CN108101358A - Glass composition - Google Patents

Glass composition Download PDF

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Publication number
CN108101358A
CN108101358A CN201711350671.0A CN201711350671A CN108101358A CN 108101358 A CN108101358 A CN 108101358A CN 201711350671 A CN201711350671 A CN 201711350671A CN 108101358 A CN108101358 A CN 108101358A
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Prior art keywords
glass
mgo
cao
sio
glass composition
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CN201711350671.0A
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CN108101358B (en
Inventor
毛露路
匡波
郝良振
孙伟
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CDGM Glass Co Ltd
Chengdu Guangming Optoelectronics Co Ltd
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Chengdu Guangming Optoelectronics 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
    • G11B5/8404—Processes or apparatus specially adapted for manufacturing record carriers manufacturing base layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, glass

Abstract

The present invention provides a kind of Young's modulus and the glass composition of the high temperature viscosity higher, relatively low than playing coefficient and excellent bubble degree.Glass composition, composition represents by weight percentage, contains：SiO2：30 46%, B2O3：0.5 6%, Al2O3：10 30%, CaO：4 20%, MgO：2 15%, Y2O3：13 32%, Al2O3/B2O3For 4 36.The present invention uses common industrial chemicals, pass through the content of reasonable arrangement each component, make glass of the present invention is higher than 34 than bullet coefficient, Young's modulus is in more than 100Gpa, possess relatively low high temperature viscosity and excellent bubble degree, made suitable for hard disk substrate and other need the field of high Young's modulus material.

Description

Glass composition
Technical field
The present invention relates to a kind of Young's modulus and than playing the high glass composition of coefficient, and it possesses relatively low high temperature viscosity With excellent bubble degree, suitable for making hard disk substrate and field of semiconductor package.
Background technology
The reading speed of hard disk is relevant with the rotating speed of hard disk, and the rotating speed of hard disk is faster, and reading speed is higher.Business at present The universal rotating speed of hard disk is between 5200RPM-10000RPM, to continue to lift up rotating speed, it is necessary to promote hard disk substrate material Than bullet coefficient, reason be used as make substrate material it is bigger than bullet coefficient, hand disk wafer high speed rotate in generate Deformation with regard to smaller, therefore hard disk is with regard to that can reach higher rotating speed.Due to being the ratio between young modulus of material and density than playing coefficient (than playing coefficient=Young's modulus/density), therefore, it is desirable to be promoted than playing coefficient, material just needs the Young's modulus and more of bigger Small density.At present the material used in the hard disk of rotating speed 5200RPM-10000RPM rotating speeds than bullet coefficient substantially 28-32 it Between, if the rotation speed of hard disk is needed more than 12000RPM even more than 15000RPM, glass material used needs to surpass than bullet coefficient Crossing 34 could meet.
The problem of promotion of the rotation speed of hard disk also brings electric machine main shaft abrasion drastically to increase, this requires the bases of high rotating speed hard disk Piece needs are made thinner to reduce weight, so as to reduce the service life for wearing to be promoted hard disk of electric machine main shaft.Mainstream is hard at present The Young's modulus of disk substrate is 80GPa or so, and design thickness is 0.65mm or so.To hand disk wafer thickness is thinned to 0.4mm is even more thin, that just needs substrate material to possess the Young's modulus of more than 100GPa.
The storage density of hard disk is higher and higher at present, this is just needed magnetic material sputter to substrate at higher temperatures On material, this requires hard disk substrate material possesses higher heat resistance, it is generally recognized that transition temperature (the Tg temperature of glass material Degree) it needs higher than 750 DEG C of requirements that could meet future new era seagate.In addition, in the making high temperature flow of hard disk, Especially under the higher process conditions of future temperature, if containing alkali metal ion in glass material, such as Na+、K+、Li+Deng this Pollution magnetic material is easily precipitated in a little alkali metal ions in high temperature working processes.
Currently available technology is typically using SiO2-Al2O3- RO (RO refers to alkaline earth oxide) alkali-free glass system, Although the glass system as disclosed in CN1207086A can realize less than 3.00 density and 36 or so than bullet coefficient, this The high temperature viscosity of system glass is very big, generally moors more than -600 pools 400 in the viscosity of 1400 DEG C of temperature, in process of production The technological temperature and the clarifying process of long period for needing up to 1550 DEG C -1600 DEG C exclude bubble, this means that lower Yields, shorter converter life and its higher power consumption.What is more important, such glass need to obtain good gas Bubble degree is needed using As2O3As fining agent, this is not permitted in current environmental requirement.In hard disk substrate there are bubble for Rotating speed, which is up in the reading process of 5200RPM-15000RPM, can generate deviation of gravity center, cause the problem of fatal, so hard disk base Glass sheet is very high to the requirement of bubble degree, and the bubble degree in chunk glass is in general needed to reach A0 grades and its could meet above It is required that.Bubble degree reaches A0 ranks in actual production is extremely difficult for glass described in above-mentioned document.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of Young's modulus and the high temperature viscosity higher, relatively low than playing coefficient With the glass composition of excellent bubble degree.
The technical proposal for solving the technical problem of the invention is：Glass composition, composition table by weight percentage Show, contain：SiO2：30-46%, B2O3：0.5-6%, Al2O3：10-30%, CaO：4-20%, MgO：2-15%, Y2O3：13- 32%, Al2O3/B2O3For 4-36.
Further, composition represents by weight percentage, also contains：TiO2：0-7%, ZrO2：0-5%, SrO：0- 5%th, BaO：0-5%, ZnO：0-5%, La2O3：0-15%, Sb2O3：0-2%, CeO2：0-2%, SnO2：0-2%.
Glass composition, composition are expressed as by weight percentage：SiO2：30-46%, B2O3：0.5-6%, Al2O3:10- 30%th, CaO:4-20%, MgO:2-15%, Y2O3:13-32%, TiO2:0-7%, ZrO2:0-5%, SrO:0-5%, BaO:0- 5%th, ZnO:0-5%, La2O3:0-15%, Sb2O3:0-2%, CeO2:0-2%, SnO2:0-2%, wherein Al2O3/B2O3For 4- 36。
Further, wherein：(SiO2+Al2O3)/B2O3For 10-80；And/or Al2O3/B2O3For 6-30；And/or Al2O3/ TiO2For 3-41；And/or CaO+MgO is no more than 21%；And/or CaO/MgO is 0.8-8.0；And/or (CaO+MgO)/Y2O3For 0.2-1.0；And/or (CaO+MgO+Y2O3)/SiO2For 0.5-1.5；And/or La2O3/Y2O3No more than 0.8.
Further, wherein：SiO2:32-42%, and/or B2O3:1-5%, and/or Al2O3:15-28%, and/or CaO: 5-15%, and/or MgO:3-10%, and/or Y2O3:15-30%, and/or TiO2:0.5-7%, and/or ZrO2:0-3% and/ Or SrO:0-3%, and/or BaO:0-3%, and/or ZnO:0-3%, and/or La2O3:0-9%, and/or Sb2O3:0-1%, And/or CeO2:0-1%, and/or SnO2:0-1%.
Further, wherein：(SiO2+Al2O3)/B2O3For 15-70；And/or Al2O3/B2O3For 8-20；And/or Al2O3/ TiO2For 6-30；And/or CaO+MgO is no more than 19%；And/or CaO/MgO is 0.9-5.0；And/or (CaO+MgO)/Y2O3For 0.3-0.9；And/or (CaO+MgO+Y2O3)/SiO2For 0.7-1.4；And/or La2O3/Y2O3No more than 0.4.
Further, wherein：SiO2:34-40%, and/or Al2O3:19-25%, and/or CaO:6-10%, and/or MgO:4-8%, and/or Y2O3:18-26%, and/or TiO2:1-6%, and/or ZrO2:0-2%, and/or ZnO:0-2% and/ Or La2O3:0-5%, and/or Sb2O3:0-0.5%, and/or CeO2:0-0.5%, and/or SnO2:0-0.5%.
Further, wherein：(SiO2+Al2O3)/B2O3For 20-60；And/or Al2O3/TiO2For 8-20；And/or CaO+ MgO is no more than 18%；And/or CaO/MgO is 1-2.5；And/or (CaO+MgO)/Y2O3For 0.4-0.8；And/or (CaO+MgO+ Y2O3)/SiO2For 0.8-1.3；And/or La2O3/Y2O3No more than 0.15.
Further, represent by weight percentage, SiO2、B2O3、Al2O3、CaO、MgO、Y2O3、TiO2, ZnO content conjunction Evaluation is more than 95%, is preferably more than 98%.
Further, glass is more than 34 than bullet coefficient, is preferably more than 35, further preferably more than 36；Young Modulus is 100-130Gpa, is preferably 105-125GPa, further preferably 110-120GPa.
Further, viscosity is no more than 150 pools, preferably no more than 130 pools during 1400 DEG C of glass, further preferably not More than 110 pools；Bubble degree at A0 grades and its more than, be preferably A00 grades and its more than.
Hard disk substrate is made of above-mentioned glass composition.
Above-mentioned glass composition is used for the application of semiconductor sealing-in.
The beneficial effects of the invention are as follows：Using common industrial chemicals, by the content of reasonable arrangement each component, make this hair Bright glass than bullet coefficient higher than 34, Young's modulus possesses relatively low high temperature viscosity and excellent bubble degree in more than 100Gpa, It is made suitable for hard disk substrate and other needs the field of high Young's modulus material.
Specific embodiment
Each component of glass of the present invention is described below, unless otherwise indicated, the content of each component is with weight % It represents.
SiO2It is the main Network former of glass, is the skeleton for forming glass, in this system glass, content is higher than When 46%, the thawing performance and Young's modulus of glass can decline, and high temperature viscosity steeply rises；When its content is less than 30%, glass The chemical stability of glass can reduce, the devitrification resistance of glass can rapid decrease, while the density of glass can rapid increase, cause Glass declines than bullet coefficient.Therefore, SiO in the present invention2Content be limited to 30%-46%, be preferably 32-42%, into one Step is preferably 34-40%.
System glass of the present invention belongs to alkali-free glass, and dissolution of raw material temperature is high.Glass raw material is easily being changed at thawing initial stage Material pond generates a large amount of bubble accumulations, and when bubble accumulation is serious, glass metal can overflow feed tank, can be made during continuous smelting Homogenizing, clarification, molding procedure into charging process and below stops.Inventor by sharp study, find to add in 0.5% with On B2O3Raw material can be reduced and initially melting the bubble accumulation in stage, be conducive to being smoothed out for charging process, but B2O3Add Dosage is more than 6%, can cause the decline than bullet coefficient and Young's modulus of glass, while the chemical stability of glass can decline. Therefore, B2O3Content for 0.5-6%, more preferably 1-5%.
Al2O3The Young's modulus of glass can be promoted by adding in system glass of the present invention, while can reduce the close of glass Degree, promoted glass than bullet coefficient.If its content is less than 10%, glass can be less than design in advance than bullet coefficient and Young's modulus Phase, the density of glass can also increase；If its content is higher than 30%, due to Al2O3Very indissoluble can cause the thawing of glass raw material Performance rapid decrease, the high temperature viscosity of glass steeply rise.Therefore, Al2O3Addition be limited to 10-30%, be preferably 15- 28%, further preferably 19-25%.
SiO in the present invention2And Al2O3Belong to indissoluble oxide and cause the key factor of material pond bubble accumulation.Hair A person of good sense has found according to experiment, works as SiO2、Al2O3Total amount and B2O3Ratio (SiO2+Al2O3)/B2O3It is between 10-80 When, glass bubble packing phenomenon in material disappears substantially, while glass can maintain higher heat resistance, (SiO2+Al2O3)/ B2O3Preferably 15-70, further preferably 20-60.
B2O3Addition can promote Al2O3Structure generate variation, therefore Al2O3With B2O3Relative amount selection for The high temperature viscosity of glass and than play coefficient have larger association.Work as Al2O3With B2O3Ratio Al2O3/B2O3During more than 36, glass High temperature viscosity steeply rise.Work as Al2O3/B2O3During less than 4, glass drastically declines than bullet coefficient.Therefore, Al2O3/B2O3It is excellent Elect 4-36 as, more preferably 6-30, further preferably 8-20.
A small amount of TiO2The high temperature viscosity of glass can be reduced by adding in glass, promoted glass than bullet coefficient and Young mould Amount, if its content is more than 7%, the anti-crystallization ability meeting rapid decrease of glass, therefore TiO in the present invention2Content be defined to 7% Below by way of further study show that, if TiO2Content is less than 0.5%, promotes Young's modulus, than playing coefficient and reducing high temperature The effect unobvious of viscosity.Therefore, content is preferably 0.5-7%, more preferably 1-6%.
In this system glass, due to Al2O3Content it is larger, TiO2Content can promote Al2O3Structure generate change Change, so as to cause variation of the glass than playing coefficient and devitrification resistance energy.If Al2O3With TiO2Ratio Al2O3/TiO2Higher than 41, The devitrification resistance of glass can decline, and the high temperature viscosity of glass increases；If Al2O3/TiO2Less than 3, glass can be drastically than bullet coefficient Decline, the devitrification resistance of glass also can drastically decline.Therefore, Al2O3/TiO23-41 is defined to, is preferably 6-30, further Preferably 8-20.
CaO, MgO, SrO and BaO belong to alkaline earth oxide, and proper amount of alkaline earth oxide adds in can in glass To promote the Young's modulus of glass, the high temperature viscosity of glass is reduced, while balances glass ingredient, improves the thawing performance of glass. But excessive alkaline earth oxide can reduce the devitrification resistance energy of glass, the devitrification resistance of glass can be for hard disk substrate glass It is very important for glass, reason is during the blank of hard disk substrate is made, it is necessary near softening point in glass Thin blank is pressed into after glass block is softened, if the devitrification resistance of glass can be bad, crystallization particle will be generated in glass. The physical property and surrounding glass of crystallization pellet hardness have very big difference, can thus generate defect in process, The surface roughness of substrate is made to arrive requirement.
Although above having in common that for four kinds of alkaline earth oxides can reduce high temperature viscosity, improve the thawing of glass Performance, but its ability to reducing high temperature viscosity influence the degree of glass devitrification resistance energy, to the influence degree of glass density And be inconsistent to the promotion degree of Young's modulus and its heat resistance, there is larger difference.
According to inventor's a large number of experiments the study found that MgO is added to the Young's modulus and ratio that glass can be promoted in glass Play coefficient, reduce the high temperature viscosity of glass, if but its content reduce density less than 2% and promote Young's modulus and its than bullet system Several effect unobvious；If its content is more than 15%, the devitrification resistance of glass can be decreased obviously.Therefore, content is defined to 2- 15%, it is preferably 3-10%, further preferably 4-8%.
The effect that CaO reduces high temperature viscosity in these four alkaline earth oxides is most it will be evident that it is carried simultaneously again Rise the effect of glass Young's modulus.In the present invention, if additive amount is less than 4%, glass is reached than bullet coefficient and Young's modulus Less than design requirement, while reduce the effect unobvious of glass high temperature viscosity；If its content is higher than 21%, the devitrification resistance of glass Can drastically it decline, while the chemical stability of glass, especially water resistance can rapid decreases.Therefore, content is defined to 4- 21%, it is preferably 5-15%, further preferably 6-10%.
It is found by numerous studies, if total content MgO+CaO of MgO and CaO is more than in glass composition of the present invention 21%, the heat resistance and anti-crystallization ability of glass can be reduced quickly, and preferably more than 19%, further preferably no more than 18%. In addition, if the ratio C aO/MgO of CaO and MgO is more than 8.0, glass can be reduced quickly than bullet coefficient；If CaO/MgO is less than 0.8, the devitrification resistance of glass can rapid decrease, and influence to be formed the stability of glass.Therefore, CaO/MgO is defined to 0.8- 8.0, it is preferably 0.9-5.0, further preferably 1.0-2.5.
SrO promotes glass Young's modulus, reduces the ability of density of glass less than CaO and MgO, a small amount of addition can carry The devitrification resistance energy of glass is risen, if its content is higher than 5%, the anti-crystallization ability of glass declines, and chemical stability declines, glass Cost significantly raises.Therefore its content is defined to 0-5%, is preferably 0-3%, does not add further preferably.
BaO can significantly increase the density of glass, while can cause glass compared with other three kinds of alkaline earth oxides Chemical stability be remarkably decreased.Although a small amount of addition can promote the Young's modulus of glass and devitrification resistance energy, its Content is more than 5%, can be obviously improved the density of glass, and chemical stability especially water resistance is remarkably decreased.Therefore its content 0-5% is defined to, is preferably 0-3%, does not add further preferably.
Y2O3Be added to can be obviously improved in glass glass than bullet coefficient, Young's modulus and heat resistance, while can drop The high temperature viscosity of low glass.If but its content be more than 32%, the devitrification resistance of glass can be remarkably decreased, density also can significantly on It rises.If its content is less than 13%, the high temperature viscosity of glass declines unobvious, glass than bullet coefficient, Young's modulus and heat resistance Design requirement is not achieved.Therefore, content is defined to 13-32%, is preferably 15-30%, further preferably 18-26%.
Inventor is the study found that the total content and Y of CaO and MgO2O3Relative amount can promote B in glass2O3、 Al2O3、TiO2Structure generate variation, so that great shadow can be generated than bullet coefficient, heat resistance and devitrification resistance to glass It rings.When the total content and Y of CaO, MgO2O3Ratio (CaO+MgO)/Y2O3During more than 1.0, glass is than playing coefficient and heat resistance Rapid decrease；As (CaO+MgO)/Y2O3During less than 0.2, the anti-crystallization ability rapid decrease of glass.Therefore, (CaO+MgO)/ Y2O30.2-1.0 is defined to, is preferably 0.3-0.9, further preferably 0.4-0.8.
CaO、MgO、Y2O3There is promotion than playing coefficient, Young's modulus Deng three kinds of oxides, reduce the energy of glass high temperature viscosity Power, inventor have found the aggregate value and SiO of three of the above oxide2Relative amount to the resistance to of glass high temperature viscosity and glass It is hot to have stronger association.If CaO, MgO, Y2O3Total amount and SiO2Ratio (CaO+MgO+Y2O3)/SiO2More than 1.5, The heat resistance of glass can rapid decrease；If (CaO+MgO+Y2O3)/SiO2Less than 0.5, design is not achieved in the high temperature viscosity of glass will It asks.Therefore, (CaO+MgO+Y2O3)/SiO20.5-1.5 is defined to, is preferably 0.7-1.4, further preferably 0.8-1.3.
ZrO2It is added to the anti-crystallization ability that can improve glass in glass, while the chemical stabilization of reinforcing glass on a small quantity Property.But if its content is more than 5%, and the solubility property of glass can be remarkably decreased, while glass high temperature viscosity can significantly rise, glass In easily occur not melting object.Therefore, content is defined to 0-5%, is preferably 0-3%, further preferably 0-2%, further It does not add preferably.
A small amount of ZnO is added to the high temperature viscosity that glass can be reduced in glass, while can be with the chemical stabilization of reinforcing glass Property, if but ZnO additive amount more than 5%, the Young's modulus of glass can decline, while the density of glass can rise, and cause glass Ratio bullet coefficient rapid decrease, the heat resistance of glass can decline.Therefore, ZnO content is defined to 0-5%, is preferably 0-3%, more Preferably 0-2% is not added further preferably.
Proper amount of La2O3The Young's modulus of glass can be promoted by being added in glass, while can promote the Tg temperature of glass Degree improves the heat resistance of glass, reduces the high temperature viscosity of glass.But if its content is more than 15%, and the density of glass can significantly rise So that design requirement is not achieved than bullet coefficient in glass, while the devitrification resistance of glass can be remarkably decreased.Therefore its content 0-15% is defined to, is preferably 0-9%, more elects 0-5% as, do not add further preferably.
La2O3And Y2O3Although the Young's modulus of glass can be promoted, work as La2O3With Y2O3Ratio La2O3/ Y2O3During more than 0.8, the density meeting rapid increase of glass, so as to cause the ratio bullet coefficient rapid decrease of glass, while glass is anti- Crystallization property also can rapid decrease.Therefore, La2O3/Y2O3No more than 0.8,0.4 is preferably no greater than, is further preferably not more than 0.15。
It is preferably 0-1%, further preferably in addition, the fining agent that total amount is 0-2% can be introduced in glass of the present invention For 0-0.5, Sb may be employed in fining agent2O3、CeO2、SnO2In one or more.
The present invention is obtains the especially excellent glass composition of performance, to be suitable for the manufacture of hard disk glass substrate, by weight It measures percentage to represent, wherein SiO2、B2O3、Al2O3、CaO、MgO、Y2O3、TiO2, ZnO content aggregate value be preferably 95% with On, more preferably more than 98%.
The performance of the optical glass of the present invention is described below：
The Young's modulus E of glass uses its velocity of longitudinal wave of ultrasonic test and shear wave velocity, then calculates as follows Go out.
Wherein, G=VS 2ρ
In formula：
E is Young's modulus, Pa；
G is modulus of shearing, Pa；
VTFor shear wave velocity, m/s；
VSFor shear wave velocity, m/s；
ρ is glass density, g/cm3；
The density of glass is tested by GB/T7962.20-2010 prescriptive procedures.
Glass than bullet coefficient=Young's modulus/density.
The Tg temperature of glass is tested by GB/T7962.16-2010 prescriptive procedures.
The high temperature viscosity of glass is tested using THETA Rheotronic II high-temperature viscosimeters using rotary process, numerical value list Position is dPaS (pool), and numerical value is smaller, represents that viscosity is smaller.
The devitrification resistance of glass can use following methods to test：
Laboratory sample is processed as 20*20*10mm specifications, sample is put into the analysis that temperature is Tg+200 DEG C by polishing both surfaces Brilliant stove inside holding 30 minutes after taking out cooling, then to two big mirror polish, the crystallization property of glass is judged according to following table, A grades are Preferably, E grades are worst.
The classification of crystallization and criterion
The bubble degree of glass is measured and is classified by GB/T7962.8-2010 prescriptive procedures.
By test, glass of the present invention is more than 34 than playing coefficient, is preferably more than 35, further preferably more than 36. The Young's modulus of glass is 100-130GPa, is preferably 105-125GPa, further preferably 110-120GPa.The Tg temperature of glass It spends for 740 DEG C or more, is preferably 750 DEG C or more, more preferably 760 DEG C or more.Viscosity is no more than 150 during 1400 DEG C of the glass Pool, preferably no more than 130 pools, further preferably no more than 110 pools.The die mould devitrification resistance of glass can be B classes and its with On, be preferably A classes and its more than.Glass blister degree at A0 grades and its more than, be preferably A00 grades and its more than.
The glass of the present invention is therefore particularly suitable for forming hard disk substrate and for semiconductor due to having more than performance The application of sealing-in.
Embodiment
In order to further appreciate that technical scheme, the embodiment of glass composition of the present invention will now be described.It should It should notice that there is no limit the scope of the present invention for these embodiments.
The glass composition (embodiment 1-50) shown in table 1-5 is by the ratio according to each embodiment shown in table It weighs and hybrid glass common raw material (such as oxide, hydroxide, carbonate, nitrate), mixed raw material is placed on In platinum crucible, in 1400-1450 DEG C melt 6-8 it is small when, and it is clarified, stirring and homogenizing after, obtain no bubble and Homogeneous melt glass without undissolved substance casting mold and anneals this melten glass in mold.
The composition (weight %) of 1-50 of the embodiment of the present invention, Young's modulus (E) are shown in table 1-5, than playing coefficient (E/ ρ), Tg temperature (Tg), the high temperature viscosity (K) at a temperature of 1400 DEG C, anti-crystallization grade (N), bubble degree (Q), (SiO2+Al2O3)/ B2O3Value represented with A, Al2O3/B2O3Value represented with B, Al2O3/TiO2Value represented with C, the value of CaO+MgO is represented with D, The value of CaO/MgO is represented with F, (CaO+MgO)/Y2O3Value represented with G, (CaO+MgO+Y2O3)/SiO2Value represented with M, La2O3/Y2O3Value represented with H.
Table 1
Table 2
Table 3
Table 4
Component 31 32 33 34 35 36 37 38 39 40
SiO2 33.20 38.20 36.70 41.70 31.20 44.20 35.20 39.70 33.70 42.70
B2O3 1.70 3.00 3.20 2.80 1.00 2.50 2.60 3.60 2.00 2.40
ZnO 0.00 2.50 0.00 0.00 0.00 0.00 0.00 0.00 0.30 0.00
TiO2 5.90 0.50 2.00 3.00 1.80 1.20 5.50 1.00 5.80 1.80
Al2O3 26.30 20.30 22.10 16.10 28.70 13.10 23.90 18.50 25.70 14.90
ZrO2 4.00 0.00 1.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00
Y2O3 17.20 23.20 21.40 27.40 14.30 30.40 19.60 25.00 17.80 28.60
La2O3 0.00 0.00 0.00 0.00 7.00 0.00 1.00 0.00 5.00 0.00
CaO 5.20 10.10 9.50 4.20 13.20 4.20 8.00 8.90 4.00 4.80
MgO 5.00 2.60 3.80 4.00 2.50 4.20 3.80 3.00 4.00 4.50
BaO 0.20 0.00 0.00 0.50 0.00 0.00 0.00 0.00 0.00 0.00
SrO 1.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.00 0.00
CeO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.20 0.00
SnO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.20 0.00
Sb2O3 0.30 0.10 0.30 0.30 0.30 0.20 0.30 0.30 0.30 0.30
Total (%) 100.00 100.50 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
A 35.00 19.50 18.38 20.64 59.90 22.92 22.73 16.17 29.70 24.00
B 15.47 6.77 6.91 5.75 28.70 5.24 9.19 5.14 12.85 6.21
C 4.46 40.60 11.05 5.37 15.94 10.92 4.35 18.50 4.43 8.28
D 10.20 12.70 13.30 8.20 15.70 8.40 11.80 11.90 8.00 9.30
F 1.04 3.88 2.50 1.05 5.28 1.00 2.11 2.97 1.00 1.07
G 0.39 0.63 0.60 0.51 0.55 0.64 0.49 0.64 0.31 0.62
M 0.83 0.94 0.95 0.85 0.96 0.88 0.89 0.93 0.77 0.89
H 0.00 0.00 0.00 0.00 0.49 0.00 0.05 0.00 0.28 0.00
E(GPa) 110.30 113.00 111.10 120.90 111.50 121.90 110.70 117.50 110.40 121.30
ρ(g/cm3) 3.11 3.01 3.04 3.02 3.15 3.08 3.07 3.02 3.10 3.04
E/ρ 35.47 37.54 36.55 40.09 35.40 39.57 36.06 38.91 35.61 39.88
Tg(℃) 774 786 779 804 779 817 774 794 772 810
K 56.1 90.7 85.2 99.8 39.3 108.3 76.5 94.6 60.3 103.2
N A A A A A A A A A A
Q A00 A00 A00 A00 A00 A00 A00 A00 A00 A00
Table 5

Claims (13)

1. glass composition, which is characterized in that its composition represents by weight percentage, contains：SiO2：30-46%, B2O3：0.5- 6%th, Al2O3：10-30%, CaO：4-20%, MgO：2-15%, Y2O3：13-32%, Al2O3/B2O3For 4-36.
2. glass composition as described in claim 1, which is characterized in that its composition represents by weight percentage, also contains： TiO2：0-7%, ZrO2：0-5%, SrO：0-5%, BaO：0-5%, ZnO：0-5%, La2O3：0-15%, Sb2O3：0-2%, CeO2：0-2%, SnO2：0-2%.
3. glass composition, which is characterized in that its composition is expressed as by weight percentage：SiO2：30-46%, B2O3：0.5- 6%th, Al2O3:10-30%, CaO:4-20%, MgO:2-15%, Y2O3:13-32%, TiO2:0-7%, ZrO2:0-5%, SrO: 0-5%, BaO:0-5%, ZnO:0-5%, La2O3:0-15%, Sb2O3:0-2%, CeO2:0-2%, SnO2:0-2%, wherein Al2O3/B2O3For 4-36.
4. the glass composition as described in claim 1-3 any claims, which is characterized in that wherein：(SiO2+Al2O3)/ B2O3For 10-80；And/or Al2O3/B2O3For 6-30；And/or Al2O3/TiO2For 3-41；And/or CaO+MgO is no more than 21%； And/or CaO/MgO is 0.8-8.0；And/or (CaO+MgO)/Y2O3For 0.2-1.0；And/or (CaO+MgO+Y2O3)/SiO2For 0.5-1.5；And/or La2O3/Y2O3No more than 0.8.
5. the glass composition as described in claim 1-3 any claims, which is characterized in that wherein：SiO2:32-42%, And/or B2O3:1-5%, and/or Al2O3:15-28%, and/or CaO:5-15%, and/or MgO:3-10%, and/or Y2O3: 15-30%, and/or TiO2:0.5-7%, and/or ZrO2:0-3%, and/or SrO:0-3%, and/or BaO:0-3%, and/or ZnO:0-3%, and/or La2O3:0-9%, and/or Sb2O3:0-1%, and/or CeO2:0-1%, and/or SnO2:0-1%.
6. the glass composition as described in claim 1-3 any claims, which is characterized in that wherein：(SiO2+Al2O3)/ B2O3For 15-70；And/or Al2O3/B2O3For 8-20；And/or Al2O3/TiO2For 6-30；And/or CaO+MgO is no more than 19%； And/or CaO/MgO is 0.9-5.0；And/or (CaO+MgO)/Y2O3For 0.3-0.9；And/or (CaO+MgO+Y2O3)/SiO2For 0.7-1.4；And/or La2O3/Y2O3No more than 0.4.
7. the glass composition as described in claim 1-3 any claims, which is characterized in that wherein：SiO2:34-40%, And/or Al2O3:19-25%, and/or CaO:6-10%, and/or MgO:4-8%, and/or Y2O3:18-26%, and/or TiO2: 1-6%, and/or ZrO2:0-2%, and/or ZnO:0-2%, and/or La2O3:0-5%, and/or Sb2O3:0-0.5%, and/or CeO2:0-0.5%, and/or SnO2:0-0.5%.
8. the glass composition as described in claim 1-3 any claims, which is characterized in that wherein：(SiO2+Al2O3)/ B2O3For 20-60；And/or Al2O3/TiO2For 8-20；And/or CaO+MgO is no more than 18%；And/or CaO/MgO is 1-2.5； And/or (CaO+MgO)/Y2O3For 0.4-0.8；And/or (CaO+MgO+Y2O3)/SiO2For 0.8-1.3；And/or La2O3/Y2O3No More than 0.15.
9. the glass composition as described in claim 1-3 any claims, which is characterized in that it represents by weight percentage, SiO2、B2O3、Al2O3、CaO、MgO、Y2O3、TiO2, ZnO content aggregate value for more than 95%, be preferably more than 98%.
10. the glass composition as described in claim 1-3 any claims, which is characterized in that glass is than bullet coefficient More than 34, it is preferably more than 35, further preferably more than 36；Young's modulus is 100-130Gpa, is preferably 105-125GPa, Further preferably 110-120GPa.
11. the glass composition as described in claim 1-3 any claims, which is characterized in that viscosity during 1400 DEG C of glass No more than 150 pools, preferably no more than 130 pools, further preferably no more than 110 pools；Bubble degree at A0 grades and its more than, it is excellent Elect as A00 grades and its more than.
12. hard disk substrate is made of the glass composition described in claim 1-11 any claims.
13. the glass composition described in claim 1-11 any claims is used for the application of semiconductor sealing-in.
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CN110885187A (en) * 2019-11-27 2020-03-17 成都光明光电股份有限公司 Alkali-free glass
CN112851113A (en) * 2019-11-27 2021-05-28 成都光明光电股份有限公司 Glass composition
WO2023276608A1 (en) * 2021-06-28 2023-01-05 日本電気硝子株式会社 Alkali-free glass panel

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CN1207086A (en) * 1996-09-04 1999-02-03 保谷株式会社 Glass for information recording medium substrate and glass substrate
JP2004352571A (en) * 2003-05-29 2004-12-16 Minolta Co Ltd Glass composition and glass substrate
CN1875404A (en) * 2003-10-31 2006-12-06 柯尼卡美能达精密光学株式会社 Glass substrate for an information recording medium and information recording medium employing it
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Publication number Priority date Publication date Assignee Title
CN110885187A (en) * 2019-11-27 2020-03-17 成都光明光电股份有限公司 Alkali-free glass
CN112851113A (en) * 2019-11-27 2021-05-28 成都光明光电股份有限公司 Glass composition
CN112851113B (en) * 2019-11-27 2022-04-15 成都光明光电股份有限公司 Glass composition
WO2023276608A1 (en) * 2021-06-28 2023-01-05 日本電気硝子株式会社 Alkali-free glass panel

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