BASED CRYSTALLIZED GLASS AND PRODUCTION METHOD FOR THE SAME |
US9120699B2 (en) * | 2010-05-31 | 2015-09-01 | Nippon Electric Glass Co., Ltd. | Li2O-Al2O3-SiO2 based crystallized glass and production method for the same |
WO2014027274A3 (de) * | 2012-08-14 | 2014-07-24 | BSH Bosch und Siemens Hausgeräte GmbH | Deckplatte mit integriertem topfträger für eine gaskochstelle, gaskochstelle und gaskochfeld |
WO2014027270A3 (de) * | 2012-08-14 | 2014-07-24 | BSH Bosch und Siemens Hausgeräte GmbH | Brennerdeckel und topfträger für eine gaskochstelle, gaskochstelle und gaskochfeld |
Also Published As
Publication number | Publication date |
---|---|
CN102300824A (zh) | 2011-12-28 |
EP2394970A4 (en) | 2013-06-26 |
EP2394970A1 (en) | 2011-12-14 |
US20110283738A1 (en) | 2011-11-24 |
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