CN103359934A - Deformation-resistant high-yield-point and light zirconium boron-alumina silicate glass - Google Patents

Deformation-resistant high-yield-point and light zirconium boron-alumina silicate glass Download PDF

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CN103359934A
CN103359934A CN2012100929358A CN201210092935A CN103359934A CN 103359934 A CN103359934 A CN 103359934A CN 2012100929358 A CN2012100929358 A CN 2012100929358A CN 201210092935 A CN201210092935 A CN 201210092935A CN 103359934 A CN103359934 A CN 103359934A
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glass
zro
alumina silicate
silicate glass
aforementioned
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CN103359934B (en
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张广军
范慧艳
奥利弗·霍赫赖因
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Schott Glass Technologies Suzhou Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention relates to deformation-resistant high-yield-point and light zirconium boron-alumina silicate glass and particularly relates to alumina silicate glass containing ZrO2 and B2O3. The glass has the characteristics that the elasticity modulus E is more than or equal to 60 GPa and less than or equal to 78 GPa after the glass is chemically tempered; the yield point At is more than or equal to 620 DEG C and less than or equal to 850 DEG C; the coefficient of thermal expansion (CET) is more than or equal to 7.5*10<-6>/K and less than or equal to 9.8*10<-6>/K; the density is less than or equal to 2.5 g/cm<3>; the surface pressure stress is at least 700 MPa; and the thickness of a surface stress layer is at least 25 microns. The glass has deformation resistance, is high in yield point and is light in weight.

Description

The lightweight zirconium boron-alumina silicate glass of resistance to deformation high yield strength
Invention field
The present invention relates to a kind of alumina silicate glass that contains zirconium and boron, this glass has deformation resistance, and yield point temperature is high and lightweight.The invention still further relates to by the glasswork of described zirconium boron-alumina silicate glass through the chemical tempering preparation.Described zirconium boron-alumina silicate glass can be used in mobile equipment or the non-mobile device with indicating meter, also can be used in the white domestic appliances field.
Background of invention
Cover plate is used in electronics usually, mobile electronic device, and for example among personal digital assistant, movement or cellular phone, wrist-watch, portable computer, notebook computer, digital camera, the PDA, or as the substrate glass of touch-screen, televisor.For these application, the user needs often to touch cover plate, and owing to the touch to the user, glass can produce, for example, and the problems such as surface damage, scraping and distortion.These defectives will affect the normal operation of equipment.Because frequent contact, these cover plates must have high intensity and want scrape resistant and resistance to deformation.
Strength of glass is to be determined by the system of glass and composition in essence.Thereby seek to have more high strength, more high rigidity, low fragility, anti-scratch and deformation resistance glass, at first to start with from glass system and composition, by adjusting glass composition and composition, can improve Young's modulus, hardness and the fragility of glass, thereby obtain to have the glass of high impact properties, high scratch resistance and high deformation resistance.
Traditional soda-lime-silica glass can not satisfy these requirements, for example for high strength, and the requirement of high deformation resistance and scratch resistance.
Alumina silicate glass has high strength, high rigidity, stable chemical resistant properties, low thermal expansivity, high scrape resistant and shock resistance, is suitable as the cover plate of moving device (mobile telephone, smart phone, panel computer, notebook computer, PDA).This glass also can be used as the cover plate of irremovable device (televisor, PC, MTA equipment, digital camera, wrist-watch, industrial display), cover plate, protective window, automotive window, train vehicle window, aviation machine window and the hard disk base material of touch-screen.This glass also can be applied to the white domestic appliances field simultaneously, such as refrigerator and kitchen tools etc.
After glass system and composition are determined, can utilize the method for chemical tempering further to improve strength of glass, hardness, anti-scratch and deformation resistance.
Chemical tempering is used widely as the method that improves strength of glass.Chemical tempering is to realize by the ion exchange process under the low temperature environment.Be lower than under the temperature of strain point of glass, using molten salt solution, for example NaNO 3, KNO 3, or NaNO 3And KNO 3Mixture, the temperature of described molten salt solution is 380 ℃-500 ℃, sometimes even higher.This so that the sodium ion of glass surface by from the displacement of the potassium ion of molten salt solution.These potassium ions are greater than sodium ion, thereby when sodium ion moved in the potassium nitrate solution, potassium ion was wedged in the space that is stayed by less sodium ion, and this displacement of ion is so that glass surface is in compressed state, glass surface produces stress, produces tension compensating in center of glass.This chemical tempering can obviously improve strength of glass.
Although chemical tempering has been widely used in processing glass, improve strength of glass.But the demand along with technical development and application; the glass that is used for mobile equipment or non-mobile device; the protective shield of mobile phone, smart phone, panel computer, notebook, PDA, handheld game machine, MP3 player, wrist-watch, televisor, industrial display for example; the glass of display screen or touch-screen need to have deformation resistance, thereby can protect the electronic devices and components of device interior to be without prejudice when bound pair glass is exerted pressure outside.This application requiring glass can not have large distortion under external force, and for example crooked, less distortion more can protect the electronic devices and components of device interior to be without prejudice.Simultaneously, a kind of new trend thickness that is mobile equipment or non-mobile device become more and more come thin.For example, the integral thickness of mobile phone has been reduced to 8mm, even less than 7mm.Thinner mobile equipment or non-mobile device need the cover plate of indicating meter or touch display to have high dimensional precision; particularly be not out of shape or have very little distortion at the certain pressure lower-glass, thereby can protect the internal electronic component of equipment to be without prejudice.Therefore the glass that has deformation resistance is following a kind of demand.In order to obtain having the glass of deformation resistance, must consider existing glass composition is adjusted, such as, in order to obtain having the little glass of distortion, the Young's modulus of glass (E) should be large.But consider the overall mechanical properties of glass, intensity for example, the E of glass should be in the scope of optimizing.If E is too small, can cause large distortion can destroy the device interior electronic devices and components under the pressure-acting.When E was excessive, glass became really up to the mark thereby loses its toughness, thereby caused glass resistance to cracking line extendability to reduce, and workability reduces.Consider the chemical tempering in later stage, this glass also need have high yield point temperature, the less coefficient of expansion (CTE), to guarantee that glass is indeformable in the chemical tempering process.
Thinner mobile equipment or non-mobile device also need lightweight glass as cover plate, touch-screen or show glass.Along with the development of electron device, portability is more and more come important, and weight is one of key issue.Thereby alleviating portable device weight is a kind of new development trend.But the density of common soda-lime-silica glass is greater than 2.5g/cm 3, this density can not satisfy the needs of this new development, and soda-lime-silica glass does not have good chemical tempering performance.Dol is generally less than 10 μ m behind the chemical tempering.This thickness can't satisfy cover plate, touch-screen or show the service requirements of glass.
Density is less than 2.5g/cm 3Foam glass can reduce the gross weight of equipment, equipment is easy to carry more.In the situation that apply external force or because the deadweight, particularly in the situation that large-sized touch/protection display, can reduce the distortion that produces owing to own wt, for example warpage or bending, and be conducive to be reduced in the probability that deforms in the chemical tempering process.Simultaneously, low density glass has open glass network structure, and this can accelerate the ion-exchange speed in the chemical tempering process, enhances productivity.
In addition, behind the chemical tempering, if wish described glass directly is assembled in the electron device, in mobile phone, smart phone, panel computer, notebook computer, PDA etc., the size and dimension of glass is crucial.Need glass size after processing, to change less, the glass that does not preferably have dimensional change and do not have to be out of shape.In the situation that the size of chemically toughened glass becomes increasing, this requires even more important.For example, the touch-screen on televisor or the giant display needs at least 1 * 2 meters large size chemically toughened glass, and such application requiring glass has least amount of deformation.In addition, chemical tempering is the treatment process under hot conditions, and in the chemical tempering process, glass should enough be stablized, and distortion does not have warpage or bending, and will keep size constancy.
But glass of the prior art does not have and can satisfy simultaneously chemical tempering, high deformation resistance, and namely in the chemical tempering process, glass does not deform, warpage or bending, keeps simultaneously size constancy, and high yield strength temperature and low-density requirement.
From present disclosed patent documentation, and the patent documentation of prior art described below both all can not satisfy simultaneously can chemical tempering, have again deformation resistance, high yield strength temperature and lightweight requirement, thereby can't satisfy being used for mobile equipment or the cover plate of non-mobile device or the demand of touch-screen glass.
U.S. Patent Application Publication US 2009/0142568 has described and has contained Al 2O 3And B 2O 3Alumina silicate glass, this glass has high scratch resistance, still, this glass has the high SiO greater than 64wt% 2Content.High SiO 2Content causes glass to be difficult to melting, and production cost is high, and the chemical tempering performance also is difficult to be optimized.High SiO in the glass 2Content also can increase fragility, and therefore, the resistance to cracking line extendability of this glass is not enough.SiO 2The adjustment of the deformation resistance of the glass that content is high also is restricted.Do not have between optimized network organizer and the Network former and the ratio between Network former and the Network modifier, thereby the glass with high anti-deformation power can not be provided.In the document, do not mention deformation resistance and the yield temperature of glass.
Chinese patent application CN 200910086806 discloses and has contained ZrO 2Alumina silicate glass, still, this glass does not contain B 2O 3, the fragility of this glass is high, and resistance to cracking line extendability is low.In addition, this glass comprises CaO, comprise the easy crystallization of glass of CaO, and the CaO in the glass is also unfavorable for chemical tempering.In addition, this glass also comprises the disagreeableness Sb of environment 2O 3
U.S. Patent Application Publication US 2009/0202808 has described a kind of glass of anti scuffing.But this glass comprises the SiO greater than 64wt.% 2High SiO 2Cause glass to be difficult to melting, and the chemical tempering performance also is difficult for optimizing.High SiO in the glass 2Can increase the fragility of glass, so the resistance to cracking line extendability of this glass and deformation resistance deficiency.In addition, this glass comprises CaO, and the CaO in the glass is unfavorable for chemical tempering.MgO＞the 5wt.% of glass in this patent documentation, so the MgO of high-content is also unfavorable for chemical tempering.
U.S. Patent Application Publication US 2008/0286548 and US 2009/0220761 have described the alkaline alumina silicate glass with high-mechanical property.But this glass has high fusing point, and it is difficult to melting.This glass comprises the SiO of 64-68mol.% 2(weight percent＞64wt.%), this melt temperature that raise has increased glass viscosity and number of bubbles.High SiO in the glass 2Content also can increase fragility, and therefore, the resistance to cracking line extendability of this glass and deformation resistance are not enough.
US Patent No. 4055703 has been described and has been comprised P 2O 5Glass.But this glass has high P 2O 5Concentration is 2-20wt%.P 2O 5Concentration is high, easily causes glass opaque.Therefore, this patent needs more ZnO, and still, more ZnO easily causes crystallization, also is uneconomic in addition.
US Patent No. 5674790 has been described the glass with good chemical tempering performance.But this glass has high Li 2O concentration is 8-10wt%, and this is for batch production, and cost is expensive.In addition, comprise Li 2The glass of O is directly used KNO 3Carry out chemical tempering and can not reach requirement, must carry out mixing salt or two-step approach tempering, thereby increase tooling cost, limited the purposes of this glass.
U.S. Patent Application Publication US 2011/0201490 has described and has not contained ZrO 2Alumina silicate glass, this glass fragility is low.But the hardness of this glass is low, Hv＜520Kg/mm 2, and Young's modulus is also low.This glass does not contain ZrO 2, glass hard (HRC65Yi Shang) is low, is very easy to by scratch, and can causes the glass deformation resistance very poor under so low Young's modulus, can produce very large deflection under external force, and impact is used.
Summary of the invention
The present inventor has found a kind of glass composition of novelty, can solve defective of the prior art, thereby a kind of have deformation resistance, high yield strength temperature and lightweight zirconium boron-alumina silicate glass can be provided.
The present inventor finds, introduces the multiple network organizer in alumina silicate glass, rather than the simple SiO that uses as Network former 2And Al 2O 3, can optimize the glass network structure, make glass have high deformation resistance, high yield strength temperature, low density, low fragility, high resistance to crack extension ability and high chemical tempering ion-exchange capacity.Adjust B 2O 3, P 2O 5, ZrO 2With SiO 2, Al 2O 3Ratio, can make glass can have optimum performance combination.
The present inventor finds, adds ZrO 2And B 2O 3Can improve the glass deformation resistance, anti scuffing ability and cracking resistance line expanding ability reduce fragility, and optimize simultaneously and adjustment and P 2O 5, Al 2O 3, SiO 2Content and proportionlity, can make glass have simultaneously the chemical tempering of being more suitable for, higher deformation resistance, high yield strength temperature and low density.
Glass of the present invention is applicable to chemical tempering.This zirconium boron-alumina silicate glass has following performance: Young's modulus 60GPa≤E≤78GPa behind the chemical tempering; 620 ℃≤At of yield-point≤850 ℃; Thermal expansivity is 7.5 * 10 -6/ K≤CTE≤9.8 * 10 -6/ K; Density≤2.5g/cm 3Bearing stress (CS) is at least 700MPa; Surface stress layer thickness (Dol) is at least 25 μ m.
Zirconium boron-the alumina silicate glass that possesses this performance is the glass material of a kind of high elastic coefficient, high rigidity and low fragility.This glass material does not have distortion, warpage or bending in the chemical tempering process, and can keep size constancy.In addition, this glass has low density, is easy to carry.
In the present invention, except as otherwise noted, the weight percentage of all components is all based on the gross weight of glass all components, and glass all components sum is 100%.
Therefore, the invention provides following technical scheme.
The invention provides a kind of ZrO of containing 2And B 2O 3Alumina silicate glass, described glass comprises:
Figure BDA0000149491600000071
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 51wt.%,
0.004≤ZrO 2/Al 2O 3＜0.2，
0.07≤B 2O 3/SiO 2≤0.25，
0.16≤(P 2O 5+Al 2O 3)/SiO 2≤0.75。
On the other hand, the invention provides a kind of ZrO of containing 2And B 2O 3Alumina silicate glass, described glass comprises:
Figure BDA0000149491600000072
Figure BDA0000149491600000081
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 39wt.%,
0.005≤ZrO 2/Al 2O 3≤0.17，
0.07≤B 2O 3/SiO 2≤0.2，
0.2≤(P 2O 5+Al 2O 3)/SiO 2≤0.6。
Another aspect of the invention provides a kind of ZrO of containing 2And B 2O 3Alumina silicate glass, described glass comprises:
Figure BDA0000149491600000082
Figure BDA0000149491600000091
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 33wt.%,
0.01≤ZrO 2/Al 2O 3≤0.14，
0.07≤B 2O 3/SiO 2≤0.19，
0.23≤(P 2O 5+Al 2O 3)/SiO 2≤0.55。
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, 52wt.%≤SiO wherein 2≤ 61wt.%, preferred 52wt.%≤SiO 2≤ 59wt.%, more preferably 52wt.%≤SiO 2≤ 58wt.%.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, 0.2wt.%≤ZrO wherein 2≤ 1.5wt.%, preferred 0.5wt.%≤ZrO 2≤ 1wt.%.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, 4.5wt.%≤B wherein 2O 3≤ 8wt.%, preferred 4.5wt.%≤B 2O 3≤ 7.5wt.%.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, 20.5wt.%≤ZrO wherein 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 33wt.%, preferred 21wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 33wt.%.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, 0.015≤ZrO wherein 2/ Al 2O 3≤ 0.1, preferred 0.02≤ZrO 2/ Al 2O 3≤ 0.1.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, the Young's modulus of described glass is 60GPa≤E≤78GPa, preferred 69GPa＜E≤78GPa, more preferably 70GPa≤E≤78GPa.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, the yield-point of described glass is 620 ℃≤At≤850 ℃, is preferably 630 ℃≤At≤830 ℃, more preferably 650 ℃≤At≤800 ℃.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, the density≤2.50g/cm of wherein said glass 3, preferred≤2.49g/cm 3, more preferably≤2.45g/cm 3
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, under external force, deformation values≤5mm, preferred≤1mm, more preferably≤0.5mm.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, the thermal expansivity 7.5 * 10 of wherein said glass -6/ K≤CTE≤9 * 10 -6/ K, preferred 7.5 * 10 -6/ K≤CTE≤8.8 * 10 -6/ K.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, Dol behind the chemical tempering 〉=25 μ m, preferred Dol 〉=30 μ m, more preferably Dol 〉=35 μ m, Dol 〉=40 μ m most preferably.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, CS 〉=700MPa behind the chemical tempering, preferred CS 〉=800MPa, more preferably CS 〉=900MP, CS 〉=1000MPa most preferably.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, hardness 〉=530MPa behind the chemical tempering, preferred 〉=580MPa, more preferably 〉=650MPa, most preferably 〉=700MPa.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, the chemical tempering temperature is 350 ℃～490 ℃, the chemical tempering time is 1～16h; Preferred chemical tempering temperature is 350 ℃～490 ℃, and the chemical tempering time is 2～12h; More preferably the chemical tempering temperature is 400～480 ℃, and the chemical tempering time is 2～8h.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, described glass is thin glass, thickness≤5.0mm, preferred≤4.0mm, more preferably≤2.0mm, particularly preferably≤1.0mm.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, described glass can pass through several different methods, for example draws under little float glass process, glass tube down-drawing, the discharge orifice and draws method production under method or the melting.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass in making mobile telephone, smart phone, panel computer, notebook computer, PDA, televisor, PC, MTA machine, industrial display as the purposes of cover plate.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass for the manufacture of the purposes in touch-screen cover plate, protective window, automotive window, train vehicle window, aviation machine window, the hard disk base material.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass be used for the purposes in white domestic appliances field, as being used for refrigerator or kitchen tools.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, it can be used as the cover plate of moving electronic components, portable device or the backboard of notebook.
The present invention also provides a kind of ZrO of containing 2And B 2O 3And do not contain Li 2The alumina silicate glass of O and CaO is characterised in that described glass behind chemical tempering, and Young's modulus is 60GPa≤E≤78GPa, and yield-point is 620 ℃≤At≤850 ℃, and density is≤2.5g/cm 3
On the other hand, the invention provides a kind of alumina silicate glass, be characterised in that described glass is behind chemical tempering:
Young's modulus 60GPa≤E≤78GPa;
620 ℃≤At of yield-point≤850 ℃;
Thermal expansivity 7.5 * 10 -6/ K≤CTE≤9.8 * 10 -6/ K;
Density≤2.5g/cm 3
Bearing stress CS 〉=700MPa;
Surface stress layer thickness Dol 〉=25 μ m.
The aforementioned described ZrO that contains in two aspects in the present invention 2And B 2O 3Alumina silicate glass, be characterised in that described glass consists of:
Figure BDA0000149491600000121
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 51wt.%,
0.004≤ZrO 2/Al 2O 3＜0.2，
0.07≤B 2O 3/SiO 2≤0.25，
0.16≤(P 2O 5+Al 2O 3)/SiO 2≤0.75。
Be further characterized in that described glass consists of:
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 39wt.%,
0.005≤ZrO 2/Al 2O 3≤0.17，
0.07≤B 2O 3/SiO 2≤0.2，
0.2≤(P 2O 5+Al 2O 3)/SiO 2≤0.6。
Be characterised in that further described glass consists of:
Figure BDA0000149491600000132
Figure BDA0000149491600000141
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 33wt.%,
0.01≤ZrO 2/Al 2O 3≤0.14，
0.07≤B 2O 3/SiO 2≤0.15，
0.23≤(P 2O 5+Al 2O 3)/SiO 2≤0.55。
Another aspect of the invention provides a kind of ZrO that contains that can be used in chemical tempering 2And B 2O 3Alumina silicate glass, as common mobile equipment or non-mobile device protective shield, when touch-screen or display screen, under external force, deformation values≤5mm, preferred≤1mm, more preferably≤0.5mm.
Aforementioned schemes contain ZrO 2And B 2O 3Alumina silicate glass, be characterised in that described glass consists of:
Figure BDA0000149491600000142
Figure BDA0000149491600000151
Wherein, 23wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 51wt.%,
0.004≤ZrO 2/Al 2O 3≤0.16，
0.07≤B 2O 3/SiO 2≤0.25，
0.16≤(P 2O 5+Al 2O 3)/SiO 2≤0.75。
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, described glass can be by chemical tempering, Dol behind the chemical tempering 〉=25 μ m and CS 〉=700MPa, wherein preferred Dol 〉=30 μ m, more preferably Dol 〉=35 μ m, Dol 〉=40 μ m most preferably.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, described glass can be by chemical tempering, Dol behind the chemical tempering 〉=25 μ m and CS 〉=700MPa, wherein preferred CS 〉=800MPa, more preferably CS 〉=900MP, CS 〉=1000MPa most preferably.
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, be characterised in that described glass is behind chemical tempering:
Young's modulus 70GPa≤E≤78GPa;
630 ℃≤At of yield-point≤850 ℃;
Thermal expansivity 7.5 * 10 -6/ K≤CTE≤9 * 10 -6/ K;
Density≤2.49g/cm 3
The described ZrO that contains of aforementioned arbitrary scheme in the present invention 2And B 2O 3Alumina silicate glass, as common mobile equipment or non-mobile device protective shield, when touch-screen or display screen, be characterised in that described glass is behind chemical tempering:
Under external force, deformation values≤5mm, preferred≤1mm, more preferably≤0.5mm;
Young's modulus 70GPa≤E≤78GPa;
620 ℃≤At of yield-point≤850 ℃;
Thermal expansivity 7.5 * 10 -6/ K≤CTE≤9 * 10 -6/ K;
Density≤2.5g/cm 3
Bearing stress CS 〉=700MPa;
Surface stress layer thickness Dol 〉=25 μ m.
Glass of the present invention also is suitable as for example cover plate of personal digital assistant, movement or cellular phone, wrist-watch, portable computer and notebook computer, digital camera, PDA, or is used as the substrate glass of touch-screen.Described glass is applicable electronic substrate, for example hard disk done also.Described glass has high impact properties, high rigidity, high elastic coefficient, low fragility, high deformation resistance, high yield strength temperature and low density.Described glass is suitable for the ion-exchange by chemical tempering.
Detailed description of the Invention
The present invention relates to contain ZrO 2And B 2O 3Alumina silicate glass, its Young's modulus behind chemical tempering is 60GPa≤E≤78GPa; Yield-point is 620 ℃≤At≤850 ℃; Thermal expansivity is 7.5 * 10 -6/ K≤CTE≤9.8 * 10 -6/ K; Density≤2.5g/cm 3Stress (CS) is at least 700MPa; Surface stress layer thickness (Dol) is at least 25 μ m.In addition, described glass has deformation resistance, yield point temperature is high and lightweight, and this glass fragility is low simultaneously, Young's modulus is high, resistance to cracking line extendability is good and hardness is high.
SiO 2The Network former of commonly using, in soda-lime-silica glass, SiO 2It is main Network former.In alumina silicate glass, SiO 2And Al 2O 3It is main Network former.But simple SiO 2And Al 2O 3The glass fragility that Network former forms is large, and the ion-exchanging efficiency of intensity, deformation resistance and chemical tempering is not high enough.By introducing ZrO 2, B 2O 3And further introduce P 2O 5Network structure is adjusted, can be formed the network structure of optimization, make glass have high deformation resistance, high yield temperature, low density, low fragility, high resistance to crack extension ability and high chemical tempering ion-exchange capacity.Adjust B 2O 3, P 2O 5, ZrO 2With SiO 2, Al 2O 3Ratio, can make glass can have optimum performance combination.
Introduce ZrO 2, use ZrO 2Replace part Al 2O 3, can change the glass microtexture, improve the Young's modulus of glass, reduce the CTE of glass, effectively control ZrO 2And Al 2O 3Ratio can improve non-deformability and the yield point temperature of glass.
Introduce B 2O 3, use B 2O 3Replace part SiO 2, can change the glass reticulated structure, thereby can improve CTE and the fragility of glass.Effectively control B 2O 3And SiO 2Ratio can change the glass network structure, optimizes glass properties, reaches the CTE that reduces, optimize glass and the purpose of glass fragility, raising glass resistance to crack extension ability.
Further, can introduce P 2O 5, adjust (P 2O 5+ Al 2O 3)/SiO 2Content and ratio can improve the chemical tempering ion-exchange performance, optimize simultaneously deformation resistance, thermal expansivity and the yield point temperature of glass, and make glass can obtain suitable melt temperature and the performance of optimization.
Strength of glass can characterize with stress (CS) and layer thickness (Dol).Need in actual applications high CS and high Dol.Usually, be higher than the CS of 700MPa and to be higher than 25 Dol be favourable.
Yield-point among the present invention (At) is defined as the starting point temperature of glass deformation.The deformation point temperature may be defined as on the thermal expansion curve of being measured by dilatometer, and deformation point is the point of elongation vanishing.When temperature reached yield-point, glass began deliquescing.Glass even can deform because of deadweight.If yield-point is low, in hot environment, the probability of glass deformation is large; Any little distortion all can affect the shape and size of the finished product.
Yield-point is generally 620 ℃≤At≤850 ℃.The chemical tempering temperature is 380-600 ℃, comprises cryochemistry tempering and pyrochemistry tempering, and the chemical tempering time is 1-30 hour.Chemical tempering is ion exchange process, and the temperature of chemical tempering is higher, and the speed of ion-exchange is faster.Yield-point should be than the high 250-300 of chemical tempering temperature ℃.If the difference of yield-point and chemical tempering temperature is little, stress can occur lax.Differing greatly of yield-point and chemical tempering temperature then can reduce the lax probability of stress, also can reduce the probability of distortion.Yield-point can be easily definite by dilatometer, thereby can estimate the upper limit of chemical tempering temperature.On the other hand, the cover plate with high yield strength can be used on the device that moves under hot environment, and for example, the glass with high yield strength can be used on the airline, and this glass does not soften under fricative high temperature.
Deformation resistance is included in the distortion under load (pressure, the surging force) effect among the present invention, the change of shape in the chemical tempering process and the variation of size in the chemical tempering process.Deformation resistance refer to glass under above-mentioned any condition indeformable or the distortion less than threshold value.Deformability in the chemical tempering process refers to the increase of glass size after ion-exchange or reduces.For example, at K +Displacement Na +It is large that rear size becomes.Usually, 7.5 * 10 -6/ K≤CTE≤9.8 * 10 -6The glass of/K can keep size constancy in the chemical tempering process, and Young's modulus is at 60GPa≤E≤78GPa behind the chemical tempering, and glass deformation will be very little, thereby can protect electronic component to avoid infringement under certain load.The Young's modulus of glass is defined as glass in recoverable deformation in the stage, the ratio of normal stress and corresponding normal strain.
The deformation resistance of glass is described below:
Glass is placed on two point of suppon or two support edges on, span between two point of suppon or the support edge is the maximum length L of glass, load forces F is applied to the top side of glass, glass is not level when having load forces, this horizontal plane is called the original water plane, along with load forces increases, glass deforms, and the distance between deformation point and the original water plane is deformation values.Deformation values is larger, and glass more easily is out of shape, and deformation resistance is just lower.
When described glass is used as the indicating meter of moving device, the diagonal lines≤500mm of described glasswork ,≤300mm ,≤200mm ,≤120mm ,≤100mm ,≤95mm ,≤90mm ,≤80mm ,≤75mm ,≤70mm ,≤60mm; Area≤the 500cm of described glasswork 2,≤300cm 2,≤100cm 2,≤50cm 2When thickness is 0.2mm-3mm, deformation values≤5mm ,≤3mm ,≤1mm ,≤0.5mm ,≤0.1mm.
If when the moving device, moving device means little size, the size of mobile display≤12 inch ,≤9.7 inches ,≤4.3 inches ,≤3.8 inches.
For the cover plate that is used for moving device, when glass size≤12 inch ,≤9.7 inches ,≤4.3 inches ,≤3.8 inches, when the thickness of glass was 0.2mm-3mm, the glass deformation value was≤5mm ,≤3mm ,≤1mm ,≤0.5mm ,≤0.1mm.
For other device, TV for example, large-sized indicating meter etc., size is usually larger.The size of indicating meter 〉=12 inch, 〉=20 inches, 〉=30 inches, 〉=42 inches, 〉=55 inches or 〉=60 inches.
For being used for the indicating meter cover plate, when glass size 〉=12 inch, 〉=20 inches, 〉=30 inches, 〉=42 inches, 〉=55 inches or 〉=60 inches, when thickness of glass was 1-5mm, the glass deformation value was≤10mm ,≤5mm ,≤3mm ,≤1mm ,≤0.5mm ,≤0.1mm.
Example among the present invention just is used for illustrating advantage of the present invention and characteristic, can not be regarded as limitation of the scope of the invention.
The rigidity of material is defined as the required stress of relative deformation of material production unit elasticity.It is exosyndrome material opposing elastic deformability's mechanical performance index.
Glass has the ability of certain resistance to deformation among the present invention, and enough rigidity is namely arranged.
The resistance to deformation zirconium boron-alumina silicate glass that is used for chemical tempering, rigidity is at about 0.75MPam 0.5-0.85MPam 0.5Scope in, preferably at about 0.83MPam 0.5To about 0.85MPam 0.5Scope in.Rigidity is less than 0.75MPam 0.5, the glass non-deformability is lower, and greater than 0.85MPam 0.5The difficulty that will cause owing to too high stress glass processing.
When the fragility of glass was defined as the following applying load of transition temperature, any plastic deformation that can observe does not occur glass, and (strain stress was 10 -4Below), i.e. fracture.The fragility of glass is larger, is easy to do not having in the situation premonitory at stressed rear glass and suddenly breaks, thereby cause personal injury and property damage.
Be used for the resistance to deformation zirconium boron-alumina silicate glass of chemical tempering, fragility is 6-9 μ m behind the chemical tempering -0.5, preferred 6-8.5 μ m -0.5, more preferably 6-8 μ m -0.5Fragility is less than 6 μ m -0.5, glass hard (HRC65Yi Shang) is too little and be unfavorable for glass processing, easily produce scratch and crackle in application, and fragility is greater than 9 μ m -0.5Then glass resistance to cracking line extended capability can be very poor, and after glass was cracked by external force, crackle is expansion at once, causes glass breaking.
The present invention relates to deformation resistance, high yield temperature and low density glass, described glass is to contain ZrO 2And B 2O 3Alumina silicate glass.Young's modulus 60GPa≤E≤78GPa behind this resistance to deformation glass chemistry toughening; 620 ℃≤At of yield-point≤850 ℃; Thermal expansivity 7.5 * 10 -6/ K≤CTE≤9.8 * 10 -6/ K; Density≤2.5g/cm 3Described glass is suitable for chemical tempering, and is suitable for preparing the glasswork of chemical tempering.
Glass of the present invention does not contain Li 2O and CaO.
In addition, described glass be suitable for preparing thickness≤5.0mm ,≤4.0mm ,≤2.0mm ,≤1.0mm ,≤the thin glass of 0.5mm.
Described glass environmental friendliness, and do not contain As 2O 3And Sb 2O 3Described glass can be produced with the float glass process technology.
SiO 2Be main glass forming substances, and be single-component maximum in the glass, can form strong reticulated structure.Al 2O 3And B 2O 3It also is glass forming substances.P 2O 5At least can be with four kinds of form crystallizations, modal polymorph comprises P 4O 10Molecule, other polymorph is polymerization.P 2O 5Feature weak reticulated structure is provided.Strong reticulated structure is disadvantageous for ion-exchange, causes the reduction of ion-exchange speed and the degree of depth.Weak reticulated structure then can reduce the stability of glass.Therefore, should optimize strong reticulated structure and weak reticulated structure.As 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 51wt.%, preferred 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 39wt.%, more preferably 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3During≤33wt.%, high Dol not only can be obtained, and high CS can be obtained.Simultaneously, can improve deformation resistance, intensity, the reduction glass fragility of glass.Further, ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3Summation is 20.5wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 33wt.%, preferred 21wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 33wt.%.
SiO 2Content be 45-＜64wt.%, be preferably 50-63.5wt%, more preferably 52-62wt%.SiO 2In these glass, exist as netted forming agent with the amount of 45wt% at least.Cross low SiO 2Can adversely affect the weather resistance of glass.The glass of many prior aries comprises the SiO that is higher than 64wt% 2Tetrahedron SiO 4 -Be the primary structure unit in the glass, tight and harder, such structure causes the more crisp and resistance to cracking line extendability of glass to reduce, and has simultaneously the ion-exchange speed of reduction.In addition, SiO 2Ratio increase to and be higher than 64wt% and can cause transition temperature and melt temperature to raise.SiO 2Amount be that 50-63.5wt% helps to reduce CTE.Further, SiO 2Content can be 52wt.%≤SiO 2≤ 61wt.%, preferred 52wt.%≤SiO 2≤ 59wt.%, more preferably 52wt.%≤SiO 2≤ 58wt.%.
Al 2O 3Content in the scope of＞10-28wt%.Al 2O 3Deformation resistance, thermal expansivity, thermotolerance, ion-exchange performance and Young's modulus etc. for improvement glass are effective.But, work as Al 2O 3Content when increasing, the devitrification crystal often precipitates in glass, thermal expansivity becomes too little so that is difficult to and is consistent with material around, and viscosity at high temperature becomes higher, is difficult to produce.Al 2O 3Be lower than Young's modulus and strength decreased that 10wt% will cause glass, thermal expansivity becomes large and yield temperature point step-down.
ZrO 2Can improve the chemical stability of glass, increase viscosity, hardness, and reduce thermal expansivity, reduce glass fragility.ZrO 2Content be 0.01-2wt.%.ZrO 2＞2wt.% easily causes glass crystallization, and ZrO 2The glass of＜0.01wt.% does not have high chemical stability.ZrO2 content is 0.1wt.%≤ZrO 2≤ 2wt.%, preferred 0.1wt.%≤ZrO 2≤ 2wt.%, more preferably 0.1wt.%≤ZrO 2≤ 1.5wt.%.Further, 0.2wt.%≤ZrO 2≤ 1.5wt.%, preferred 0.5wt.%≤ZrO 2≤ 1wt.%.
Further, 0.004≤ZrO 2/ Al 2O 3＜0.2 can increase and keep glass to have high Young's modulus, improves CTE and the fragility of glass deformation resistance, reduction glass.Only comprise Al 2O 3Glass fragility large, this causes the possibility of glass breaking to increase.An amount of some ZrO that add 2, so that 0.004≤ZrO 2/ Al 2O 3＜0.2, glass will have the Young's modulus and 7.5 * 10 of 60GPa≤E≤78GPa -6/ K≤CTE≤9.8 * 10 -6The thermal expansivity of/K.By adding ZrO 2, Dol and CS are improved, and the intensity of glass also is improved simultaneously.ZrO 2The acid proof mode of composition and silicon-dioxide is similar, therefore, contains ZrO 2Glass often have good acid resistance, even in the situation that dioxide-containing silica low also be like this.Simultaneously, the tempering ability of the oxide glass of mixing usually with comprise equivalent Al 2O 3Or ZrO 2TERNARY GLASS identical.ZrO 2/ Al 2O 3Be 0.004≤ZrO 2/ Al 2O 3＜0.2, preferred 0.005≤ZrO 2/ Al 2O 3≤ 0.17, more preferably 0.01≤ZrO 2/ Al 2O 3≤ 0.14.Further, 0.015≤ZrO 2/ Al 2O 3≤ 0.1, preferred 0.02≤ZrO 2/ Al 2O 3≤ 0.1.
Use B 2O 3Replace part SiO 2Can improve CTE and the fragility of glass.0.07≤B 2O 3/ SiO 2≤ 0.25 can reduce CTE and the fragility that reduces glass.Use B 2O 3Replace SiO 2Can change the glass reticulated structure.SiO 4Tetrahedron and [3] BO 3(the stratiform trihedron structure of [3] expression two-dimensional space) plane triangle does not need charge compensation, so they form open reticulated structure.[3] the specific plane structure of B unit also helps greatly densification.[3] B Plain Triangular Element is introduced SiO 2In the major network shape structure so that reticulated structure hardness step-down, so that under stress, densification occurs.Open reticulated structure and two dimensional structure cause densification easier, and this has reduced CTE, density and the fragility of glass.B 2O 3In the scope of 4-15wt%.B 2O 3Has the effect that reduces melt temperature, high temperature viscosity and density as effective fusing assistant.B 2O 3Glass density be can reduce, reduce thermal expansivity, heat-resisting cataclysm and chemical resistant properties increased.Add B 2O 3Can reduce fragility and density.Further, B 2O 3/ SiO 2Be 0.07≤B 2O 3/ SiO 2≤ 0.25, preferred 0.07≤B 2O 3/ SiO 2≤ 0.2, more preferably 0.07≤B 2O 3/ SiO 2≤ 0.19.
In glass composition of the present invention, the glass properties for realizing optimizing realizes purpose of the present invention, and having been found that increases P in the glass 2O 5The velocity of ion exchange of glass is improved.SiO 2Be main glass forming substances, and be single component maximum in the glass, can form strong reticulated structure.P 2O 5It also is glass forming substances.P 2O 5At least can be with four kinds of form crystallizations.Modal polymorph comprises P 4O 10Molecule.Other polymorph is polymerization, but in all cases, phosphorus atom is linked to each other by tetrahedral Sauerstoffatom, and one of them Sauerstoffatom forms terminal P=O key.The combining form of this phosphorus oxygen key and unlike existing with the silicon-oxy tetrahedron structure in some silicate, but adopt by interconnective P 6O 6The laminate structure that ring forms.P 2O 5Feature weak reticulated structure is provided.Strong reticulated structure is disadvantageous for ion-exchange, causes the reduction of ion-exchange speed and the degree of depth.But weak reticulated structure can reduce the stability of glass.Therefore, should optimize strong reticulated structure and weak cancellated ratio and composition.Make up rightly strong and weak glass forming substances and can improve ion-exchange speed and the degree of depth.P 2O 5By opening glass structure and increase velocity of diffusion keying action has been played in the raising of glass tempering performance.P 2O 5Be 0-8wt%, preferred 0-4wt%, more preferably 0.1-2wt%.P 2O 5Increase also advantageously increased yield-point and adjusted glass melting temperature.But P 2O 5＞8wt.% will have a negative impact to chemical resistant properties and the product uniform ingredients degree of glass, simultaneously P 2O 5＞8wt.%, glass is easy to devitrification.From the viewpoint of batch production cost, surpass a large amount of P that needs 2O 5Undesirable.
Further, adjust P 2O 5, Al 2O 3And SiO 2Ratio can optimize the glass tempering performance.0.16≤(P 2O 5+ Al 2O 3)/SiO 2≤ 0.75 can increase speed, increase Dol, increase CS and the flexural strength of ion-exchange.(P 2O 5+ Al 2O 3)/SiO 2For 0.16-0.75, preferred 0.2-0.6, more preferably the glass of 0.23-0.55 can obtain suitable melt temperature and high Young's modulus, and then described glass can obtain Dol 〉=25 μ m behind chemical tempering and CS is 〉=700MPa.
Na 2O exists with fusing assistant, and the position of exchange is provided for subsequently ion-exchange.Na 2O＞20wt.% can reduce the chemical resistant properties of glass, and glass should contain at least 9% Na usually 2O remains on practical level with the melt temperature with glass, and makes glass have significant ion-exchange performance.
Thereby MgO reduces the component that the glass high temperature viscosity improves meltability and formability, and can improve strain point and Young's modulus.In addition, in the alkaline earth metal oxide component, MgO more can improve ion-exchange performance significantly.Correspondingly, wish that usually content is in the scope of 0-＜3.5%.
In glass composition, there is not CaO.On the one hand, use CaO easily to make devitrification of glass, produce devitrification, on the other hand, CaO has obvious negative impact to chemical tempering.
SrO is the component that can consider with various purposes adding.But when containing these a large amount of components, in some cases, the density of glass and thermal expansivity increase, and increased devitrification resistance is deteriorated, and cracking frequency uprises, and the degree of depth of compressive stress layer shoals after the ion-exchange.
K 2O can make the reduced viscosity of high temperature lower-glass, thereby improves meltability and the moldable property of glass, reduces cracking frequency.In addition, K 2O also is the composition that improves devitrification behavior.K 2In the 0-8wt.% scope, when being higher than 8wt%, increased devitrification resistance is deteriorated usually for the content of O.
TiO 2Can make the reduced viscosity of high temperature lower-glass, thereby improve the meltability of glass.TiO 2Content usually in the 0-5wt.% scope, when being higher than 5wt%, the easy crystallization of glass.
Glass of the present invention can comprise a small amount of conventional finings.The total amount of the finings that adds preferably mostly is most 2.0wt%, more preferably mostly is most 1.0wt%, and this tittle is the amount with respect to other remaining ingredient of glass, but add-on is wanted so that glass composition components is 100wt%.Can comprise at least a as finings (amount with wt% is added in all the other glass ingredients in addition) in the following composition according to glass of the present invention:
CeO 2 0.01-＜0.2％
F 2 0-0.5％
SnO 2 0.01-0.5％
。
In order to help to eliminate formation of gaseous inclusions, it is favourable adding other chemical clarification agent.This class finings is filled the bubble of the early origin that contains gas, thereby has increased their climbing speeds when melting.Typical finings includes but not limited to: arsenic oxide arsenoxide, weisspiessglanz, stannic oxide and Cs2O; Metal halide; Metal sulfate etc.But arsenic and antimony are considered to poisonous material usually, and glass of the present invention does not contain arsenic and antimony.
Embodiment
The employed starting material of the test of the embodiment of the invention are (all available from Chemical Reagent Co., Ltd., Sinopharm Group, Suzhou, chemical grade) such as oxide compound, oxyhydroxide, carbonate and nitrate.
The transition temperature T of glass is measured in the test of the embodiment of the invention at the thermal dilatometer of anti-relaxation the (DIL402PC of anti-the relaxation) gWith thermal expansivity CTE.After glass sample made bar-shaped sample about 50mm, be completed from room temperature take speed as 5 ℃/min is warming up to.
Measure the density of glass by Archimedes' principle.Glass sample is put into the volume change of the also accurate measuring vessel water of container that fills water, thereby obtained the volume of sample.The example weight that utilization can accurately be measured obtains density data divided by volume.
The sample chemical tempering.Level small-sized salt bath furnace in chamber carries out (diameter 250 * 250mm, degree of depth 400mm) and carries out tempering by experiment.Sample is positioned on the special protection against corrosion stainless steel specimen holder.At KNO 3Under 370-480 ℃, carry out 4-8 hour ion exchange treatment in the salt bath.
The stress of glass and the stressor layers degree of depth are by FSM6000 and determination of polarized light microscopy.
The CMT6503 type universal testing machine test that the Young's modulus of glass is provided by Mei Tesi industrial system company limited.
The hardness of glass is tested by HXD-1000 Vickers' hardness instrument.
Embodiments of the invention for example understand advantages and features of the invention, and these embodiment can not think any limitation of the invention.
Table 1 is the illustrative embodiments in preferred compositing range.The glass of describing in an embodiment prepares according to following steps:
After weighing and mixing, mixture is put into platinum crucible.With its melting in 1600-1660 ℃ electric smelter, then be cast in the stainless steel mould that is preheated to 500～600 ℃ of suitable temperature, then slowly cooling forms glass.
When carrying out the deformation resistance assessment, for embodiments of the invention, sample L is 20mm.Sample L elects 20mm as, is for advantages and features of the invention are described, the sample L among these embodiment can not think any limitation of the invention.
Glass in the comparative example has low-yield or low E or high-density or low Dol or low CS.That is to say, the glass of prior art can not satisfy the needs of high yield strength, high E, low density, high Dol and high CS simultaneously.
Figure BDA0000149491600000271
Figure BDA0000149491600000281
Figure BDA0000149491600000291
Figure BDA0000149491600000301
The contrast of table 3. embodiment and comparative example
Composition/wt.% Embodiment 1 Comparative example 1 Comparative example 2
SiO 2 55.10 73.00 75.62
Al 2O 3 21.16 0.27 1.17
Na 2O 11.19 13.70 14.38
K 2O 3.04 0.03 0.26
ZrO 2 0.69
CeO 2 0.10
SnO 2 0.38
F 2
B 2O 3 7.10
P 2O 5 1.24
MgO 4.00
CaO 9.00 0.05
ZnO 8.52
ZrO 2/Al 2O 3 0.033 0 0
B 2O 3/SiO 2 0.129 0 0
(P 2O 5+Al 2O 3)/SiO 2 0.407 0.004 0.015
ZrO 2+Al 2O 3+P 2O 5+B 2O 3(wt.％) 30.20 0.27 1.17
The Performance Ratio of embodiment and comparative example is more as shown in table 4.
Table 4
Embodiment 1 Comparative example 1 Comparative example 2
Density (g/cm 3) 2.39 2.52 2.54
Tg(℃) 600 560 570
CTE(1×10 -6K -1) 8.40 8.60 9.93
At (yield-point) ℃ 730 610 630
Young's modulus (GPa) (behind the tempering) 73 72 70
Thickness (mm) 0.71 0.71 0.71
Deformation values under 30N (mm) 0.070 0.085 0.090
Hardness (MPa) 700 530 550
The chemical tempering time (hour) 6 6 6
The chemical tempering temperature (℃) 420 420 420
Dol(μm) 42 7 10
CS(MPa) 970 607 590

Claims (34)

1. one kind contains ZrO 2And B 2O 3Alumina silicate glass, described glass comprises:
Figure FDA0000149491590000011
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 51wt.%,
0.004≤ZrO 2/Al 2O 3＜0.2，
0.07≤B 2O 3/SiO 2≤0.25，
0.16≤(P 2O 5+Al 2O 3)/SiO 2≤0.75。
2. the ZrO that contains according to claim 1 2And B 2O 3Alumina silicate glass, described glass comprises:
Figure FDA0000149491590000012
Figure FDA0000149491590000021
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 39wt.%,
0.005≤ZrO 2/Al 2O 3≤0.17，
0.07≤B 2O 3/SiO 2≤0.2，
0.2≤(P 2O 5+Al 2O 3)/SiO 2≤0.6。
3. the ZrO that contains according to claim 1 2And B 2O 3Alumina silicate glass, described glass comprises:
Figure FDA0000149491590000022
Figure FDA0000149491590000031
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 33wt.%,
0.01≤ZrO 2/Al 2O 3≤0.14，
0.07≤B 2O 3/SiO 2≤0.19，
0.23≤(P 2O 5+Al 2O 3)/SiO 2≤0.55。
4. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, 52wt.%≤SiO wherein 2≤ 61wt.%, preferred 52wt.%≤SiO 2≤ 59wt.%, more preferably 52wt.%≤SiO 2≤ 58wt.%.
5. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, 0.2wt.%≤ZrO wherein 2≤ 1.5wt.%, preferred 0.5wt.%≤ZrO 2≤ 1wt.%.
6. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, 4.5wt.%≤B wherein 2O 3≤ 8wt.%, preferred 4.5wt.%≤B 2O 3≤ 7.5wt.%.
7. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, 20.5wt.%≤ZrO wherein 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 33wt.%, preferred 21wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 33wt.%.
8. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, 0.015≤ZrO wherein 2/ Al 2O 3≤ 0.1, preferred 0.02≤ZrO 2/ Al 2O 3≤ 0.1.
9. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, the Young's modulus of described glass is 60GPa≤E≤78GPa, preferred 69GPa＜E≤78GPa, more preferably 70GPa≤E≤78GPa.
10. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, the yield-point of described glass is 620 ℃≤At≤850 ℃, is preferably 630 ℃≤At≤830 ℃, more preferably 650 ℃≤At≤800 ℃.
11. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, the density≤2.50g/cm of wherein said glass 3, preferred≤2.49g/cm 3, more preferably≤2.45g/cm 3
12. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, under external force, deformation values≤5mm, preferred≤1mm, more preferably≤0.5mm.
13. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, the thermal expansivity 7.5 * 10 of wherein said glass -6/ K≤CTE≤9 * 10 -6/ K, preferred 7.5 * 10 -6/ K≤CTE≤8.8 * 10 -6/ K.
14. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, Dol behind the chemical tempering 〉=25 μ m, preferred Dol 〉=30 μ m, more preferably Dol 〉=35 μ m, Dol 〉=40 μ m most preferably.
15. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, CS 〉=700MPa behind the chemical tempering, preferred CS 〉=800MPa, more preferably CS 〉=900MP, CS 〉=1000MPa most preferably.
16. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, hardness 〉=530MPa behind the chemical tempering, preferred 〉=580MPa, more preferably 〉=650MPa, most preferably 〉=700MPa.
17. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, the chemical tempering temperature is 350 ℃～490 ℃, the chemical tempering time is 1～16h; Preferred chemical tempering temperature is 350 ℃～490 ℃, and the chemical tempering time is 2～12h; More preferably the chemical tempering temperature is 400～480 ℃, and the chemical tempering time is 2～8h.
18. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, described glass is thin glass, thickness≤5.0mm, preferred≤4.0mm, more preferably≤2.0mm, particularly preferably≤1.0mm.
19. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, described glass can pass through several different methods, for example draws under little float glass process, glass tube down-drawing, the discharge orifice and draws method production under method or the melting.
20. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass in making mobile telephone, smart phone, panel computer, notebook computer, PDA, televisor, PC, MTA machine, industrial display as the purposes of cover plate.
21. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass for the manufacture of the purposes in touch-screen cover plate, protective window, automotive window, train vehicle window, aviation machine window, the hard disk base material.
22. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass be used for the purposes in white domestic appliances field, as being used for refrigerator or kitchen tools.
23. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, it can be used as the cover plate of moving electronic components, portable device or the backboard of notebook.
24. one kind contains ZrO 2And B 2O 3And do not contain Li 2The alumina silicate glass of O and CaO is characterised in that described glass behind chemical tempering, and Young's modulus is 60GPa≤E≤78GPa, and yield-point is 620 ℃≤At≤850 ℃, and density is≤2.5g/cm 3
25. alumina silicate glass according to claim 24 is characterised in that described glass is behind chemical tempering:
Young's modulus 60GPa≤E≤78GPa;
620 ℃≤At of yield-point≤850 ℃;
Thermal expansivity 7.5 * 10 -6/ K≤CTE≤9.8 * 10 -6/ K;
Density≤2.5g/cm 3
Bearing stress CS 〉=700MPa;
Surface stress layer thickness Dol 〉=25 μ m.
26. according to aforementioned claim 24 or the 25 described ZrO that contain 2And B 2O 3Alumina silicate glass, be characterised in that described glass consists of:
Figure FDA0000149491590000061
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 51wt.%,
0.004≤ZrO 2/Al 2O 3＜0.2，
0.07≤B 2O 3/SiO 2≤0.25，
0.16≤(P 2O 5+Al 2O 3)/SiO 2≤0.75。
27. according to aforementioned claim 24 or the 25 described ZrO that contain 2And B 2O 3Alumina silicate glass, be characterised in that described glass consists of:
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 39wt.%,
0.005≤ZrO 2/Al 2O 3≤0.17，
0.07≤B 2O 3/SiO 2≤0.2，
0.2≤(P 2O 5+Al 2O 3)/SiO 2≤0.6。
28. according to aforementioned claim 24 or the 25 described ZrO that contain 2And B 2O 3Alumina silicate glass, be characterised in that described glass consists of:
Figure FDA0000149491590000081
Wherein, 20wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 33wt.%,
0.01≤ZrO 2/Al 2O 3≤0.14，
0.07≤B 2O 3/SiO 2≤0.15，
0.23≤(P 2O 5+Al 2O 3)/SiO 2≤0.55。
29. ZrO that contains that can be used in chemical tempering 2And B 2O 3Alumina silicate glass, as common mobile equipment or non-mobile device protective shield, when touch-screen or display screen, under external force, deformation values≤5mm, preferred≤1mm, more preferably≤0.5mm.
30. according to the described ZrO that contains of aforementioned claim 29 2And B 2O 3Alumina silicate glass, be characterised in that described glass consists of:
Figure FDA0000149491590000082
Figure FDA0000149491590000091
Wherein, 23wt.%≤ZrO 2+ B 2O 3+ P 2O 5+ Al 2O 3≤ 51wt.%,
0.004≤ZrO 2/Al 2O 3≤0.16，
0.07≤B 2O 3/SiO 2≤0.25，
0.16≤(P 2O 5+Al 2O 3)/SiO 2≤0.75。
31. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, described glass can be by chemical tempering, Dol behind the chemical tempering 〉=25 μ m and CS 〉=700MPa, wherein preferred Dol 〉=30 μ m, more preferably Dol 〉=35 μ m, Dol 〉=40 μ m most preferably.
32. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, described glass can be by chemical tempering, Dol behind the chemical tempering 〉=25 μ m and CS 〉=700MPa, wherein preferred CS 〉=800MPa, more preferably CS 〉=900MP, CS 〉=1000MPa most preferably.
33. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, be characterised in that described glass is behind chemical tempering:
Young's modulus 70GPa≤E≤78GPa;
630 ℃≤At of yield-point≤850 ℃;
Thermal expansivity 7.5 * 10 -6/ K≤CTE≤9 * 10 -6/ K;
Density≤2.49g/cm 3
34. according to each described ZrO that contains in the aforementioned claim 2And B 2O 3Alumina silicate glass, as common mobile equipment or non-mobile device protective shield, when touch-screen or display screen, be characterised in that described glass is behind chemical tempering:
Under external force, deformation values≤5mm, preferred≤1mm, more preferably≤0.5mm;
Young's modulus 70GPa≤E≤78GPa;
620 ℃≤At of yield-point≤850 ℃;
Thermal expansivity 7.5 * 10 -6/ K≤CTE≤9 * 10 -6/ K;
Density≤2.5g/cm 3
Bearing stress CS 〉=700MPa;
Surface stress layer thickness Dol 〉=25 μ m.
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