CN104370469B

CN104370469B - A kind of colour devitrified glass of ultralow-expansion coefficient high transparent and preparation method thereof

Info

Publication number: CN104370469B
Application number: CN201410585489.3A
Authority: CN
Inventors: 蒋达光
Original assignee: Individual
Current assignee: Individual
Filing date: 2014-10-28
Publication date: 2017-01-04
Anticipated expiration: 2034-10-28

Abstract

The solvent of the colour devitrified glass of a kind of ultralow-expansion coefficient high transparent, by weight percentage devitrified glass is: include the SiO of 65～69%₂, 19～the Al of 20%₂O₃, 3.1～the Li of 4.2%₂The B of O, 3～4.5%₂O₃, 0.1～the Na of 0.4%₂The K of O, 0.1～0.4%₂The TiO of the ZnO of the BaO of the MgO of O, 0.3～0.5%, 0.6～1.4%, 0.6～1.4%, 1.0～1.7%₂, 1.0～the ZrO of 1.3%₂, 0.4～the P of 0.8%₂O₅, 0.3～the CeO of the F of 0.8% and 0.02～0.3%₂；In the case of solvent weight is 100%, another addition is less than the coloring agent of solvent gross weight 4%.The colour devitrified glass transparency of the present invention is high, the coefficient of expansion is ultralow and can make the goods of big size or labyrinth.

Description

A kind of colour devitrified glass of ultralow-expansion coefficient high transparent and preparation method thereof

Technical field

The present invention relates to a kind of Li₂O～Al₂O₃～SiO₂Microcrystalline glass in series technical field, concretely relate to colour devitrified glass of a kind of ultralow-expansion coefficient high transparent and preparation method thereof, this colour devitrified glass and colour devitrified glass goods thereof can be used in requiring under the coldest extreme thermal environment in the flameproof ware of super-low expansion coefficient, the high grade of transparency etc., crystallized glass article that be suitable as big size or labyrinth, that can be used safely in diet cooking industry, such as the cooker of open firing, kitchen tools, tableware and laboratory heating vessels such as steaming and decocting kitchen tools pot, frying pan, baking pots.

Background technology

Devitrified glass is chemical analysis and melts exigent specific composition glass, becomes at a certain temperature and have microcrystal composite mutually equally distributed with glass, also referred to as glass-ceramic after heat treatment.It has the premium properties such as low-expansion coefficient, mechanical strength height, chemical stability and Heat stability is good, use temperature height and hard wear resistant.Owing to glass composition in very large range adjusts, the crystalline phase of precipitation is tiny and is evenly distributed, because microcrystal glass material has many, other material cannot substituted superior function.Compared with quartz glass, devitrified glass has more preferable air-tightness owing to having separated out the crystallite of fine uniform, and therefore obtains higher mechanical strength；Simultaneously, the coefficient of expansion of devitrified glass in very large range can be adjusted by controlling the composition of crystalline phase, the glass kind that is obtained by of ultra-low-expansion glass ceramic separates out β～the eucryptite that C direction of principal axis is negative expansion, β～quartz solid solution, the crystalline phase such as α～eucryptite, with have just expanding participate in glass combined and obtain close to the zero thermal expansion even material of negative expansion, devitrified glass be by glass in heat treatment process controlling crystallizing and obtain the polycrystalline of residual glass phase and fix material, the crystallite crystalline phase separated out in glass is little and is evenly distributed, making microcrystal glass material have other materials many cannot substituted superior function, thus in national defence, aviation, transport, building, the field such as scientific research and life of production is as structural material, technologic material, electrically insulating material, optical materials etc. obtain and apply widely.

Current devitrified glass, major part is building decoration material, handicraft etc., also some is that the goods such as the heating plate disc for electromagnetic oven, microwave oven etc., baking sheet are (such as patent documentation 1: number of patent application is 200510034455.6, patent documentation 2: number of patent application is 200510079037.9), but the viscosity of this devitrified glass glass in its manufacture process is high, be not suitable for manufacturing the moulded products of compressing big size or labyrinth, such as steaming and decocting kitchen tools pot etc..And in the formula of devitrified glass, the most all select traditional arsenic oxide arsenoxide and/or stibium oxide to make glass fining agent, and exist environment and the pollution of glass, be also unsuitable for the heating vessels such as the cooker for diet cooking, kitchen tools, tableware.

Its Patent Literature 1(number of patent application is 200510034455.6) open a kind of microcrystalline glass formula, select TiO₂、ZrO₂And P₂O₅The combination of three kinds of Nucleating Agents, improves crystallization temperature scope, but does not has explanation to be suitable for making compressing big size or the crystallized glass articles of labyrinth such as steaming and decocting kitchen tools pot.Patent documentation 2(number of patent application is 200510079037.9) open a kind of microcrystalline glass formula, add the ratio of clarifier arsenic oxide arsenoxide and stibium oxide, improve transparency.Patent documentation 3(number of patent application is 200710029525.8) open a kind of microcrystalline glass formula, add yittrium oxide, reduce crystallization temperature.Patent documentation 4(number of patent application is 201010184813.2) disclose a kind of purplish-red glass-ceramic containing neodymium formula, using neodymium nitrate as coloring agent, and improve the content of lithium oxide, reduce the molten temperature processed of glass.Wherein neodymium element is used as nuclear reaction refuse.Patent documentation 5(number of patent application is 201110118778.9) open a kind of microcrystalline glass formula, add fluorine element, and potassium ion exchange treatment process.Patent documentation 2, patent documentation 3, patent documentation 4 and patent documentation 5 all selected arsenic oxide arsenoxide and or stibium oxide as clarifier, cannot be solved it be difficult to environment and the pollution problem of glass, this kind of crystallized glass article as heating vessels such as diet the cooking cooker of industry, kitchen tools, tablewares；Also it is difficult to as making compressing big size or the crystallized glass articles of labyrinth such as steaming and decocting kitchen tools pot.

Conventional devitrified glass is all milky or black, and mostly is edematus, owing to product color is dull, it is difficult to meet modern consumption crowd to the products such as cooker, kitchen tools, tableware double requirements in terms of using function and outward appearance art.

Summary of the invention

It is an object of the invention to the defect existed for prior art, it is provided that colour devitrified glass of ultralow-expansion coefficient high transparent of a kind of suitable for making big size or labyrinth and preparation method thereof.

It is an object of the invention to solve by the following technical programs:

The colour devitrified glass of a kind of ultralow-expansion coefficient high transparent, including parent glass, Nucleating Agent, clarifier and coloring agent, it is characterised in that: the solvent of devitrified glass by weight percentage is: include the SiO of 65～69%₂, 19～the Al of 20%₂O₃, 3.1～the Li of 4.2%₂The B of O, 3～4.5%₂O₃, 0.1～the Na of 0.4%₂The K of O, 0.1～0.4%₂The parent glass of the ZnO composition of the BaO and 0.6～1.4% of the MgO of O, 0.3～0.5%, 0.6～1.4%, 1.0～the TiO of 1.7%₂, 1.0～the ZrO of 1.3%₂, 0.4～the P of 0.8%₂O₅The Nucleating Agent formed with the F of 0.3～0.8%, and 0.02～the CeO of 0.3%₂As clarifier, CeO₂Incorporation make the visible light transmissivity of this devitrified glass when thickness is less than 4mm not less than 94.0%；In the case of above-mentioned solvent weight is 100%, another addition is less than the coloring agent of solvent gross weight 4%, and coloring agent is SrO, Y₂O₃、V₂O₅、Cr₂O₃、La₂O₃、MnO₂、Fe₂O₃、Co₂O₃、Ni₂O₃, one or more mixture in CuO；Above-mentioned frit through melted, molding, Crystallizing treatment i.e. can obtain containing the composition of β-quartz solid solution be Li₂O-Al₂O₃-2SiO₂Colour devitrified glass.

CeO in above-mentioned colour devitrified glass component₂With SiO₂The ratio CeO of content₂/SiO₂It is 0.0003～0.0043；CeO in above-mentioned colour devitrified glass component₂With Al₂O₃The ratio CeO of content₂/Al₂O₃It is 0.0010～0.0158.

CeO in above-mentioned colour devitrified glass component₂、SiO₂、Al₂O₃Weight percentage sum CeO of three₂+SiO₂+Al₂O₃=85.1～88.3%.

A kind of preparation method of the colour devitrified glass of ultralow-expansion coefficient high transparent, it is characterised in that: described preparation method is carried out in the steps below: (1) is according to the formula dispensing of colour devitrified glass；(2) mixing；(3) melted: solid glass raw material input melt temperature to be the melting furnace of 1400～1500 DEG C and keeps more than 24 hours, obtains the high temp glass stock solution of melting；(4) cooling: high temp glass stock solution is cooled to 1300～1330 DEG C；(5) molding: using die apparatus by compressing for original sheet glass for the high temp glass stock solution after cooling, forming temperature is 1250～1300 DEG C；(6) annealing: original sheet glass being put into annealing furnace and makes annealing treatment, annealing furnace takes staged to lower the temperature, design temperature 600～500 DEG C, more than 30 minutes time, naturally cools to room temperature, the original sheet glass of the thermal stress that has i.e. been eliminated the most slowly；(7) heat treatment: put into by original sheet glass and carry out heat treatment in high temperature furnace, heat treatment can generate homogeneous low bulk β-quartz solid solution crystallite in original sheet glass after terminating, it is thus achieved that has the colour devitrified glass of ultralow-expansion coefficient high transparent characteristic；(8) deburring；(9) inspection；(10) stamp；(11) dry；(12) product inspection；(13) packaging；(14) warehouse-in.

The described melting furnace in step (3) is electric smelter or crucible furnace or flame furnace.

By clarifier CeO in the described melting process in step (3)₂Remove the bubble and foreign body produced when solid glass raw material melts.

The described annealing natural cooling time in step (6) is not less than 1 hour.

The described heat treatment process in step (7) is divided into microcrystals to separate out and crystallite is grown up two stages, and the temperature needed for microcrystals precipitation phase is 550～650 DEG C, and the persistent period is 1～3h；Temperature needed for the crystallite stage of growth is 700～750 DEG C, and the persistent period is 1～2h.

The described molding in step (5) can by compressing for high temp glass stock solution for have big size or labyrinth, the diet cooking cooker of industry, kitchen tools, tableware and former of laboratory heating vessel glass can be used for.

The present invention has the following advantages compared to existing technology:

1, the present invention selects Cheap rare-earth environment-friendly type glass fining agent CeO₂Replace traditional arsenic oxide arsenoxide and stibium oxide, CeO₂Oxygen can be decomposited when glass high-temperature fusion, it it is a kind of strong oxidizer, there is clarification, bubble and the colored element of trace can be removed, add transparency and the intensity of colour devitrified glass, improve the thermostability of colour devitrified glass, also eliminate arsenic oxide arsenoxide etc. to environment and the pollution of glass simultaneously, it is adaptable to produce the colour devitrified glass goods that diet cooking is relevant；Additionally CeO₂Ce⁴⁺Radius is big, ligancy is high, for high field strength ions, it is difficult to enter the network-like parent of colour devitrified glass parent, can be only between network space, the network structure destroying colour devitrified glass parent, the netted contiguity of reduction colour devitrified glass parent and the effect of viscosity, therefore CeO can be played₂Can effectively reduce the transition temperature of colour devitrified glass and maximum recrystallization temperature, thus effectively reduce the high temperature viscosity of colour devitrified glass, forming temperature is reduced to less than 1300 DEG C, 150 DEG C are reduced than similar colour devitrified glass, the reduction of forming temperature not only can improve the service life of mould, and can effectively solve the problem that during the colour devitrified glass goods producing the big size such as steaming and decocting kitchen tools pot or labyrinth, molding is difficult.

2, the present invention selects TiO₂、ZrO₂、P₂O₅With F as Nucleating Agent the formula proportion that optimizes Nucleating Agent so that the microcrystals of this colour devitrified glass separates out more uniform；With MgO, ZnO, BaO and B₂O₃Mixture be flux or chemical stabilizer, and by adding as the metal-oxide K of flux₂O and Na₂O, is reduced to 1400～1500 DEG C by the melt temperature of colour devitrified glass raw material, greatly reduces the melt temperature of colour devitrified glass, 200 DEG C are reduced than similar colour devitrified glass, save production cost, further promote the precipitation containing lithium crystalline phase simultaneously, thus reduce heat treatment temperature.

3, the colour devitrified glass of the present invention is compared with conventional lithium aluminosilicate glass, optimizes and improves SiO₂Content between 65%～69%, reduce Li₂The content of O, between 3.1%～4.2%, controls the content of MgO below 0.5% simultaneously, controls the content of ZnO below 1.4%, thus effectively reduces thermal coefficient of expansion, reaches ± 1.0 × 10^-7/ K, compared to existing technology in its thermal coefficient of expansion of transparent glass-ceramics ± 5.0 × 10^-7/ K, super-low expansion characteristic is obviously improved, i.e. heatproof is effective；Caloric impact temperature has brought up to 1000 DEG C simultaneously, excellent in cushion effect, it is applicable not only to the colour devitrified glass goods such as the cooker of long-time open firing, kitchen tools, tableware, laboratory heating vessel, and colour devitrified glass goods are long for service life, safe to use.

4, the colour devitrified glass of the present invention is compared with conventional lithium aluminosilicate glass, on the basis of optimizing devitrified glass solvent formula proportion, in the case of solvent weight is 100%, another addition is less than the coloring agent of solvent gross weight 4%, and coloring agent is SrO, Y₂O₃、V₂O₅、Cr₂O₃、La₂O₃、MnO₂、Fe₂O₃、Co₂O₃、Ni₂O₃, the mixture of one or more transition metal oxide in CuO；Employing transition metal oxide is coloring agent, by common ion coloring phenomenon colour devitrified glass glass mutually in produce need color, transition metal and some bivalent metal oxides are (such as MgO, FeO, ZnO, CaO, SrO etc.) and the binary system of silicon dioxide, new stable oxide can be constituted after high-temperature digestion be incorporated in vitreous body, ordered arrangement after controlled micro crystallization, the either large or small stable immiscible range being formed on liquidus curve, the miscible district of diacidic base earth metal silicate system and metastable miscible district, containing transition metal (such as Fe, Co, Ni, Cu etc.) glass, in phase process, transition elements almost all is enriched in stable microfacies (such as high-alkali phase or alkali boron phase) drop, rather than in substrate glass；This selectable enriched character of transition elements so that the colour devitrified glass product after coloring, even with in articles for daily use aspects such as cooker, kitchen tools, tablewares, the most also will not separate out harmful substance, more not result in harm.

Accompanying drawing explanation

One of devitrified glass kitchen tools Cooker structure schematic diagram that accompanying drawing 1 is prepared for the present invention；

The two of the devitrified glass kitchen tools Cooker structure schematic diagram that accompanying drawing 2 is prepared for the present invention.

Wherein: 1 oral area；2 handle portions；3 wall portions；Bottom 4.

Detailed description of the invention

Below in conjunction with embodiment, the present invention is further illustrated.

The colour devitrified glass of a kind of ultralow-expansion coefficient high transparent, the solvent including parent glass, Nucleating Agent, clarifier and coloring agent, by weight percentage devitrified glass is: include the SiO of 65～69%₂, 19～the Al of 20%₂O₃, 3.1～the Li of 4.2%₂The B of O, 3～4.5%₂O₃, 0.1～the Na of 0.4%₂The K of O, 0.1～0.4%₂The parent glass of the ZnO composition of the BaO and 0.6～1.4% of the MgO of O, 0.3～0.5%, 0.6～1.4%, 1.0～the TiO of 1.7%₂, 1.0～the ZrO of 1.3%₂, 0.4～the P of 0.8%₂O₅The Nucleating Agent formed with the F of 0.3～0.8%, and 0.02～the CeO of 0.3%₂As clarifier, CeO₂Incorporation make the visible light transmissivity of this devitrified glass when thickness is less than 4mm not less than 94.0%, wherein CeO₂With SiO₂The ratio CeO of content₂/SiO₂Be 0.0003～0.0043, CeO₂With Al₂O₃The ratio CeO of content₂/Al₂O₃It is 0.0010～0.0158 and CeO₂、SiO₂、Al₂O₃Weight percentage sum CeO of three₂+SiO₂+Al₂O₃=85.1～88.3%；In the case of above-mentioned solvent weight is 100%, another addition is less than the coloring agent of solvent gross weight 4%, and coloring agent is SrO, Y₂O₃、V₂O₅、Cr₂O₃、La₂O₃、MnO₂、Fe₂O₃、Co₂O₃、Ni₂O₃, one or more mixture in CuO；Above-mentioned frit through melted, molding, Crystallizing treatment i.e. can obtain containing the composition of β-quartz solid solution be Li₂O-Al₂O₃-2SiO₂Colour devitrified glass.

In above-mentioned material, SiO₂The very few coefficient of expansion can become big, and crossing melt temperature at most can uprise；Al₂O₃Being to constitute crystallite main constituent, too low chemical durability declines, too high, and glass viscosity becomes big melt temperature and uprises；Li₂O content is too low can crystallinity die down, and the coefficient of expansion becomes big, the too strong easily devitrification of too high then crystallinity, manufactures clear glass difficulty；B₂O₃There is relatively low melt temperature, the surface tension of crystallite molten state can be reduced, improve the mechanical strength of micro-crystal board material and resistance to chemical attack and thermal coefficient of expansion can be reduced, it is also possible to improving raw materials melt and reduction melt temperature and forming temperature, but too high be difficult to transparent；Na₂O can improve frit meltbility, and too high easy thermal coefficient of expansion becomes greatly thus thermal characteristics declines；MgO can form eutectic compound, has and improves viscosity effect, it is also possible to improving frit meltbility and preventing and treating bubble defect occurs, but too high then thermal coefficient of expansion becomes big, hot property declines；Too high being also easy to makes coloring thicken and reduce the transparency；BaO is strong flux, and it can promote the stroke of glassy state and reduce thermal coefficient of expansion and the melt temperature of micro-crystal board material；And Na₂O、K₂O、MgO、ZnO、B₂O₃The melting temperature of mother glass all can be reduced as flux, ZnO can suppress split-phase, hinder overall crystallize, the stroke of glassy state in crystallite can be promoted, and improve crystallite face resistance to chemical attack and the elasticity of micro-crystal board material, and reduce crystallizing glass sheet material thermal coefficient of expansion, improve product break resistance, improve yield rate；Cerium oxide decolours for glass, replaces the arsenicum sablimatum decolorising agent that tradition uses, not only improves efficiency, but also avoid the pollution of arsenicum sablimatum；TiO is nucleators, and too high karyomorphism becomes to slow, and too high easy generation impurity colours, and is difficult to transparent；ZrO₂Also being nucleators, core becomes to slow, and too high easy generation impurity colours, and is difficult to transparent；P₂O₅There is ZrO₂Fluxing action, prevents devitrification；F has cerium sulphate crystal function, and fluorine is effective Nucleating Agent, can improve nucleation and Crystallization Process, and fluoride also can be introduced in glass as flux thus reduces glass high-temperature viscosity.

The preparation method of the colour devitrified glass of a kind of ultralow-expansion coefficient high transparent, this preparation method is carried out in the steps below: (1) is according to the formula dispensing of colour devitrified glass；(2) mixing；(3) melted: solid glass raw material to be put in the electric smelter or crucible furnace or flame furnace that melt temperature is 1400～1500 DEG C and keep more than 24 hours, by clarifier CeO₂Remove the bubble and foreign body produced when solid glass raw material melts, obtain the high temp glass stock solution of melting；(4) cooling: high temp glass stock solution is cooled to 1300～1330 DEG C；(5) molding: using die apparatus by compressing for original sheet glass for the high temp glass stock solution after cooling, forming temperature is 1250～1300 DEG C；(6) annealing: original sheet glass is put into annealing furnace and makes annealing treatment, annealing furnace takes staged to lower the temperature, design temperature 600～500 DEG C, more than 30 minutes time, naturally cool to room temperature the most slowly, the natural cooling time is not less than 1 hour, the original sheet glass of the thermal stress that has i.e. been eliminated；(7) heat treatment: original sheet glass is put into and carries out heat treatment in high temperature furnace, this heat treatment process is divided into microcrystals to separate out and crystallite is grown up two stages, temperature needed for microcrystals precipitation phase is 550～650 DEG C, persistent period is 1～3h, temperature needed for the crystallite stage of growth is 700～750 DEG C, persistent period is 1～2h, heat treatment can generate homogeneous low bulk β-quartz solid solution crystallite in original sheet glass after terminating, it is thus achieved that has the colour devitrified glass of ultralow-expansion coefficient high transparent characteristic；(8) deburring；(9) inspection；(10) stamp；(11) dry；(12) product inspection；(13) packaging；(14) warehouse-in.Additionally the molding in step (5) can by compressing for high temp glass stock solution for have big size or labyrinth, the diet cooking cooker of industry, kitchen tools, tableware and former of laboratory heating vessel glass can be used for.In above-mentioned preparation process, the crystallization temperature of crystallite heat treatment, not higher than 750 DEG C, is because when crystallization temperature is higher than 750 DEG C, and β-quartz solid solution will be gradually converted into β-spodumene solid solution.

Devitrified glass of present invention offer and preparation method thereof is be provided below by specific embodiment.

Embodiment one

The purple devitrified glass of a kind of ultralow-expansion coefficient high transparent, the solvent including parent glass, Nucleating Agent, clarifier and coloring agent, by weight percentage devitrified glass is: include the SiO of 68.0%₂, the Al of 19.4%₂O₃, the Li of 3.30%₂O, the B of 3.77%₂O₃, the Na of 0.40%₂O, the K of 0.11%₂The parent glass that O, the MgO of 0.30%, the ZnO of the BaO of 0.69% and 0.61% form, the TiO of 1.30%₂, the ZrO of 1.10%₂, the P of 0.40%₂O₅With 0.60% the Nucleating Agent that forms of F, and the CeO of 0.02%₂As clarifier, wherein CeO₂With SiO₂The ratio CeO of content₂/SiO₂=0.0003、CeO₂With Al₂O₃The ratio CeO of content₂/Al₂O₃=0.0010 and CeO₂、SiO₂、Al₂O₃Weight percentage sum CeO of three₂+SiO₂+Al₂O₃=87.42%；In the case of above-mentioned solvent weight is 100%, this purple devitrified glass it is possible to additionally incorporate the Co into solvent gross weight 0.5%₂O₃As coloring agent.

The preparation method of the purple devitrified glass of a kind of ultralow-expansion coefficient high transparent, this preparation method is carried out in the steps below: (1) is according to the formula dispensing of above-mentioned purple devitrified glass；(2) mixing；(3) melted: solid glass raw material to be put in the electric smelter or crucible furnace or flame furnace that melt temperature is 1480 DEG C and keep more than 24 hours, by clarifier CeO₂Remove the bubble and foreign body produced when solid glass raw material melts, obtain the high temp glass stock solution of melting；(4) cooling: high temp glass stock solution is cooled to 1320 DEG C；(5) molding: use die apparatus by compressing for kitchen tools pot original sheet glass (such as accompanying drawing 1 and Fig. 2) for the high temp glass stock solution after cooling, this kitchen tools pot is made up of oral area 1, handle portion 2, wall portion 3 and bottom 4, wherein a diameter of 260 mm of oral area 1, a diameter of 250mm in bottom 4, a height of 170 mm in wall portion 3, wall portion 3 thickness are 4 mm, and forming temperature is 1280 DEG C；(6) annealing: original sheet glass is put into annealing furnace and makes annealing treatment, annealing furnace takes staged to lower the temperature, design temperature 600～500 DEG C, more than 30 minutes time, naturally cool to room temperature the most slowly, the natural cooling time is not less than 1 hour, the blue original sheet glass of the thermal stress that has i.e. been eliminated；(7) heat treatment: original sheet glass is put into and carries out heat treatment in high temperature furnace, this heat treatment process is divided into microcrystals to separate out and crystallite is grown up two stages, temperature needed for microcrystals precipitation phase is 620 DEG C, persistent period is 2h, temperature needed for the crystallite stage of growth is 720 DEG C, persistent period is 1.5h, and heat treatment can generate homogeneous low bulk β-quartz solid solution crystallite after terminating in kitchen tools pot original sheet glass, it is thus achieved that has the purple devitrified glass of ultralow-expansion coefficient high transparent characteristic；(8) deburring；(9) inspection；(10) stamp；(11) dry；(12) product inspection；(13) packaging；(14) warehouse-in.

The chromaticity coordinate of this purple devitrified glass is: x=0.331, y=0.325, z=0.344.

Embodiment two

The yellow microcrystalline glass of a kind of ultralow-expansion coefficient high transparent, the solvent including parent glass, Nucleating Agent, clarifier and coloring agent, by weight percentage devitrified glass is: include the SiO of 65.0%₂, the Al of 20.0%₂O₃, the Li of 3.60%₂O, the B of 4.50%₂O₃, the Na of 0.20%₂O, the K of 0.28%₂The parent glass that O, the MgO of 0.50%, the ZnO of the BaO of 1.40% and 0.76% form, the TiO of 1.66%₂, the ZrO of 1.20%₂, the P of 0.50%₂O₅With 0.30% the Nucleating Agent that forms of F, and the CeO of 0.10%₂As clarifier, wherein CeO₂With SiO₂The ratio CeO of content₂/SiO₂=0.0015、CeO₂With Al₂O₃The ratio CeO of content₂/Al₂O₃=0.0050 and CeO₂、SiO₂、Al₂O₃Weight percentage sum CeO of three₂+SiO₂+Al₂O₃=85.10%；In the case of above-mentioned solvent weight is 100%, this yellow microcrystalline glass it is possible to additionally incorporate the Ni into solvent gross weight 1.6%₂O₃As coloring agent.

The preparation method of the yellow microcrystalline glass of a kind of ultralow-expansion coefficient high transparent, this preparation method is carried out in the steps below: (1) is according to the formula dispensing of above-mentioned yellow microcrystalline glass；(2) mixing；(3) melted: solid glass raw material to be put in the electric smelter or crucible furnace or flame furnace that melt temperature is 1400 DEG C and keep more than 24 hours, by clarifier CeO₂Remove the bubble and foreign body produced when solid glass raw material melts, obtain the high temp glass stock solution of melting；(4) cooling: high temp glass stock solution is cooled to 1300 DEG C；(5) molding: use die apparatus by compressing for kitchen tools pot original sheet glass (such as accompanying drawing 1 and Fig. 2) for the high temp glass stock solution after cooling, this kitchen tools pot is made up of oral area 1, handle portion 2, wall portion 3 and bottom 4, wherein a diameter of 260 mm of oral area 1, a diameter of 250mm in bottom 4, a height of 170 mm in wall portion 3, wall portion 3 thickness are 4 mm, and forming temperature is 1250 DEG C；(6) annealing: original sheet glass is put into annealing furnace and makes annealing treatment, annealing furnace takes staged to lower the temperature, design temperature 600～500 DEG C, more than 30 minutes time, naturally cool to room temperature the most slowly, the natural cooling time is not less than 1 hour, the original sheet glass of the yellow of the thermal stress that has i.e. been eliminated；(7) heat treatment: original sheet glass is put into and carries out heat treatment in high temperature furnace, this heat treatment process is divided into microcrystals to separate out and crystallite is grown up two stages, temperature needed for microcrystals precipitation phase is 550 DEG C, persistent period is 1h, temperature needed for the crystallite stage of growth is 700 DEG C, persistent period is 1h, and heat treatment can generate homogeneous low bulk β-quartz solid solution crystallite in original sheet glass after terminating, it is thus achieved that has the yellow microcrystalline glass of ultralow-expansion coefficient high transparent characteristic；(8) deburring；(9) inspection；(10) stamp；(11) dry；(12) product inspection；(13) packaging；(14) warehouse-in.

The chromaticity coordinate of this yellow microcrystalline glass is: x=0.427, y=0.415, z=0.158.

Embodiment three

The claret devitrified glass of a kind of ultralow-expansion coefficient high transparent, the solvent including parent glass, Nucleating Agent, clarifier and coloring agent, by weight percentage devitrified glass is: include the SiO of 66.0%₂, the Al of 19.5%₂O₃, the Li of 4.20%₂O, the B of 3.40%₂O₃, the Na of 0.10%₂O, the K of 0.40%₂The parent glass that O, the MgO of 0.32%, the ZnO of the BaO of 0.60% and 0.73% form, the TiO of 1.70%₂, the ZrO of 1.30%₂, the P of 0.80%₂O₅With 0.80% the Nucleating Agent that forms of F, and the CeO of 0.15%₂As clarifier, wherein CeO₂With SiO₂The ratio CeO of content₂/SiO₂=0.0023、CeO₂With Al₂O₃The ratio CeO of content₂/Al₂O₃=0.0077 and CeO₂、SiO₂、Al₂O₃Weight percentage sum CeO of three₂+SiO₂+Al₂O₃=85.65%；In the case of above-mentioned solvent weight is 100%, this claret devitrified glass it is possible to additionally incorporate the Nd into solvent gross weight 4.0%₂O₃As coloring agent.

The preparation method of the claret devitrified glass of a kind of ultralow-expansion coefficient high transparent, this preparation method is carried out in the steps below: (1) is according to the formula dispensing of above-mentioned claret devitrified glass；(2) mixing；(3) melted: solid glass raw material to be put in the electric smelter or crucible furnace or flame furnace that melt temperature is 1430 DEG C and keep more than 24 hours, by clarifier CeO₂Remove the bubble and foreign body produced when solid glass raw material melts, obtain the high temp glass stock solution of melting；(4) cooling: high temp glass stock solution is cooled to 1310 DEG C；(5) molding: use die apparatus by compressing for kitchen tools pot original sheet glass (such as accompanying drawing 1 and Fig. 2) for the high temp glass stock solution after cooling, this kitchen tools pot is made up of oral area 1, handle portion 2, wall portion 3 and bottom 4, wherein a diameter of 260 mm of oral area 1, a diameter of 250mm in bottom 4, a height of 170 mm in wall portion 3, wall portion 3 thickness are 4 mm, and forming temperature is 1290 DEG C；(6) annealing: original sheet glass is put into annealing furnace and makes annealing treatment, annealing furnace takes staged to lower the temperature, design temperature 600～500 DEG C, more than 30 minutes time, naturally cool to room temperature the most slowly, the natural cooling time is not less than 1 hour, the original sheet glass of the claret of the thermal stress that has i.e. been eliminated；(7) heat treatment: original sheet glass is put into and carries out heat treatment in high temperature furnace, this heat treatment process is divided into microcrystals to separate out and crystallite is grown up two stages, temperature needed for microcrystals precipitation phase is 580 DEG C, persistent period is 2h, temperature needed for the crystallite stage of growth is 740 DEG C, persistent period is 1.5h, and heat treatment can generate homogeneous low bulk β-quartz solid solution crystallite in original sheet glass after terminating, it is thus achieved that has the claret devitrified glass of ultralow-expansion coefficient high transparent characteristic；(8) deburring；(9) inspection；(10) stamp；(11) dry；(12) product inspection；(13) packaging；(14) warehouse-in.

The chromaticity coordinate of this claret devitrified glass is: x=0.327, y=0.307, z=0.366.

Being detected by the colour devitrified glass product obtaining above-mentioned three groups of embodiments and comparative example, the performance parameter table obtaining colour devitrified glass product is as follows:

By finding after upper table is analyzed, use the colour devitrified glass finished product for preparing of raw material components of the present invention all meet when the thickness of crystallized glass article is 4mm visible light transmissivity not less than 94.0%, thermal coefficient of expansion in the range of 50～400 DEG C, be entirely located in-1.0～+1.0 × 10^-7In the range of/K and all can prepare molding large scale product.

The colour devitrified glass of the present invention and the key technical indexes of goods thereof be: density is 2.59g/cm³；Thermal coefficient of expansion: (20～800 DEG C) :-1.0～+1.0 × 10^-7/K；Caloric impact temperature can reach 1000 DEG C；When the thickness of crystallized glass article is 4mm, visible light transmissivity is not less than 94.0%；Temperature is used to use 1000h transparency constant continuously when 900 DEG C；Impact strength: weighing 378 grams of solid steel balls with diameter 2cm, a height of 20.0cm free-falling bump does not ruptures for 3 times.

Above example is only the technological thought that the present invention is described, it is impossible to limiting protection scope of the present invention with this, every technological thought proposed according to the present invention, any change done on the basis of technical scheme, within each falling within scope；The technology that the present invention is not directed to all can be realized by prior art.

Claims

1. the preparation method of the colour devitrified glass of a ultralow-expansion coefficient high transparent, it is characterized in that: this colour devitrified glass includes that the solvent of parent glass, Nucleating Agent, clarifier and coloring agent, by weight percentage devitrified glass is: include the SiO of 65～69%₂, 19～the Al of 20%₂O₃, 3.1～the Li of 4.2%₂The B of O, 3～4.5%₂O₃, 0.1～the Na of 0.4%₂The K of O, 0.1～0.4%₂The parent glass of the ZnO composition of the BaO and 0.6～1.4% of the MgO of O, 0.3～0.5%, 0.6～1.4%, 1.0～the TiO of 1.7%₂, 1.0～the ZrO of 1.3%₂, 0.4～the P of 0.8%₂O₅The Nucleating Agent formed with the F of 0.3～0.8%, and 0.02～the CeO of 0.3%₂As clarifier, CeO₂Incorporation make the visible light transmissivity of this devitrified glass when thickness is less than 4mm not less than 94.0%；In the case of above-mentioned solvent weight is 100%, another addition is less than the coloring agent of solvent gross weight 4%, and coloring agent is SrO, Y₂O₃、V₂O₅、Cr₂O₃、La₂O₃、MnO₂、Fe₂O₃、Co₂O₃、Ni₂O₃, one or more mixture in CuO；Above-mentioned frit through melted, molding, Crystallizing treatment i.e. can obtain containing the composition of β-quartz solid solution be Li₂O-Al₂O₃-2SiO₂Colour devitrified glass；CeO in above-mentioned colour devitrified glass component₂With SiO₂The ratio CeO of content₂/SiO₂It is 0.0003～0.0043；CeO in above-mentioned colour devitrified glass component₂With Al₂O₃The ratio CeO of content₂/Al₂O₃It is 0.0010～0.0158；CeO in above-mentioned colour devitrified glass component₂、SiO₂、Al₂O₃Weight percentage sum CeO of three₂+SiO₂+Al₂O₃=85.1～88.3%；

Described preparation method is carried out in the steps below: (1) is according to the formula dispensing of colour devitrified glass；(2) mixing；(3) melted: solid glass raw material input melt temperature to be the melting furnace of 1400～1500 DEG C and keeps more than 24 hours, obtains the high temp glass stock solution of melting；(4) cooling: high temp glass stock solution is cooled to 1300～1330 DEG C；(5) molding: using die apparatus by compressing for original sheet glass for the high temp glass stock solution after cooling, forming temperature is 1250～1300 DEG C；(6) annealing: original sheet glass being put into annealing furnace and makes annealing treatment, annealing furnace takes staged to lower the temperature, design temperature 600～500 DEG C, more than 30 minutes time, naturally cools to room temperature, the original sheet glass of the thermal stress that has i.e. been eliminated the most slowly；(7) heat treatment: put into by original sheet glass and carry out heat treatment in high temperature furnace, heat treatment can generate homogeneous low bulk β-quartz solid solution crystallite in original sheet glass after terminating, it is thus achieved that has the colour devitrified glass of ultralow-expansion coefficient high transparent characteristic；(8) deburring；(9) inspection；(10) stamp；(11) dry；(12) product inspection；(13) packaging；(14) warehouse-in.

The preparation method of the colour devitrified glass of ultralow-expansion coefficient high transparent the most according to claim 1, it is characterised in that: the described melting furnace in step (3) is electric smelter or crucible furnace or flame furnace.

The preparation method of the colour devitrified glass of ultralow-expansion coefficient high transparent the most according to claim 1, it is characterised in that: by clarifier CeO in the described melting process in step (3)₂Remove the bubble and foreign body produced when solid glass raw material melts.

The preparation method of the colour devitrified glass of ultralow-expansion coefficient high transparent the most according to claim 1, it is characterised in that: the described annealing natural cooling time in step (6) is not less than 1 hour.

The preparation method of the colour devitrified glass of ultralow-expansion coefficient high transparent the most according to claim 1, it is characterized in that: the described heat treatment process in step (7) is divided into microcrystals to separate out and crystallite is grown up two stages, temperature needed for microcrystals precipitation phase is 550～650 DEG C, and the persistent period is 1～3h；Temperature needed for the crystallite stage of growth is 700～750 DEG C, and the persistent period is 1～2h.

The preparation method of the colour devitrified glass of ultralow-expansion coefficient high transparent the most according to claim 1, it is characterised in that: the described molding in step (5) can by compressing for high temp glass stock solution for have big size or labyrinth, the diet cooking kitchen tools of industry, tableware and former of laboratory heating vessel glass can be used for.