CN107902909A

CN107902909A - Devitrified glass and its substrate

Info

Publication number: CN107902909A
Application number: CN201711248375.XA
Authority: CN
Inventors: 原保平; 于天来; 聂小兵
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: CDGM Glass Co Ltd; Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2017-12-01
Filing date: 2017-12-01
Publication date: 2018-04-13
Anticipated expiration: 2037-12-01
Also published as: CN111348833A; CN111348833B; CN107902909B

Abstract

The present invention provides a kind of devitrified glass and its substrate, has low liquidus temperature, its component % by weight compositions contain：SiO₂60~80%；Al₂O₃4~20%；Li₂O 0~15%；Na₂O is more than 0 but less than or equal to 12%；K₂O 0~5%；ZrO₂More than 0 but less than or equal to 5%；P₂O₅0~5%；TiO₂0~10%, and crystalline phase contains from R₂SiO₃、R₂Si₂O₅、R₂TiO₃、R₄Ti₅O₁₂、R₃PO₃、RAlSi₂O₆、RAlSiO₄O₁₀、R₂Al₂Si₂O₈、R₄Al₄Si₅O₁₈, quartz and quartz solid solution in more than a kind.The liquidus temperature of devitrified glass of the present invention is below 1450 DEG C, and thermal conductivity is in more than 2w/mk, Vickers hardness 600kgf/mm²More than, suitable for portable electric appts and optical device.

Description

Devitrified glass and its substrate

Technical field

A kind of substrate the present invention relates to devitrified glass and using the devitrified glass as base material, in particular, the present invention relates to one Kind has high thermal conductivity, the devitrified glass of higher-strength suitable for the protection component such as portable electric appts or optical device And substrate.

Background technology

For portable electric appts such as smart mobile phone, plate PC and other optical devices, need to be protected using rear cover Protect internal electronic device.It is used for the protection materials of rear cover for these, in particular for requiring the electronics with wireless signal to set It is standby, it is desirable to there is higher thermal conductivity, different personal colors and higher intensity, can be used under rugged environment, and And processing performance is good.In the past, for back shroud protection materials usually using metal, but metal back cover plate can seriously affect signal Receiving, can only be designed to segmented, with the development of 5G signals, metal back cover cannot use.

As the ceramic material for not influencing signal, there is good texture and higher thermal conductivity, but compared to for glass, Processability is poor, and cost is higher.The thermal conductivity of simple glass is relatively low at present, insufficient strength is high, limits it as electronic equipment The use of rear cover material.

Devitrified glass is also referred to as glass ceramics, is that one kind is crystallized by being heat-treated to glass to be separated out in inside glass Material.Devitrified glass can possess the physics value that can not be obtained in glass by the crystallization in inner dispersion.It is for example, right In mechanical strengths such as Young's modulus, fracture toughnesses, to hot propertys such as the etching characteristic of acid or alkaline liquid, thermal coefficient of expansions, Rising and disappearance of glass transition temperature etc..Devitrified glass has the mechanical performance of higher, and due to shape in glass Into crystallite, the thermal conductivity of glass can be improved, but conventional devitrified glass due to thermal conductivity and intensity it is poor, be not suitable for above-mentioned Protection materials.In addition, conventional devitrified glass is since the viscosity of its raw glass is higher, or increased devitrification resistance is higher, therefore productivity It is relatively low, it is difficult to above-mentioned protection materials.

Japanese Patent Laid-Open 2014-114200 discloses a kind of crystallite glass substrate for information recording carrier, The crystallite glass substrate can not obtain enough compression stress values after chemical tempering is implemented, it is impossible to form deeper stressor layers.

With SiO₂-Li₂O-Al₂O₃-K₂O-ZnO-P₂O₅-ZrO₂For the lithium bisilicate devitrified glass of system development, lithium bisilicate Crystal is evenly distributed in glass matrix, forms interlocking tabular crystal microstructure, not only can Anticrack, but also material can be made Intensity and fracture toughness substantially increase, while also retains preferable optical property, currently used for dentistry and wave filter.

Lithium bisilicate glass ceramics has preferable intensity and toughness, and strong by carrying out chemical rigidifying or physics Change, more preferable devitrified glass intensity effect can be produced, available for smart mobile phone, plate PC and other optical devices etc. just Take formula electronic equipment cover sheet, but due to lithium bisilicate devitrified glass when pristine glass is molded easy crystallization, only flowing Moulding by casting is carried out under the situation of body, cooling rate is fast, could when being molded not crystallization, therefore cannot be led well Draw, overflow, rolling, blowing and lower pulling shaping, it is impossible to carry out large batch of production, cause production efficiency low.

The content of the invention

The technical problems to be solved by the invention are to provide a kind of devitrified glass and its substrate, have low liquidus temperature.

The technical proposal for solving the technical problem of the invention is：Devitrified glass, its component % by weight compositions contain： SiO₂60~80%；Al₂O₃4~20%；Li₂O 0~15%；Na₂O is more than 0 but less than or equal to 12%；K₂O 0~5%； ZrO₂More than 0 but less than or equal to 5%；P₂O₅0~5%；TiO₂0~10%, and crystalline phase contains from R₂SiO₃、R₂Si₂O₅、 R₂TiO₃、R₄Ti₅O₁₂、R₃PO₃、RAlSi₂O₆、RAlSiO₄O₁₀、R₂Al₂Si₂O₈、R₄Al₄Si₅O₁₈, quartz and quartz solid solution More than a kind of middle selection, wherein, R is more than a kind selected from Li, Na, K.

Further, also contain：B₂O₃0~5%；And/or MgO 0~2%；And/or ZnO 0~2%；And/or CaO 0 ~5%；And/or BaO 0~5%；And/or FeO 0~3%；And/or SnO₂0~2%；And/or SrO 0~5%；And/or La₂O₃0~10%；And/or Y₂O₃0~10%；And/or Nb₂O₅0~10%；And/or Ta₂O₅0~10%；And/or WO₃ 0 ~5%.

Devitrified glass, its component % by weight compositions are：SiO₂60~80%；Al₂O₃4~20%；Li₂O 0~ 15%；Na₂O is more than 0 but less than or equal to 12%；ZrO₂More than 0 but less than or equal to 5%；P₂O₅0~5%；TiO₂0~ 10%；B₂O₃0~5%；K₂O 0~5%；MgO 0~2%；ZnO 0~2%；CaO 0~5%；BaO 0~5%；FeO 0 ~3%；SnO₂0~2%；SrO 0~5%；La₂O₃0~10%；Y₂O₃0~10%；Nb₂O₅0~10%；Ta₂O₅0~ 10%；WO₃0~5%；Fining agent 0~5%, and crystalline phase contains from R₂SiO₃、R₂Si₂O₅、R₂TiO₃、R₄Ti₅O₁₂、R₃PO₃、 RAlSi₂O₆、RAlSiO₄O₁₀、R₂Al₂Si₂O₈、R₄Al₄Si₅O₁₈, select more than a kind in quartz and quartz solid solution, wherein, R is more than a kind selected from Li, Na, K.

Further, SiO₂65~78%；And/or Al₂O₃5~18%；And/or Li₂O 0~12%；And/or Na₂O 0.5~10%；And/or ZrO₂0.4~3%；And/or P₂O₅0.4~3%；And/or TiO₂2~9.5%；And/or B₂O₃ 0 ~4%；And/or K₂O 0.5~4%；And/or MgO is more than 0 but less than or equal to 2%；And/or ZnO is more than 0 but is less than or waits In 2%；And/or CaO 0~4%；And/or BaO 0~4%；And/or FeO 0~1%；And/or SnO₂0.01~1%；With/ Or SrO 0~3%；And/or La₂O₃0~9%；And/or Y₂O₃0~9%；And/or Nb₂O₅0~8%；And/or Ta₂O₅0~ 8%；And/or WO₃0~2%；And/or fining agent contains As₂O₃、Sb₂O₃、CeO₂And selected from the group of F, Cl, NOx, SOx More than one, content be 0~5%.

Further, SiO₂/Li₂O is 4~10；And/or ZrO₂/Li₂O is 0~0.5；And/or Al₂O₃/(Na₂O+Li₂O) For 0.5~2；And/or Li₂O/Na₂O is 0.8~8；And/or ZrO₂+P₂O₅+TiO₂For 1~16%.

Further, SiO₂68~75%；And/or Al₂O₃6~15%；And/or Li₂O 6~10%；And/or Na₂O 2 ~8%；And/or ZrO₂0.8~2%；And/or P₂O₅0.8~2%；And/or TiO₂3~9%；And/or B₂O₃0~be less than 2%；And/or K₂O 0.8~3%；And/or CaO 0~3%；And/or BaO0~3%；And/or SnO₂0.05~0.4%；With/ Or SrO 0~1%；And/or La₂O₃More than 0 but less than or equal to 8%；And/or Y₂O₃More than 0 but less than or equal to 8%；With/ Or Nb₂O₅0~5%；And/or Ta₂O₅0~5%；And/or WO₃0~1%；And/or fining agent 0~2%.

Further, SiO₂/Li₂O is 4.5~9.5；And/or ZrO₂/Li₂O is more than 0 but less than 0.35；And/or Al₂O₃/(Na₂O+Li₂O it is) 0.7~1.8；And/or Li₂O/Na₂O is 1.5~7.5；And/or ZrO₂+P₂O₅+TiO₂For 2~12.

Further, Na₂O 4~8%, is preferably greater than 5% but less than or equal to 8%；And/or Al₂O₃7~15%；With/ Or ZrO₂1~2%；And/or P₂O₅1~2%；And/or TiO₂5~8.5%；And/or K₂O 1~3%；And/or CaO 0~ 1%；And/or BaO 0~1%；And/or SnO₂0.05~0.2%；And/or fining agent 0~1%；And/or SiO₂/Li₂O is 5 ~9；And/or ZrO₂/Li₂O is more than 0 but less than or equal to 0.30；And/or Al₂O₃/(Na₂O+Li₂O it is) 1~1.5；And/or Li₂O/Na₂O is 2~7, preferably Li₂O/Na₂O is 2~6.

Further, also containing NiO and/or Ni₂O₃, total amount is no more than 6%, and preferably more than 4%, do not surpass more preferably 3% is crossed, total amount lower limit is more than 0.1%；Or contain Pr₂O₅, content is no more than 8%, and preferably more than 6%, do not surpass more preferably 5% is crossed, content lower limit is more than 0.4%；Or contain CoO and/or Co₂O₃, total amount is no more than 2%, and preferably more than 1.8%, Total amount lower limit is more than 0.05%；Or contain Cu₂O and/or CeO₂, total amount is no more than 4%, preferably more than 3%, total Lower limit is measured more than 0.5%；Or contain Fe₂O₃, content is no more than 8%, preferably more than 5%, more preferably no more than 3%；Or contain There is Fe₂O₃And CoO, CoO are no more than 0.3%；Or contain Fe₂O₃And Co₂O₃, Co₂O₃No more than 0.3%；Or contain Fe₂O₃、CoO And NiO；Or contain Fe₂O₃、Co₂O₃And NiO；Or contain Fe₂O₃, CoO and Co₂O₃, wherein, CoO and Co₂O₃Total amount lower limit exists More than 0.2%；Or contain Fe₂O₃, CoO, NiO and Co₂O₃；Or contain MnO₂, content be no more than 4%, preferably within 3%, contain Lower limit is measured more than 0.1%；Or contain Er₂O₃, content is no more than 8%, and preferably within 6%, content lower limit is more than 0.4%； Or contain Nd₂O₃, content is no more than 8%, and preferably within 6%, content lower limit is more than 0.4%；Or contain Er₂O₃、Nd₂O₃With MnO₂, Er₂O₃Content is within 6%, Nd₂O₃Content is within 4%, MnO₂Within 2%, the lower limit of its total amount exists content More than 0.9%；Or contain Cr₂O₃, for content no more than 4%, preferred content is no more than 3%, and more preferably content is no more than 2%, content Lower limit is more than 0.2%；Or contain V₂O₅, content is no more than 4%, and preferred content is no more than 3%, and more preferably content is no more than 2%, its content lower limit is more than 0.2%.

Further, Li₂Si₂O₅The weight % that crystalline phase accounts for devitrified glass is 20~40%, is preferably 20~35%, more excellent Elect 20~30% as, more preferably 20~25%.

Further, the weight % that quartz and quartz solid solution crystalline phase account for devitrified glass is 15~30%, is preferably 20 ~30%, more preferably 25~30%.

Further, the Li₂Si₂O₅Crystalline phase and quartz and quartz solid solution are principal crystalline phase, and its total content is micro- The weight % that devitrified glass is accounted in crystal glass is less than 50%, is preferably less than 48%, and more preferably less than 46%.

Further, LiAlSi₄O₁₀The weight % that crystalline phase accounts for devitrified glass is no more than 15%.

Further, the upper limit of glass liquidus temperature is 1450 DEG C, is preferably 1400 DEG C, more preferably 1380 DEG C, optimal Elect 1320 DEG C as.

Further, the thermal conductivity of glass room temperature (25 DEG C) is in more than 2w/mk.

Crystallite glass substrate, is made using above-mentioned devitrified glass through chemical tempering.

Further, Vickers hardness (Hv) is 600kgf/mm²More than, it is preferably 650kgf/mm²More than, more preferably 700kgf/mm²More than.

Further, the steel ball of 32g is fallen to the crystallite glass substrate and will not be broken from the height of 500mm, it is excellent Choosing height is more than 650mm, and more preferably height is more than 800mm.

Further, three-point bending strength is more than 450Mpa, be preferably more than 600Mpa, more preferably 800Mpa with On.

Further, compressive stress layers are formed by ion-exchange treatment, the compression stress value of the compressive stress layers is More than 300Mpa, is preferably more than 400Mpa, more preferably more than 500Mpa.

Further, the thickness of the compressive stress layers is more than 1 μm, is preferably more than 5 μm, more preferably more than 8 μm.

The beneficial effects of the invention are as follows：The liquidus temperature of the devitrified glass of the present invention is below 1450 DEG C, in the heat of room temperature Vickers hardness (Hv) of the conductance after more than 2w/mk, tempering is 600kgf/mm²More than.The devitrified glass or substrate of the present invention Component is protected suitable for portable electric appts and optical device etc., especially as back shroud, there is higher heat-conductivity and intensity, It is transparent or can have different personal colors.The devitrified glass of the present invention is due to higher thermal conductivity, being also used as Heat Conduction Material uses, furthermore it is also possible to for outer frame member of portable electric appts with the peculiar shape of glass material etc. Other decorations.

Embodiment

The devitrified glass of the present invention is the material for having crystalline phase and glass phase, it is different from amorphous solid.Devitrified glass Crystalline phase can be carried out by the peak angle that occurs in the X-ray diffraction pattern of X-ray diffraction analysis and by TEMEDX Distinguish.The devitrified glass of the present invention, crystalline phase contain R₂SiO₃、R₂Si₂O₅、R₂TiO₃、R₄Ti₅O₁₂、R₃PO₃、RAlSi₂O₆、 RAlSiO₄O₁₀、R₂Al₂Si₂O₈、R₄Al₄Si₅O₁₈, quartz and quartz solid solution in more than a kind, wherein, in R Li, Na, K More than a kind.

Wherein, above-mentioned Li₂Si₂O₅Crystalline phase is lithium bisilicate crystalline phase, is to be based on [Si₂O₅] tetrahedral array rhomboidal crystal, The shape of crystal is flat or tabular, and in the inside of devitrified glass, lithium bisilicate crystalline phase is the interlocking of random No yield point Microstructure, path bends when forcing the crackle to pass through crystal, so as to prevent the extension of crackle, improves devitrified glass Intensity and toughness, compared to glass phase, lithium bisilicate crystalline phase has high thermal conductivity, so as to improve devitrified glass thermal conductivity.This hair In bright devitrified glass, Li₂Si₂O₅The weight % that crystalline phase accounts for devitrified glass is 20~40%, is preferably 20~35%, more preferably For 20~30%, more preferably 20~25%.

Quartz and quartz solid solution crystalline phase belong to tripartite's either hexagonal crystal system, are deposited in devitrified glass with balled form , the extension of micro-crack can be further prevented, improves devitrified glass bending strength and toughness, compared to glass phase, quartz and stone English solid solution crystalline phase has high thermal conductivity, so as to improve devitrified glass thermal conductivity.Quartz and quartz solid solution in devitrified glass The weight % that body crystalline phase accounts for devitrified glass is 15~30%, is preferably 20~30%, more preferably 25~30%.

The present invention passes through the control to crystallization process and constituent content, Li₂Si₂O₅Crystalline phase and quartz and quartz solid solution For principal crystalline phase, and weight % that its total content accounts for devitrified glass in devitrified glass is less than 50%, and research is found, such as the oikocryst For the content of phase more than 50%, crystal content is higher in glass, causes the tempering effect of devitrified glass bad, it is impossible to play increasing Add the effect of strength of glass, the intensity of glass, preferably Li can be reduced on the contrary₂Si₂O₅Crystalline phase and quartz and quartz solid solution add up to Content is less than 48%, more preferably less than 46%.

Petalite LiAlSi₄O₁₀It is monoclinic crystal, is connected by Li with Al tetrahedrons with folding Si₂O₆The stratiform of layer The three-dimensional frame structure of structure, has the relatively low coefficient of expansion, can be used for the thermal-shock resistance for improving devitrified glass, is crystallite The auxiliary crystalline phase of glass, it accounts for the weight % of devitrified glass no more than 15% in devitrified glass.

The present inventor is in repetition test and research, the special component for forming devitrified glass, by being contained Amount and content ratio are defined as particular value and it is separated out specific crystalline phase, and the crystallite of the present invention has been obtained with relatively low cost Glass or crystallite glass substrate.In the following, the compositing range of each component of devitrified glass of the present invention is illustrated.In this specification In, if all total using the glass substance relative to the composition for being converted into oxide without specified otherwise, the content of each component The weight % of amount is represented.Herein, described " composition for being converted into oxide " refers to, as the present invention devitrified glass composition into Point raw material and the oxide, complex salt, the metal fluoride that use all decompose when melting and are changed into the situation of oxide Under, using the material total amount of the oxide as 100%.In addition, when being only called glass in the present specification, include crystallization sometimes Preceding bare glass.

SiO₂It is the neccessary composition for the glass net structure to form the devitrified glass of the present invention, and the heat for passing through bare glass Processing can become the neccessary composition of composition crystalline phase.If its amount, less than 60%, the chemical durability of obtained glass is poor, resistance to Increased devitrification resistance is also poor.Therefore, SiO₂The lower limit of content is preferably 60%, is more preferably 65%, and more preferably 68%.It is another Aspect, by making SiO₂Content be less than 80%, can suppress excessive viscosity rise reduces with meltbility.Therefore, SiO₂Contain The upper limit of amount is preferably 80%, is more preferably 78%, and more preferably 75%.

Al₂O₃With SiO₂Equally it is the component to form glass net structure, it contributes to stablize bare glass, improves chemistry The important component of durability, also can further improve the thermal conductivity of glass, but if its content is less than 4%, then ineffective.Cause This, Al₂O₃The lower limit of content is 4%, is preferably 5%, more preferably 6%, more preferably 7%.On the other hand, if Al₂O₃Content more than 20%, then meltbility and devitrification resistance reduce.Therefore, Al₂O₃The upper limit of content is 20%, is preferably 18%, more preferably 15%.

Li₂O is the optional member for the low-temperature melting properties and formability for improving glass, and also can by the heat treatment of bare glass Enough neccessary compositions as crystalline phase required for composition.But if its content is less than 6%, then ineffective.On the other hand, if mistake Contain Li more₂O, then be easy to produce the reduction of chemical durability or the rise of average coefficient of linear expansion.Therefore, Li₂O contains The upper limit of amount is preferably 15%, more preferably 12%, more preferably 10%.Chemical tempering is being carried out by ion exchange When, if containing Li in devitrified glass₂O components, then it is highly effective in terms of deeper compressive stress layers are formed.

Na₂O is to improve low-temperature melting properties and the optional member of formability, but contains Na too much₂O easily causes chemistry resistance to Long property reduces or average coefficient of linear expansion rise, therefore, Na₂The upper limit of O content is preferably 12%, and more preferably 10%, it is optimal Elect 8% as.When carrying out chemical tempering by ion exchange, contain Na in devitrified glass₂O components, make the Na in devitrified glass⁺ Ion and K⁺Ion exchange is highly effective in terms of compressive stress layers are formed.Therefore, chemical tempering is being carried out by ion exchange When, Na₂The lower limit of O content is more than 0, is preferably 0.5%, and more preferably 2%, more preferably 4%, are most preferably more than 5%.

P₂O₅Split-phase can be carried out in glass and forms nucleus, and the cold melt for contributing to improve glass is hanked Point.P₂O₅The lower limit of content is preferably greater than 0, and more preferably 0.4%, more preferably 0.8%, are most preferably 1%, but such as Fruit contains P too much₂O₅, then it is easy to the reduction of generation devitrification resistance and the split-phase of glass.Therefore, P₂O₅The upper limit of content is excellent Elect 5% as, more preferably 3%, it is most preferably 2%.

ZrO₂Have the function that crystallization separates out and form nucleus, the chemical durability for still helping to improve glass is hanked Point.ZrO₂The lower limit of content is preferably greater than 0, and more preferably 0.4%, more preferably 0.8%, are most preferably 1%, but such as Fruit contains ZrO too much₂, then the devitrification resistance of glass be easily reduced.Therefore, ZrO₂The upper limit of content is preferably 5%, more excellent Elect 3% as, be most preferably 2%.

TiO₂It is a kind of viscosity for contributing to reduction devitrified glass, raising chemical durability, reduces the optional of liquidus temperature Component, due to Li in glass₂O and Na₂O total contents are more, cause the easy crystallization of glass, add TiO₂After can effective heat absorbing glass Free oxygen, become Network former, reduce the liquidus temperature of glass.TiO₂The lower limit of content is preferably greater than 0, more preferably 2%, more preferably 3%, are still more preferably 5%, most preferably more than 6%.On the other hand, excessive TiO₂Cannot Completely into glass network, devitrification of glass can be caused.Therefore, TiO₂The upper limit of content is 10%, is preferably 9.5%, more preferably For 9%, most preferably 8.5%.

In the present invention, desired crystalline phase in order to obtain, thus improve crystallite glass substrate thermal conductivity and hardness, it is necessary to Control SiO₂Content relative to Li₂The ratio of O content, i.e. make SiO₂/Li₂The value of O is 4~10.In order to be easier to obtain institute State effect, SiO₂/Li₂The lower limit of the value of O is preferably 4, and more preferably 4.5, it is most preferably 5；SiO₂/Li₂The upper limit of the value of O is excellent Elect 10 as, more preferably 9.5, it is most preferably 9.

In the present invention, in order to obtain uniform tiny and more crystalline phases in glass, so as to improve devitrified glass base The thermal conductivity and bending strength of plate, it is necessary to control ZrO₂Content relative to Li₂The ratio of O content, i.e. make ZrO₂/Li₂O's It is worth for 0~0.5, is preferably greater than 0 but less than 0.35, more preferably higher than 0 but less than or equal to 0.30.

In the present invention, good tempering effect in order to obtain, so as to improve the intensity of crystallite glass substrate, it is necessary to control Al processed₂O₃Content relative to LiO₂And Na₂The ratio of O total contents, i.e. Al₂O₃/(Na₂O+Li₂O the lower limit of value) is preferably 0.5, more preferably 0.7, are most preferably 1；Al₂O₃/(Na₂O+Li₂O the upper limit of value) is preferably 2, and more preferably 1.8, it is optimal Elect 1.5 as.

Devitrification resistance and meltbility when in the present invention, in order to make fusing are with formability preferably, it is necessary to control Li₂O Relative to Na₂The ratio of O, i.e. make Li₂O/Na₂The value of O is preferred for 0.8~8.In order to be easier to obtain the effect, Li₂O/ Na₂The lower limit of the value of O is preferably 0.8, and more preferably 1.5, it is most preferably 2；Li₂O/Na₂The upper limit of the value of O is preferably 8, more excellent Elect 7.5 as, more preferably 7, it is most preferably 6.

In the present invention, in order to which uniform crystallization can be separated out, ZrO is controlled₂、P₂O₅And TiO₂Total content, i.e. ZrO₂+ P₂O₅+TiO₂For 1~16%.In order to be easier to obtain the effect, ZrO₂+P₂O₅+TiO₂The lower limit of value be preferably 1%, most Preferably 2%；ZrO₂+P₂O₅+TiO₂The upper limit of value be preferably 16%, more preferably 12%.

B₂O₃Contribute to the viscosity of reduction glass, improve the meltability and formability of glass, improve glass tempering performance, because This can be used as optional component to add.If contain B too much₂O₃, then the chemical durability of devitrified glass be easily reduced, it is easy to Suppress the precipitation of desired crystallization.Therefore, B₂O₃The upper limit of content is preferably 5%, and more preferably 4%, most preferably less than 2%.

K₂O contributes to improve the low-temperature melting properties of glass and the optional member of formability, but if containing K too much₂O, Then it is easy to produce the reduction of chemical durability and the rise of average coefficient of linear expansion.Therefore, K₂The upper limit of O content is preferably 5%, more preferably 4%, are most preferably 3%.When carrying out chemical tempering by ion exchange, if making to contain in devitrified glass K₂O, then it is highly effective in terms of deeper compressive stress layers are formed.Therefore, when carrying out chemical tempering by ion exchange, K₂O The lower limit of content is preferably greater than 0, and more preferably 0.5%, more preferably 0.8%, are most preferably 1%.

MgO helps to suppress bare glass crystallization when reducing viscosity and the shaping of glass, also has and improves cold melt Effect, is optional member, the lower limit of content of MgO is preferably greater than 0；But if content of MgO is excessive, devitrification resistance may be caused Decline, undesirable crystal can be obtained after crystallization, causes devitrified glass hydraulic performance decline, therefore, the upper limit of content of MgO is preferably 2%.

ZnO can improve the meltdown property of glass, improve the chemical stability of glass, be optional member, the lower limit of ZnO content Preferably greater than 0；On the other hand, the upper limit of ZnO content is controlled below 2%, increased devitrification resistance reduction can be suppressed.

CaO contributes to improve the optional member of the cold melt of glass, but if containing CaO too much, then resistance to mistake Permeability is easily reduced.Therefore, the upper limit of CaO content is preferably 5%, more preferably 4%, more preferably 3%, most preferably For 1%.

BaO contributes to improve the optional member of the cold melt of glass, but if containing BaO too much, then resistance to mistake Permeability is easily reduced.Therefore, the upper limit of BaO contents is preferably 5%, more preferably 4%, more preferably 3%, most preferably For 1%.

FeO can play a role as fining agent, therefore can arbitrarily contain, but if excessively containing FeO, then easily occur Hyperchromia makes the platinum of glass melting set that alloying occur.Therefore, the upper limit of FeO contents is preferably 3%, more preferably 1%.

SnO₂It is effect and the optional member that makes crystallization separate out the effect to form nucleus that can be played as fining agent. Therefore, SnO₂The lower limit of content is preferably greater than 0, and more preferably 0.01%, it is most preferably 0.05%；But if contain too much SnO₂, then the devitrification resistance of glass be easily reduced.Therefore, SnO₂The upper limit of content is preferably 2%, and more preferably 1%, into one Step is preferably 0.4%, is most preferably 0.2%.

SrO is the optional member for the cold melt for improving glass, but if excessively containing SrO, then devitrification resistance is held very much Easily reduce.Therefore, the upper limit of SrO contents is preferably 5%, and more preferably 3%, it is most preferably 1%.

La₂O₃It is the optional member for improving devitrified glass hardness, it is a small amount of to add the fusion temperature that reduce glass, and Liquidus temperature is reduced to a certain extent, but if excessively containing La₂O₃, then devitrification resistance be easily reduced.Therefore, La₂O₃Contain Scope is measured below 10%, preferably below 9%, is more preferably higher than 0 but less than or equal to 8%.

Y₂O₃It is the optional member for improving the hardness of devitrified glass, chemical stability and thermal conductivity, a small amount of add can reduce The fusion temperature of glass, and liquidus temperature is reduced to a certain extent, but if excessively containing Y₂O₃, then devitrification resistance be easy to Reduce.Therefore, Y₂O₃Content below 10%, preferably below 9%, more preferably higher than 0 but less than or equal to 8%.

Nb₂O₅It is the optional member for the mechanical strength for improving devitrified glass, but if containing Nb too much₂O₅, then devitrification Property is easily reduced.Therefore, Nb₂O₅The upper limit of content is preferably 10%, and more preferably 8%, it is most preferably 5%.

Ta₂O₅It is the optional member for the mechanical strength for improving glass, but if containing Ta too much₂O₅, then devitrification resistance is very It is easily reduced.Therefore, Ta₂O₅The upper limit of content is preferably 10%, and more preferably 8%, it is most preferably 5%.

WO₃It is the optional member for the mechanical strength for improving glass, but if containing WO too much₃, then devitrification resistance be easy to Reduce.Therefore, WO₃The upper limit of content is preferably 5%, and more preferably 2%, it is most preferably 1%.

In the devitrified glass of the present invention, As can also be contained as fining agent₂O₃、Sb₂O₃、CeO₂And from F, Cl, The one or two or more kinds selected in the group of NOx, SOx.But the upper limit for clarifying agent content is preferably 5%, more preferably 2%, Most preferably 1%.

The devitrified glass of the present invention can add certain colouring agent, prepare the devitrified glass of different colours.

Use NiO and/or Ni₂O₃For colouring agent, brown or green glass-ceramic are used to prepare, two kinds of components can be independent Using or be used in mixed way, content is usually no more than 6% respectively for it, preferably more than 4%, more preferably no more than 3%, its distinguish Content lower limit more than 0.1%, if NiO and Ni₂O₃It is used in mixed way, then NiO and Ni₂O₃Total amount be usually no more than 6%, if content, more than 6%, colouring agent cannot be dissolved in glass very well.

Use Pr₂O₅As green glass composition colouring agent, it is used alone, general content is no more than 8%, preferred content No more than 6%, more preferably no more than 5%, its content lower limit is more than 0.4%, and as content is less than 0.4%, then glass colour is not Substantially.

Use CoO and/or Co₂O₃For colouring agent, blue glass ceramics are used to prepare, two kinds of colouring agent components can be independent Using or be used in mixed way, its content respectively is all usually no more than 2%, preferably more than 1.8%, if content exceedes 2%, colouring agent cannot be dissolved in glass very well, when being such as used in mixed way, CoO and Co₂O₃Total amount is no more than 2%, its containing respectively Lower limit is measured more than 0.05%, is such as less than 0.05%, glass colour unobvious.

Use Cu₂O and/or CeO₂For colouring agent, prepare yellow microcrystalline glass, two kinds of colouring agent components be used alone or It is used in mixed way, Cu is used alone₂O, content is no more than 4%, preferably more than 3%, if content easily makes glass more than 4% Crystallization；CeO is used alone₂, content is usually no more than 4%, and preferably more than 3%, if content is more than 4%, glassy lustre is bad. If two kinds of colouring agents are used in mixed way, its total amount is usually no more than 4%, and content lower limit is more than 0.5%.

Fe is used alone₂O₃For colouring agent；Or use Fe₂O₃With two kinds of colouring agents being used in mixed way of CoO；Or use Fe₂O₃And Co₂O₃Two kinds of colouring agents being used in mixed way；Or use Fe₂O₃, tri- kinds of colouring agents being used in mixed way of CoO and NiO；Or Person uses Fe₂O₃、Co₂O₃With tri- kinds of colouring agents being used in mixed way of NiO；Or use Fe₂O₃, CoO and Co₂O₃Three kinds are used in mixed way Colouring agent；Or use Fe₂O₃, CoO, NiO and Co₂O₃Four kinds of colouring agents being used in mixed way, it is micro- to prepare black and smoky gray Crystal glass.Fe is used alone₂O₃Coloring, content are no more than 8%, preferably more than 5%, more preferably no more than 3%.CoO and Co₂O₃There is absorption in visible ray, the blackness of glass can be deepened, generally and Fe₂O₃When being used in mixed way, CoO and Co₂O₃Content point Bu Chaoguo not 0.3%, CoO and Co₂O₃Total amount lower limit is more than 0.2%.NiO has absorption in visible ray, can deepen glass Blackness, its content is no more than 1% when generally mixing with use.

Use MnO₂For colouring agent, purple devitrified glass is prepared, content is usually no more than 4%, preferably within 3%, its Content lower limit more than 0.1%, as content be less than 0.1%, glass colour unobvious.

Use Er₂O₃For colouring agent, pink colour devitrified glass is used to prepare, 8% is usually no more than using content, preferably 6% Within.Due to rare earth element er₂O₃Coloration efficiency is low, more than 8% the color of glass can not be made further when using content Deepen, increase the cost of glass on the contrary, its content lower limit is such as less than 0.4%, glass colour unobvious more than 0.4%.

Use Nd₂O₃For colouring agent, aubergine glass composition is prepared, 8% is usually no more than using content, preferably 6% Within.Due to rare earth element nd₂O₃Coloration efficiency is low, has exceeded 8% using content, and the color of glass can not be made further Deepen, increase the cost of glass on the contrary, its content lower limit is such as less than 0.4%, glass colour unobvious more than 0.4%.

Use Er₂O₃、Nd₂O₃And MnO₂Mixed colorant, prepares red glass devitrified glass, and Er ions are in 400- in glass 500nm has absorption, and Mn ions mainly have absorption at 500nm, and Nd ions mainly have strong absorption, three kinds of materials at 580nm Mixing, red glass composition can be prepared, due to Er₂O₃And Nd₂O₃Coloured for rare earth, colorability is weaker, Er₂O₃Make Dosage is within 6%, Nd₂O₃Usage amount is within 4%, and Mn ion colorings are strong, MnO₂In the range of 2%, it uses mixed usage amount The lower limit of colouring agent total amount is closed more than 0.9%.

Use Cr₂O₃As green glass composition colouring agent, it is used alone, general content is no more than 4%, preferred content No more than 3%, more preferably content is no more than 2%, its content lower limit is more than 0.2%, as content is less than 0.2%, then glass face Color unobvious.

Use V₂O₅As yellow green glass composition colouring agent, it is used alone, general content is no more than 4%, preferred content No more than 3%, more preferably content is no more than 2%, its content lower limit is such as less than 0.2% more than 0.2%, then glass colour is not Substantially.

In the devitrified glass of the present invention, form, can be only made of mentioned component, but do not damaging seriously as glass In the range of glass performance, other compositions can also be added.For example, TeO can be added₂、Bi₂O₃、GeO₂Deng component.

The devitrified glass of the present invention has following characteristics.

The devitrified glass devitrification resistance of the present invention is higher, more specifically, has relatively low liquidus temperature.That is, it is of the invention The upper limit of glass liquidus temperature be preferably 1450 DEG C, more preferably 1400 DEG C, more preferably 1380 DEG C, are most preferably 1320℃.Thus, even if flowing out melten glass at a lower temperature, can also reduce from molten condition formed glass when mistake Thoroughly.Further, since can also make forming of glass even if the melting temperature for reducing glass, therefore platinum device and mould hair can be suppressed Raw deterioration, but also the energy expended during forming of glass can be reduced, reduce the production cost of glass.

On the other hand, do not have particular determination, glass produced by the present invention to the lower limit of the glass liquidus temperature of the present invention The lower limit of liquidus temperature be preferably 1000 DEG C, more preferably 1100 DEG C, be most preferably 1200 DEG C.

Above-mentioned liquidus temperature is the index of devitrification resistance, in the present specification, using the value measured using the following method as liquid Phase temperature.First, the glass sample of 30cc chips of glass shapes is put into the platinum crucible that capacity is 50ml, keeps, makes at 1500 DEG C It is in complete molten condition；Then, after when being cooled to set point of temperature and holding 12 is small, it is fetched into outside stove and is cooled down, There is nodeless mesh in observation glass surface and glass, observation is carried out in units of every 10 DEG C respectively up to 1000 DEG C, in the regulation In temperature, the minimum temperature can't see crystallization is used as liquidus temperature.

Less than 1200 DEG C glass components of liquidus temperature are carried out with the test of high temperature viscosity, liquid phase temperature-viscosity is tested, presses According to SJT11040-1996 standards, after glass reaches maximum temperature fusing, rotor is declined 23mm and enters glass melt In, rotate at the same time, with the reduction of temperature, the increase of glass viscosity, when the torque of rotor reaches the 80% of setting torque, meeting is certainly It is dynamic to stop measurement, the viscosity of glass is obtained by calculation.

The thermal conductivity of devitrified glass of the present invention is more than 2W/mk.

The crystallite glass substrate of the present invention, can form compressive stress layers by ion-exchange treatment, implement chemical tempering. When forming compressive stress layers, the compression stress value of compressive stress layers is preferably more than 300Mpa.Due to such compression Stress value, can suppress the extension of crackle and improve mechanical strength.Therefore, when implementing chemical tempering, crystallite glass of the invention The compression stress value of the compressive stress layers of glass substrate is preferably more than 300Mpa, more preferably more than 400Mpa, is most preferably More than 500Mpa.

The thickness of the compressive stress layers of the crystallite glass substrate of the present invention, is preferably more than 1 μm.Since compressive stress layers have There is such thickness, therefore deeper crackle is produced on crystallite glass substrate, can also suppress crack growth or substrate Fracture.Therefore, the thickness of compressive stress layers is preferably more than 1 μm, more preferably more than 5 μm, is most preferably more than 8 μm.

The Vickers hardness (Hv) of the crystallite glass substrate of the present invention is preferably more than 600.Due to such hardness, because This can suppress that cut occurs, and can improve mechanical strength.Therefore, the Vickers hardness (Hv) of devitrified glass of the invention is preferred It is most preferably more than 700 for more than 600, more preferably more than 650.

The crystallite glass substrate of the present invention, is preferably, even if falling the steel ball of 32g to devitrified glass from the height of 500mm Substrate will not be broken.Due to such impact resistance, under being born when being used as protection component Impact when falling or colliding.Therefore, even if the steel ball drop of 32g will not be made the whereabouts that crystallite glass substrate is broken Highly, preferably height is more than 500mm, and more preferably height is more than 650mm, and most preferably height is more than 800mm.

The three-point bending strength of the crystallite glass substrate of the present invention, is preferably 450Mpa.Due to curved with such 3 points Qu Qiangdu, when bearing enough pressure, glass will not be broken glass.Therefore, three-point bending strength is preferably 450Mpa More than, more preferably more than 600Mpa, is most preferably more than 800Mpa.

The devitrified glass of the present invention can be prepared by the following method：Raw material is mixed according to component ratio scope It is even, uniform mixture is put into the crucible of platinum system or quartz system, the fusing difficulty formed according to glass, in electric furnace or combustion Melted in steam stove when progress 5~24 is small within the temperature range of 1250~1550 DEG C, after stirring makes its uniform, be down to appropriate temperature Spend and be cast in mould, Slow cooling forms.

The bare glass of the devitrified glass of the present invention can be molded by well-known method.

The bare glass of the devitrified glass of the present invention, carries out Crystallizing treatment, in inside glass after shaping or after processing and forming Equably separate out crystallization.The Crystallizing treatment can be carried out by 1 stage, can also be carried out by 2 stages, it is preferable to employ 2 stages carry out Crystallizing treatment.The processing of nucleation technique is carried out at a temperature of the 1st, then the higher than nucleation technological temperature the 2nd At a temperature of carry out crystal growth technique processing.The Crystallizing treatment carried out at a temperature of the 1st is known as the 1st Crystallizing treatment, will be The Crystallizing treatment carried out at a temperature of 2nd is known as the 2nd Crystallizing treatment.

In order to make devitrified glass obtain desired physical property, preferable heat treatment condition is：

Crystallizing treatment is carried out above by 1 stage, can continuously carry out core formation process and crystalline growth technique. That is, Crystallizing treatment temperature as defined in being warming up to, after heat treatment temperature is reached, is kept for the regular hour, then by its temperature Cool down again.The temperature of the Crystallizing treatment is preferably at 500~700 DEG C, in order to separate out desired crystalline phase, more preferably For 550~680 DEG C, the retention time at a temperature of Crystallizing treatment, is preferably 0~8h, more preferably 1~6h.

When carrying out Crystallizing treatment above by 2 stages, the 1st temperature is preferably 500~700 DEG C, and the 2nd temperature is preferably 650~850 DEG C.Retention time at a temperature of the 1st, is preferably 0~24h, is most preferably 2~15h.Guarantor at a temperature of the 2nd The time is held, is preferably 0~10h, is most preferably 2~5h.

The above-mentioned retention time 0 divides, and refers to start to cool down or heated up again less than 1 minute after its temperature is reached.

The bare glass or devitrified glass of the present invention, can use the methods of grinding or polishing and manufacture glass shaping body. It is lamellar by the way that glass shaping body is processed into, the crystallite glass substrate using the devitrified glass of the present invention as base material can be made. But the method for manufacturing glass shaping body, is not limited to these methods.

The present invention crystallite glass substrate, can be prepared at a certain temperature using the methods of hot bending or die mould to be formed it is various Shape, wherein hot bending temperature and the temperature of die mould are less than the temperature of crystallization.But the method for manufacturing the variously-shaped body of glass, and it is unlimited Due to these methods.

The devitrified glass of the present invention is crystallized except through precipitation and improved outside mechanical property, can also be answered by forming compression Power layer obtains the intensity of higher.The forming method of compressive stress layers has chemical tempering process, i.e.,：Deposit the top layer of crystallite glass substrate Alkaline components swap reaction with alkaline components bigger than its ionic radius, in top layer formation compressive stress layers.In addition The ion implantation of the top layer injection ion of also oriented crystallite glass substrate, and crystallite glass substrate is heated, then The hot tempering method quickly cooled down.

The embodiment of the present invention (1~table of table 8) is prepared via a method which：First, the raw material as various composition, selection Respective oxide, hydroxide, carbonate, nitrate, fluoride, chloride, hydroxide and metaphosphoric acid chemical combination The raw materials such as thing, according to component ratio scope, raw material is uniformly mixed, and uniform mixture is put into the crucible of platinum system or quartz system In, according to glass form fusing difficulty, in electric furnace or gas furnace within the temperature range of 1250~1550 DEG C carry out 5~ 24 melt when small, after stirring makes its uniform, are down to appropriate temperature and are cast in mould, Slow cooling obtains bare glass.

For obtained bare glass, in order to carry out karyomorphism into and crystallization, implement the heat in 1 stage or 2 stages respectively Processing manufacture devitrified glass, wherein, embodiment 15,18,20 and 22 carries out the heat treatment in 1 stage, and other embodiment carries out 2 ranks The heat treatment of section.In 1~table of table 8, the heat treatment condition in the 1st stage is recorded in " nucleation technique " column, at the heat in the 2nd stage Manage bar part is recorded in " crystallization process " column, and the temperature of heat treatment and the retention time at a temperature of it are as described in table.

The crystalline phase of devitrified glass in embodiment before chemical tempering, using X-ray diffraction analysis device, by X-ray The angle of the peak value shown on diffraction pattern, analyze crystalline phase in crystallite glass substrate.

Prepared devitrified glass is cut and ground, 36 × 29 × 0.7mm specification thin slices are obtained, to opposite face Parallel polished is carried out, the devitrified glass after polishing is then immersed in KNO₃Chemical tempering is carried out in fused salt, obtains crystallite glass Glass substrate.Wherein, the temperature and soaking time of fused salt are soaked, as described in " chemical tempering condition " column in table.

Implement the compression stress value on surface and the thickness of compressive stress layers of the crystallite glass substrate of chemical tempering, utilize glass Glass surface stress instrument FSM-6000 is measured.It is by 1.53, Photoelasticity constant of the refractive index of sample as determination condition 28.5 [(nm/cm)/Mpa] are calculated.

The Vickers hardness of crystallite glass substrate in embodiment, with the diamond quadrangular pyramid pressure head that opposite face angle is 136 ° Load (N) divided by the surface area calculated by concave length gauge when being pressed into the depression of Pyramid on experiment face (mm²) value represent.Test load is set to be 100 (N), the retention time is to carry out 15 (seconds).For with " chemical tempering condition " Embodiment, be to be carried out on the substrate after chemical tempering.

Height of the fall ball in embodiment represents, rubber is placed on after being polished to two surface of substrate of 36 × 29 × 0.8mm On film, the steel ball of 32g is set to be fallen from specified altitude, the maximum falling sphere for the impact that substrate does not occur to be broken and can bear is high Degree.Specifically, test and come into effect from height of the fall ball 650mm, in cases where no fracturing is occurring, by 700mm, 750mm, 800mm, 850mm and 900mm change height.For the embodiment with " chemical tempering condition ", with the substrate after chemical tempering For subjects.The test data of 900mm is recorded as in embodiment, even if representing to make steel ball fall base from the height of 900mm Plate does not also occur to be broken and bear impact.

Three-point bending strength in 1~table of table 8, using microcomputer controlled electronic universal tester CMT6502, glass size 36 × 29 × 0.7mm, is tested using ASTM C 158-2002 as standard.

The thermal conductivity of devitrified glass in 1~table of table 8, is measured using Conduction Coefficient Detector Basing device LFA447.With room temperature (25 DEG C) and sample specification are Φ 12.7mm × 1.5mm as determination condition, execution《JC/T675-1997 glass material heat conduction system Number test method》Standard.

Color in embodiment is to observe by the naked eye the color of 36 × 29 × 0.8mm sheet glass.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

It can be seen from above-described embodiment that the present invention devitrified glass room temperature (25 DEG C) thermal conductivity in 2W/mk More than, there is high thermal conductivity, preferable bending strength and hardness, good drop resistant to hinder performance, while the crystallite glass of the present invention Glass can also have good personal color.The devitrified glass or substrate that the present invention obtains, suitable for portable electric appts and light The protection component such as equipment is learned, especially as back shroud.

Claims

1. devitrified glass, it is characterised in that its component % by weight compositions contain：SiO₂60~80%；Al₂O₃4~20%； Li₂O 0~15%；Na₂O is more than 0 but less than or equal to 12%；K₂O 0~5%；ZrO₂More than 0 but less than or equal to 5%；P₂O₅ 0~5%；TiO₂0~10%, and crystalline phase contains from R₂SiO₃、R₂Si₂O₅、R₂TiO₃、R₄Ti₅O₁₂、R₃PO₃、RAlSi₂O₆、 RAlSiO₄O₁₀、R₂Al₂Si₂O₈、R₄Al₄Si₅O₁₈, select more than a kind in quartz and quartz solid solution, wherein, R be from Li, More than a kind selected in Na, K.

2. devitrified glass as claimed in claim 1, it is characterised in that also contain：B₂O₃0~5%；And/or MgO 0~2%； And/or ZnO 0~2%；And/or CaO 0~5%；And/or BaO 0~5%；And/or FeO 0~3%；And/or SnO₂0~ 2%；And/or SrO 0~5%；And/or La₂O₃0~10%；And/or Y₂O₃0~10%；And/or Nb₂O₅0~10%；With/ Or Ta₂O₅0~10%；And/or WO₃0~5%.

3. devitrified glass, it is characterised in that its component % by weight, which is formed, is：SiO₂60~80%；Al₂O₃4~20%；Li₂O 0~15%；Na₂O is more than 0 but less than or equal to 12%；ZrO₂More than 0 but less than or equal to 5%；P₂O₅0~5%；TiO₂0~ 10%；B₂O₃0~5%；K₂O 0~5%；MgO 0~2%；ZnO 0~2%；CaO 0~5%；BaO 0~5%；FeO 0 ~3%；SnO₂0~2%；SrO 0~5%；La₂O₃0~10%；Y₂O₃0~10%；Nb₂O₅0~10%；Ta₂O₅0~ 10%；WO₃0~5%；Fining agent 0~5%, and crystalline phase contains from R₂SiO₃、R₂Si₂O₅、R₂TiO₃、R₄Ti₅O₁₂、R₃PO₃、 RAlSi₂O₆、RAlSiO₄O₁₀、R₂Al₂Si₂O₈、R₄Al₄Si₅O₁₈, select more than a kind in quartz and quartz solid solution, wherein, R is more than a kind selected from Li, Na, K.

4. the devitrified glass as described in claim 1-3 any claims, it is characterised in that SiO₂65~78%；And/or Al₂O₃5~18%；And/or Li₂O 0~12%；And/or Na₂O 0.5~10%；And/or ZrO₂0.4~3%；And/or P₂O₅ 0.4~3%；And/or TiO₂2~9.5%；And/or B₂O₃0~4%；And/or K₂O 0.5~4%；And/or MgO be more than 0 but Less than or equal to 2%；And/or ZnO is more than 0 but less than or equal to 2%；And/or CaO 0~4%；And/or BaO 0~4%； And/or FeO 0~1%；And/or SnO₂0.01~1%；And/or SrO 0~3%；And/or La₂O₃0~9%；And/or Y₂O₃ 0~9%；And/or Nb₂O₅0~8%；And/or Ta₂O₅0~8%；And/or WO₃0~2%；And/or fining agent contains As₂O₃、Sb₂O₃、CeO₂And selected from the group of F, Cl, NOx, SOx more than one, content be 0~5%.

5. the devitrified glass as described in claim 1-3 any claims, it is characterised in that SiO₂/Li₂O is 4~10；With/ Or ZrO₂/Li₂O is 0~0.5；And/or Al₂O₃/(Na₂O+Li₂O it is) 0.5~2；And/or Li₂O/Na₂O is 0.8~8；And/or ZrO₂+P₂O₅+TiO₂For 1~16%.

6. the devitrified glass as described in claim 1-3 any claims, it is characterised in that SiO₂68~75%；And/or Al₂O₃6~15%；And/or Li₂O 6~10%；And/or Na₂O 2~8%；And/or ZrO₂0.8~2%；And/or P₂O₅ 0.8~2%；And/or TiO₂3~9%；And/or B₂O₃0~it is less than 2%；And/or K₂O 0.8~3%；And/or CaO 0~ 3%；And/or BaO 0~3%；And/or SnO₂0.05~0.4%；And/or SrO 0~1%；And/or La₂O₃It is more than 0 but small In or equal to 8%；And/or Y₂O₃More than 0 but less than or equal to 8%；And/or Nb₂O₅0~5%；And/or Ta₂O₅0~5%； And/or WO₃0~1%；And/or fining agent 0~2%.

7. the devitrified glass as described in claim 1-3 any claims, it is characterised in that SiO₂/Li₂O is 4.5~9.5； And/or ZrO₂/Li₂O is more than 0 but less than 0.35；And/or Al₂O₃/(Na₂O+Li₂O it is) 0.7~1.8；And/or Li₂O/Na₂O For 1.5~7.5；And/or ZrO₂+P₂O₅+TiO₂For 2~12%.

8. the devitrified glass as described in claim 1-3 any claims, it is characterised in that Na₂O 4~8%, preferably greater than 5% but less than or equal to 8%；And/or Al₂O₃7~15%；And/or ZrO₂1~2%；And/or P₂O₅1~2%；And/or TiO₂5~8.5%；And/or K₂O 1~3%；And/or CaO 0~1%；And/or BaO 0~1%；And/or SnO₂0.05~ 0.2%；And/or fining agent 0~1%；And/or SiO₂/Li₂O is 5~9；And/or ZrO₂/Li₂O is more than 0 but is less than or equal to 0.30；And/or Al₂O₃/(Na₂O+Li₂O it is) 1~1.5；And/or Li₂O/Na₂O is 2~7, preferably Li₂O/Na₂O is 2~6.

9. the devitrified glass as described in claim 1-3 any claims, it is characterised in that also containing NiO and/or Ni₂O₃, Total amount is no more than 6%, preferably more than 4%, more preferably no more than 3%, and total amount lower limit is more than 0.1%；Or contain Pr₂O₅, content is no more than 8%, and preferably more than 6%, more preferably no more than 5%, content lower limit is more than 0.4%；Or contain CoO and/or Co₂O₃, total amount is no more than 2%, and preferably more than 1.8%, total amount lower limit is more than 0.05%；Or contain Cu₂O and/or CeO₂, total amount is no more than 4%, and preferably more than 3%, total amount lower limit is more than 0.5%；Or contain Fe₂O₃, Content is no more than 8%, preferably more than 5%, more preferably no more than 3%；Or contain Fe₂O₃And CoO, CoO are no more than 0.3%；Or Contain Fe₂O₃And Co₂O₃, Co₂O₃No more than 0.3%；Or contain Fe₂O₃, CoO and NiO；Or contain Fe₂O₃、Co₂O₃And NiO；Or Contain Fe₂O₃, CoO and Co₂O₃, wherein, CoO and Co₂O₃Total amount lower limit is more than 0.2%；Or contain Fe₂O₃, CoO, NiO and Co₂O₃；Or contain MnO₂, content is no more than 4%, and preferably within 3%, content lower limit is more than 0.1%；Or contain Er₂O₃, contain Amount is no more than 8%, and preferably within 6%, content lower limit is more than 0.4%；Or contain Nd₂O₃, content be no more than 8%, preferably exist Within 6%, content lower limit is more than 0.4%；Or contain Er₂O₃、Nd₂O₃And MnO₂, Er₂O₃Content is within 6%, Nd₂O₃Content Within 4%, MnO₂Content is within 2%, and the lower limit of its total amount is more than 0.9%；Or contain Cr₂O₃, content is no more than 4%, preferred content is no more than 3%, and more preferably content is no more than 2%, and content lower limit is more than 0.2%；Or contain V₂O₅, content No more than 4%, preferred content is no more than 3%, and more preferably content is no more than 2%, its content lower limit is more than 0.2%.

10. the devitrified glass as described in claim 1-3 any claims, it is characterised in that Li₂Si₂O₅Crystalline phase accounts for crystallite glass The weight % of glass is 20~40%, is preferably 20~35%, more preferably 20~30%, more preferably 20~25%.

11. the devitrified glass as described in claim 1-3 any claims, it is characterised in that quartz and quartz solid solution The weight % that crystalline phase accounts for devitrified glass is 15~30%, is preferably 20~30%, more preferably 25~30%.

12. the devitrified glass as described in claim 1-3 any claims, it is characterised in that the Li₂Si₂O₅Crystalline phase and stone English and quartz solid solution are principal crystalline phase, and the weight % that its total content accounts for devitrified glass in devitrified glass is less than 50%, Preferably less than 48%, more preferably less than 46%.

13. the devitrified glass as described in claim 1-3 any claims, it is characterised in that LiAlSi₄O₁₀Crystalline phase accounts for crystallite The weight % of glass is no more than 15%.

14. the devitrified glass as described in claim 1-3 any claims, it is characterised in that the upper limit of glass liquidus temperature It it is preferably 1400 DEG C for 1450 DEG C, more preferably 1380 DEG C, be most preferably 1320 DEG C.

15. the devitrified glass as described in claim 1-3 any claims, it is characterised in that the heat of glass room temperature (25 DEG C) Conductance is in more than 2w/mk.

16. crystallite glass substrate, is made using the devitrified glass described in any rights of claim 1-15 through chemical tempering.

17. crystallite glass substrate as claimed in claim 16, it is characterised in that Vickers hardness (Hv) is 600kgf/mm²More than, Preferably 650kgf/mm²More than, more preferably 700kgf/mm²More than.

18. crystallite glass substrate as claimed in claim 16, it is characterised in that by the steel ball of 32g from the height of 500mm fall to The crystallite glass substrate will not be broken, and preferably height is more than 650mm, and more preferably height is more than 800mm.

19. crystallite glass substrate as claimed in claim 16, it is characterised in that three-point bending strength is more than 450Mpa, excellent Elect more than 600Mpa as, more preferably more than 800Mpa.

20. crystallite glass substrate as claimed in claim 16, it is characterised in that compression stress is formed by ion-exchange treatment Layer, the compression stress value of the compressive stress layers be more than 300Mpa, be preferably more than 400Mpa, be more preferably 500Mpa with On.

21. crystallite glass substrate as claimed in claim 20, it is characterised in that the thickness of the compressive stress layers for 1 μm with On, it is preferably more than 5 μm, more preferably more than 8 μm.