CN107382054A - Alumina silicate glass and its preparation method and application - Google Patents
Alumina silicate glass and its preparation method and application Download PDFInfo
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- CN107382054A CN107382054A CN201710683419.5A CN201710683419A CN107382054A CN 107382054 A CN107382054 A CN 107382054A CN 201710683419 A CN201710683419 A CN 201710683419A CN 107382054 A CN107382054 A CN 107382054A
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- alumina silicate
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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
- C03C3/076—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
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1218—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or structure of the substrate
Abstract
The present invention relates to glass manufacturing area, discloses alumina silicate glass and its preparation method and application.On the basis of the integral molar quantity of the alumina silicate glass, in terms of oxide, the alumina silicate glass contains：SiO2：62~68%, Al2O3：11~15%, B2O3：0~4%, MgO：5~15%, CaO：1~10%, SrO：3~9%, ZnO：0.01~1%, MoO3：0.001~0.5%.The alumina silicate glass prepared using the method for the present invention is green, with good heat endurance, higher annealing point temperature and relatively low fusion temperature and forming temperature can be had concurrently, glass still has higher mechanical strength after being thinned, moreover, the resistance to chemical corrosion of the alumina silicate glass is excellent.
Description
Technical field
The present invention relates to glass manufacturing area, and in particular to alumina silicate glass and its preparation method and application.
Background technology
With the fast development of photovoltaic industry, the demand of various display devices is constantly being increased, such as active matrix
The active matrix liquid crystal of liquid crystal display (AMLCD), Organic Light Emitting Diode (OLED) and application low-temperature polysilicon silicon technology is shown
(LTPS TFT-LCD) device, these display devices are all based on using thin film semiconductor material production thin film transistor (TFT) (TFT) skill
Art.The silicon substrate TFT of main flow can be divided into non-crystalline silicon (a-Si) TFT, polysilicon (p-Si) TFT and monocrystalline silicon (SCS) TFT, wherein non-
Crystal silicon (a-Si) TFT is the technology of present main flow TFT-LCD applications, and its procedure for producing can be complete at a temperature of 300~450 DEG C
Into.It is no more than 300ppi display product for picture element density, non-crystalline silicon (a-Si) TFT is masterly；But work as picture element density
After 400ppi, it is necessary to the higher polycrystalline silicon technology support of electron mobility.LTPS (p-Si) TFT is needed during processing procedure
Repeatedly to be handled at a temperature of 450~600 DEG C, substrate must can not occur significantly to deform in multiple high temp processing procedure,
It is proposed that higher requirement, namely substrate there must be sufficiently small " heat receipts to base plate glass heat endurance and dimensional stability
Contracting ".The influence factor of base plate glass thermal contraction mainly has three：In a first aspect, base plate glass is at processing temperatures with higher
Viscosity (i.e. higher annealing point temperature)；Second aspect, good annealing is have passed through during molding substrate；The third aspect,
Temperature and processing time in panel making technology.For glass manufacturer, controllable factor is first aspect and second
Aspect.It is main in current existing technique for the application of low-temperature polysilicon silicon technology (LTPS) technique for first aspect
If by increasing glass former (such as SiO2) content improve the annealing point temperature of silicate glass, but such do
Method will make it that the rise of high temperature melting temperature is more.It for second aspect, can ensure fully to anneal in technique at present, but anneal
Segment length is longer, namely needs longer production line.To sum up, the heat endurance of the glass substrate manufactured by current routine techniques
Bad, annealing point temperature or relatively low, the annealing point temperature that technology can ensure mostly at present is 720 DEG C or so；For
Some preferable techniques, although improving annealing point temperature, it can't take into account and both improve annealing point temperature, and relatively reduce
Adding does not increase the effect of fusion temperature and forming temperature even, cause the practicality of alumina silicate glass to have a greatly reduced quality, product it is good
Rate is not high, increase energy consumption, manufacture is difficult, is unfavorable for industrialized production, and because the length of shaping area is longer, so as to elongate
The length of production line, add the cost of manufacture.
In addition, with the popularization of smart mobile phone and tablet personal computer, the epoch of intelligent mobile are opened.Conventional mobile phone limitation
In communication function, but the performance of the smart machine at present including smart mobile phone and tablet personal computer approaches with notebook so that people
By radio communication convenience all the time not perform and enjoy higher level commercial affairs and recreation.Such
Under trend, display performance requirement is also improved constantly, image quality especially to intelligent movable equipment, out of doors visual
Performance requirement is also being lifted, while in order to mitigate the use burden of portable equipment, thinning turn into of weight, thickness can not
The main trend avoided.Under the leading of this trend, display panel is sent out to the direction that lightening, ultra high-definition is shown
Exhibition, panel making technology manage temperature development to higher height；Monolithic glass passes through PROCESS FOR TREATMENT simultaneously, thickness reach 0.25mm,
0.2mm, 0.1mm are even more thin.The mode for making glass thinning is presently mainly chemical reduction, specifically, using hydrofluoric acid or
Buffered hydrofluoric acid solution corrodes to glass substrate, and its thinning principle is as follows：Main chemical reactions：4HF+SiO2=SiF4+
2H2O；Secondary chemical reaction：RO+2H+=R2++H2O (R represents alkaline-earth metal etc.).
The TFT-LCD base plate glass of high chemical stability is researched and developed, can be subtracted with significantly more efficient control thinning process and technique
The production costs such as few second polishing, lift product quality and yields, have larger benefit for large industrialized production.
With the development of lightening trend, in G6 generations (glass size is about 1.3 meters × 1.5 meters), in G7 generations, (glass size was about
For 1.5 meters × 1.9 meters), G7.5 generation (glass size is about 1.95 meters × 2.2 meters), G8 generation (glass size is about 2.2 meters × 2.5
Rice) etc. more advanced lines glass substrate production in, under the trend that single sheet size constantly expands, horizontal positioned glass substrate
Due to it is sagging caused by deadweight, be warped into important subject., will after glass board material shaping for the glass substrate producer
By annealing, cutting, processing, examining, a variety of links such as cleaning, the sagging of sized rectangular glass substrate will be influenceed between processing stand
The ability for loading, taking out and separating is transported in the casing of glass.For counter plate manufacturer, it is similar the problem of equally exist.Compared with
Big sag or warpage can cause to alarm in fragment rate raising and TFT-LCD preparation technologies, have a strong impact on product yield.If
At both ends supporting substrate both sides, the maximum sag of chain (S) of glass substrate can represent as follows：
K is constant, and ρ is density, and E is modulus of elasticity, and l is spaced for support, and t is thickness of glass substrate.Wherein, (ρ/E) is
Than the inverse of modulus.Refer to elasticity modulus of materials and the ratio of density than modulus, be also known as " than modulus of elasticity " or " specific stiffness ",
It is one of the important requirement of structure design to material.Material weight is lighter under explanation same stiffness higher than modulus, or phase homogeneity
The lower rigidity of amount is bigger.From above formula, when the timing of l, t mono-, ρ, which diminishes after E is increased, can reduce sag of chain, therefore should make substrate
Glass has try one's best low density and as far as possible high modulus of elasticity, that is, has as far as possible big ratio modulus.At present in production process, often
Occur mechanical strength reduction occur due to the strongly reducing for thickness of glass after being thinned, or even the problem of deformation.Reduction density,
Than modulus and intensity, reducing glass fragility turns into the factor that glass production person needs emphasis to consider for increase.
In addition, As is commonly used in current alumina silicate glass2O3, that is, the arsenic often said, environment is caused sternly
The pollution of weight.
Finally, in existing aluminosilicate production at present, often there is acid corrosion excessive velocities or excessively slow phenomenon.Cross
When fast (10%HF numerical value resistant to chemical etching is larger), exaggerated, production during small scuffing will produce in the later stage in manufacturing process
The product gone out is exactly poor product, therefore, great difficulty is brought to manufacture；But when excessively slow (10%HF numerical value resistant to chemical etching compared with
It is small), the production cycle will be elongated again, reduces production efficiency, adds cost.
The content of the invention
The invention aims to overcome existing alumina silicate glass to exist, heat endurance is bad, shaping area is long leads
Cause not high production line elongation, the mechanical strength of thinned rear glass, acid corrosion excessive velocities or pollute ring slowly and in preparation process excessively
The defects of border, there is provided a kind of alumina silicate glass and its preparation method and application, the alumina silicate glass is green, has good
Good heat endurance, can shorten shaping section length, have higher annealing point temperature and relatively low fusion temperature and shaping temperature concurrently
Degree；Glass still has higher mechanical strength after being thinned；Moreover, the resistance to chemical corrosion of the alumina silicate glass is excellent
It is good.
To achieve these goals, first aspect present invention provides a kind of alumina silicate glass, wherein, with the manosil AS
On the basis of the integral molar quantity of salt glass, in terms of oxide, the alumina silicate glass contains：
Preferably, SiO2Molar content be 64~67.5%.
Preferably, Al2O3Molar content be 12~14.5%.
Preferably, B2O3Molar content be 1~3.5%, preferably 1.51~2.99%.
Preferably, MgO molar content is 6~14%, preferably 6.5~13.5%, is more preferably 7~12%, more excellent
Elect 7.5~9.5% as.
Preferably, CaO molar content is 1~8.5%.
Preferably, SrO molar content is 3.5~8.5%, preferably 4~8%, is more preferably 4.3~7.5%, more excellent
Elect 4.6~7% as.
Preferably, ZnO molar content is 0.05~0.7%.
Preferably, MoO3Molar content be 0.005~0.3%.
Preferably, the alumina silicate glass also contains fining agent；Preferably, the fining agent be barium sulfate, barium nitrate,
At least one of strontium nitrate, tin oxide and stannous oxide；It is highly preferred that on the basis of the integral molar quantity of sillico aluminate glass,
The mole of the fining agent is not more than 1%, preferably 0.08~0.5%, more preferably 0.1~0.4%.
Preferably, the density of the alumina silicate glass is less than 2.70g/cm3, preferably 2.5~2.65g/cm3；50~
350 DEG C of thermal coefficient of expansion is less than 39 × 10-7/ DEG C, preferably 30~39 × 10-7/℃；Young's modulus is more than 80GPa, preferably
For 81~90GPa；1250 DEG C of high temperature surface tension are less than 380mN/m, preferably 320~380mN/m；
Preferably, corresponding temperature is less than 1650 DEG C, preferably 1500~1650 DEG C when viscosity is 200 pool；Viscosity is
Corresponding temperature is less than 1300 DEG C, preferably 1100~1300 DEG C during 35000 pool；Viscosity is 1013Corresponding annealing point temperature during pool
Degree is more than 750 DEG C, preferably 750~830 DEG C；
Preferably, corresponding temperature and viscosity are 10 when viscosity is 35000 pool13During pool between corresponding annealing point temperature
Difference is less than 490 DEG C, preferably smaller than 470 DEG C, is further preferably no larger than 460 DEG C, most preferably 370~460 DEG C；In 10%HF acid
Chemical resistance under (20 DEG C/20min) is 4.0~6.0mg/cm2, bubble diameter is more than 0.1mm's in per kilogram glass substrate
Bubbles number is invisible.
Present invention also offers a kind of method for preparing above-mentioned alumina silicate glass, this method includes：Raw material is mixed
To obtain compound, by the compound melt-processed, stirring discharges bubble and is homogenized glass metal, is then made annealing treatment
And cold work.
Third aspect present invention provides the base material that a kind of above-mentioned alumina silicate glass shows and illuminated as plane
Using.
The present invention alumina silicate glass, there is good heat endurance, be not easy to soften, be unlikely to deform, can have concurrently compared with
High annealing point temperature and relatively low fusion temperature and forming temperature, specifically, viscosity 1013Corresponding annealing point temperature during pool
While more than 750 DEG C can be reached, when viscosity is 200 pool, corresponding temperature is less than 1650 DEG C, and is 35000 pools in viscosity
When corresponding temperature be less than 1300 DEG C.
The alumina silicate glass of the present invention, when viscosity is 35000 pool, corresponding temperature and viscosity are 1013It is corresponding during pool
Difference between annealing point temperature is less than 490 DEG C, has relatively low forming temperature, so as to reduce the length of shaping area, contracting
The length of short production line, save energy consumption and reduce manufacturing cost.
Alumina silicate glass provided by the present invention or the alumina silicate glass prepared using method provided by the invention,
Still there is higher mechanical strength after being thinned, its density is less than 2.70g/cm3；50~350 DEG C of thermal coefficient of expansion is less than 39
×10-7/℃；Young's modulus is more than 80GPa；1250 DEG C of high temperature surface tension are less than 380mN/m.
Alumina silicate glass provided by the present invention or the alumina silicate glass prepared using method provided by the invention, tool
There is preferable resistance to chemical corrosion, the numerical value resistant to chemical etching under 10%HF sour (20 DEG C/20min) is 4.0~6.0mg/
cm2Between, bubble diameter is invisible more than 0.1mm bubbles number in per kilogram glass substrate.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of alumina silicate glass, wherein, on the basis of the integral molar quantity of the alumina silicate glass, with
Oxide meter, the alumina silicate glass contain：
In the present invention, on the basis of the integral molar quantity of the alumina silicate glass, in terms of oxide, the SiO2Mole
Content can be 62~68%, preferably 64~67.5%, specifically, for example, can be 62%, 62.5%, 62.8%,
63.4%th, 63.7%, 63.9%, 64%, 64.7%, 65%, 65.5%, 65.8%, 66.1%, 66.3%, 66.5%,
66.9%th, 67.2%, 67.5%, 68% and these numerical value in the scope that is formed of any two in any number.
SiO2For glass former, in SiO2Content be less than 62% in the case of, be unfavorable for the corrosive enhancing of endurance, can make swollen
Swollen coefficient is too high, the easy devitrification of glass, suitably improves SiO2Content contribute to glass lightweight, thermal coefficient of expansion reduces,
Annealing point temperature increases, and chemical resistance increases；But in SiO2Content be higher than 68% in the case of, with the increasing of high temperature viscosity
Add, be unfavorable for melting, in general tank furnace is difficult to meet, difficulty is brought to manufacture.
In the present invention, on the basis of the integral molar quantity of the alumina silicate glass, in terms of oxide, the Al2O3Mole
Content can be 11~15%, preferably 12~14.5%, specifically, for example, can be 11%, 11.8%, 12%, 12.3%,
12.4%th, 12.5%, 12.6%, 12.7%, 12.8%, 12.9%, 13%, 13.3%, 13.5%, 13.6%, 14.5%,
15% and these numerical value in the scope that is formed of any two in any number.Al2O3The strong of glass structure can be improved
Degree, in Al2O3Content be less than 11% in the case of, glass heat resistance is difficult to be lifted, also easily by extraneous aqueous vapor and chemistry try
The erosion of agent, the A1 of high content2O3Glass annealing point temperature, mechanical strength is contributed to increase；But in Al2O3Content be higher than
In the case of 15%, easily there is crystallization in glass, glass is difficult to melt.
In the present invention, in high-aluminum alkali-free silicate glass system, boron oxide B is used2O3Good high temperature can be brought
Fluxing effect, while be advantageous to lift glass endurance.But in low temperature viscosity area, B2O3But so that glass annealing point temperature shows
Writing reduces, and is unfavorable for the lifting of thermal stability.Therefore in balance high-temperature region viscosity, (viscosity is about 102~103Pool) and low temperature
(viscosity is about 10 to area's viscosity7~1015Pool) comprehensive consideration under, on the basis of the integral molar quantity of the alumina silicate glass, with oxygen
Compound meter, the B2O3Molar content can be 0~4%, preferably 1~3.5%, more preferably 1.51~2.99%, specifically
Ground, for example, can be 0%, 1%, 1.51%, 1.55%, 1.6%, 1.75%, 2%, 2.1%, 2.4%, 2.7%, 2.77%,
2.9%th, 2.99%, 3.5%, 3.8%, 4% and these numerical value in the scope that is formed of any two numerical value in it is any
Numerical value.
In the present invention, on the basis of the integral molar quantity of the alumina silicate glass, in terms of oxide, mole of the MgO
Content can be 5~15%, preferably 6~14%, be more preferably 6.5~13.5%, more preferably 7~12%, it is more excellent
Elect 7.5~9.5% as, specifically, such as can be 5%, 6%, 6.249%, 6.5%, 7%, 7.5%, 8%, 8.4%,
8.7%th, 8.8%, 9%, 9.305%, 9.5%, 9.8%, 10.6%, 12%, 13.5%, 14%, 15% and these numerical value
In the scope that is formed of any two numerical value in any number.
In the present invention, on the basis of the integral molar quantity of the alumina silicate glass, in terms of oxide, mole of the CaO
Content can be 1~10%, preferably 1~8.5%, specifically, for example, can be 1%, 1.112%, 1.34%, 1.695%,
1.71%th, 2.1%, 2.33%, 3.247%, 3.32%, 3.48%, 3.952%, 4.1%, 4.48%, 5.9%, 6%,
7.79%th, 8.5%, 8.62%, 10% and these numerical value in the scope that is formed of any two numerical value in any number.
In the present invention, on the basis of the integral molar quantity of the alumina silicate glass, in terms of oxide, mole of the SrO
Content can be 3~9%, preferably 3.5~8.5%, be more preferably 4~8%, more preferably 4.3~7.5%, it is more excellent
Elect 4.6~7% as, specifically, such as can be 3%, 3.5%, 4.19%, 4.3%, 4.6%, 4.8%, 5%, 5.12%,
5.2%th, 6%, 6.8%, 7%, 7.5%, 8%, 8.5%, 9% and these numerical value in the model that is formed of any two numerical value
Any number in enclosing.
In the present invention, MgO, CaO and SrO are alkaline earth oxide, and they can effectively reduce the high temperature of glass
Viscosity can also improve the annealing point temperature of glass, and MgO, SrO have raising so as to improve the meltbility of glass and formability
The characteristics of chemical stability and mechanical stability, but its content can excessively increase density, the generation of crackle, devitrification, split-phase
Rate improves.
In the present invention, on the basis of the integral molar quantity of the alumina silicate glass, in terms of oxide, mole of the ZnO
Content can be 0.01~1%, preferably 0.05~0.7%, specifically, for example, can be 0.01%, 0.03%, 0.05%,
0.08%th, 0.1%, 0.16%, 0.2%, 0.34%, 0.4%, 0.49%, 0.5%, 0.5%, 0.6%, 0.68%, 0.7%,
0.85%th, 1% and these numerical value in the scope that is formed of any two in any number.ZnO can reduce glass height
Warm viscosity (viscosity at such as 1500 DEG C), be advantageous to eliminate bubble；There are lifting intensity, hardness, increase below softening point simultaneously
The chemical resistance of glass, reduce the effect of thermal expansion coefficient of glass.In alkali-free glass system, adding appropriate ZnO helps to press down
Crystallization processed, recrystallization temperature can be reduced.ZnO in alkali-free glass, as network outer body introduce glass after, under high temperature typically with
[ZnO6] hexahedral form is present, compared with [ZnO4] tetrahedron glass structure is more loose, with the identical condition of high temperature not
Glass containing ZnO compares, and the glass viscosity containing ZnO is smaller, and atomic motion speed is bigger, can not form nucleus, it is necessary to further
Temperature is reduced, is just advantageous to the formation of nucleus, thus reduces the crystallization ceiling temperature of glass.It is more than in ZnO molar content
In the case of 1%, the annealing point temperature of glass can be greatly reduced.
In the present invention, on the basis of the integral molar quantity of the alumina silicate glass, in terms of oxide, the MoO3Mole
Content can be 0.001~0.5%, preferably 0.005~0.3%, specifically, for example, can be 0.001%, 0.003%,
0.005%th, 0.008%, 0.01%, 0.02%, 0.04%, 0.05%, 0.07%, 0.11%, 0.2%, 0.23%, 0.3%,
0.36%th, 0.4%, 0.47%, 0.5% and these numerical value in the scope that is formed of any two in any number.
MoO3High temperature surface tension can be greatly reduced, fluxing effect is played, in alkali-free glass with the surface-active of reinforcing glass
In can with part alkaline-earth metal formed fusible compound-molybdate, can be melt below at 1000 DEG C, accelerate batch in silicic acid
Reactant salt.Even if the moreover, MoO of very little concentration3Also the surface tension of silicate melt can be substantially reduced.At low temperature, due to
Mo6+Ionic radius is smaller, and field strength is larger, and Mo ligancy is 6, forms [MoO6] octahedron is filled in network gap, Ke Yizeng
Add the crosslinking degree of glass network, improve heat endurance, chemical stability and mechanical performance.But due to the original of own solubility
Cause, in MoO3Molar content be more than 0.5% in the case of, will appear from insoluble phenomenon.
In situations where it is preferred, the alumina silicate glass also contains fining agent.The fining agent can be that this area is each
The conventional fining agent of kind, such as can be at least one of barium sulfate, barium nitrate, strontium nitrate, tin oxide and stannous oxide.
In situations where it is preferred, on the basis of the integral molar quantity of sillico aluminate glass, the mole of the fining agent is little
In 1%, preferably 0.08~0.5%, more preferably 0.1~0.4%, specifically, such as can be 0.05%,
0.08%th, 0.1%, 0.13%, 0.185%, 0.19%, 0.2%, 0.25%, 0.3%, 0.4%, 0.5% and these numerical value
In the scope that is formed of any two in any number.
In the present invention, the density of the alumina silicate glass is less than 2.70g/cm3, preferably 2.5~2.65g/cm3.Should
The measure of density is with reference to ASTM C-693 methods.
In the present invention, thermal coefficient of expansion of the alumina silicate glass at 50~350 DEG C is less than 39 × 10-7/ DEG C, it is excellent
Elect 30~39 × 10 as-7/℃.The measure of the thermal coefficient of expansion is entered with reference to ASTM E-228 methods by using horizontal expander instrument
Row measure.
In the present invention, the Young's modulus of the alumina silicate glass is more than 80GPa, preferably 81~90GPa.The Young
The measure of modulus is measured with reference to ASTM C-623 methods using resonance method.
In the present invention, high temperature surface tension of the alumina silicate glass at 1250 DEG C is less than 380mN/m, is preferably
320~380mN/m.The surface tension is the measure that is carried out at 1250 DEG C by using high-temperature viscosimeter.
In the present invention, the alumina silicate glass corresponding temperature when viscosity is 200 pool is less than 1650 DEG C, is preferably
1500~1650 DEG C.The measure of the temperature determines it 200 with reference to ASTM C-965 methods by using rotation high-temperature viscosimeter
Corresponding temperature when mooring viscosity.
In the present invention, the alumina silicate glass corresponding temperature when viscosity is 35000 pool is less than 1300 DEG C, preferably
For 1100~1300 DEG C.The measure of the temperature with reference to ASTM C-965 methods, by using rotation high-temperature viscosimeter determine its
Corresponding temperature during 35000 pool viscosity.
In the present invention, the alumina silicate glass is 10 in viscosity13During pool corresponding annealing point temperature 750 DEG C with
On, preferably 750~830 DEG C.The measure of the annealing point temperature is with reference to ASTM C-336 methods, by using annealing point strain point
Tester determines its corresponding viscosity as 1013Temperature during pool.
In the present invention, the alumina silicate glass corresponding temperature and viscosity when viscosity is 35000 pool is 1013During pool
Difference between corresponding temperature is less than 490 DEG C, preferably smaller than 470 DEG C, is further preferably no larger than 460 DEG C, most preferably 370~
460℃.The assay method is as previously described.
In the present invention, chemical resistance of the alumina silicate glass under 10%HF sour (20 DEG C/20min) is
4.0~6.0mg/cm2.The chemical resistance is the test for corroding 20min progress at 20 DEG C by using 10%HF acid.
In the present invention, bubbles number of the bubble diameter more than 0.1mm refers to per kilogram alkaline earth manosil AS in per kilogram glass substrate
Bubble diameter is more than 0.1mm bubbles number in salt glass substrate.The alumina silicate glass of the present invention is in per kilogram glass substrate
Middle bubble diameter is invisible more than 0.1mm bubbles number.The bubbles number is by using the electronic balance weighing that precision is 0.01g
Mother glass weight, number of bubbles is counted using light microscope, calculate and try to achieve the gas that bubble diameter in per kilogram glass is more than 0.1mm
Steep number.
Second aspect of the present invention provides a kind of method for preparing above-mentioned alumina silicate glass, and this method includes：By raw material
Mixing is to obtain compound, and by the compound melt-processed, stirring discharges bubble and is homogenized glass metal, is then annealed
Processing and cold work.
In the present invention, the melt-processed can be carried out in the conventional container in this area, it is preferable that melt-processed
It is that tank furnace in electric smelting or electric boosting or resistance furnace are carried out, specifically, in the case of large-scale industrial production, melt-processed
It is to be carried out in the tank furnace of electric smelting or electric boosting；Under small-scale production or experimental conditions, carried out in resistance furnace.
In the present invention, the annealing can be carried out in the conventional container in this area, it is preferable that annealing
It is to carry out in the lehr.
In the present invention, the cold work can include cutting glass, edge polishing, cleaning and drying etc.
Processing.
In the preferred case, after the annealing process and before cold work, glass can also be immersed in etchant solution,
To produce the glass of required thickness.Specifically, the thickness of glass can be 10mm, 5mm, 3mm, 1mm, 0.5mm, 0.25mm,
Any number in the scope that any two numerical value in 0.2mm or 0.1mm and these numerical value is formed.
In the present invention, the method for preparing above-mentioned alumina silicate glass go for this area it is conventional it is various into
Type method, specifically, such as can be press over system, float glass process and glass tube down-drawing.In a preferred embodiment, the preparation method is
Float glass process forming method.
The application for the base material that third aspect present invention provides above-mentioned alumina silicate glass as plane and shows and illuminate.Tool
Body, the alumina silicate glass can be widely applicable for making glass substrate, photovoltaic device or light that plane shows and illuminated
Electrical part etc..
Embodiment
The present invention will be described in further detail by embodiment below, but protection scope of the present invention is not limited in
This.
In following examples and comparative example, unless stated otherwise, the compound used and reagent etc. are commercially available product.
The method that glass properties test is related to is as follows：
Reference ASTM C-693 methods, determine the density of alumina silicate glass, unit g/cm3。
With reference to ASTM E-228 methods, pass through the thermal expansion of horizontal expander instrument measure alumina silicate glass at 50-350 DEG C
Coefficient, unit 10-7/℃。
With reference to ASTM C-623 method, using resonance method, the Young's modulus of alumina silicate glass, unit GPa are determined.
By using French GBX companies model Viscodrop high-temperature viscosimeters, measure alumina silicate glass is at 1250 DEG C
Surface tension under high temperature, unit mN/m.
With reference to ASTM C-965 methods, by rotating high-temperature viscosimeter, alumina silicate glass high temperature viscosity-temperature curve is determined, its
In, the corresponding temperature in 200 pool viscosity, it is designated as Tm, unit is DEG C；The corresponding forming temperature in 35000 pool viscosity, is designated as
T35000, unit is DEG C.
With reference to ASTM C-336 methods, by using annealing point strain point tester, measure alumina silicate glass is corresponding viscous
Spend for 1013Annealing point temperature during pool, is designated as Ta, unit is DEG C.
By using 10%HF acid, corrode the chemical resistance of 20min test alumina silicate glasses at 20 DEG C, be designated as
CHF, unit mg/cm2。
Bubble diameter is more than 0.1mm bubbles number in per kilogram glass substrate, and assay method is：Service precision is 0.01g's
Electronic balance weighing mother glass weight, number of bubbles is counted using light microscope, bubble diameter in per kilogram glass is tried to achieve in calculating
Bubbles number more than 0.1mm.
Embodiment 1-20 is used for the method for illustrating the present invention.
Embodiment 1
Preparation raw material：On the basis of integral molar quantity, in terms of oxide, contain the SiO that mole is 62%2, mole be
13% Al2O3, mole be 3.8% B2O3, mole be 13.5% MgO, mole be 3.247% CaO, mole
Measure the MoO that the SrO for 4.3%, the ZnO that mole is 0.05%, mole are 0.003%3With the SnO that mole is 0.1%.
Weigh 2000g raw materials and mix, compound is poured into platinum crucible, 4h is then heated in 1550 DEG C of resistance furnaces, and use
Platinum rod is stirred to exclude bubble and be homogenized glass metal.By in the glass metal casting stainless steel cast iron grinding tool melted, formed
For defined both bulk glasses product, then glassware is annealed in the lehr 2 hours, close power supply furnace cooling to 25
℃.Glassware is cut, ground, polished, is then cleaned up and is dried with deionized water.
Obtained alumina silicate glass S1 is subjected to performance measurement, the results are shown in Table 1.
Embodiment 2-20
According to the method for embodiment 1, the difference is that, prepare alumina silicate glass according to the composition of table 1.
Obtained alumina silicate glass S2-S20 is subjected to performance measurement, the results are shown in Table 1.
Comparative example 1-6
According to the method for embodiment 1, the difference is that, prepare alumina silicate glass according to the composition of table 1.
Obtained alumina silicate glass D1-D6 is subjected to performance measurement, the results are shown in Table 1.
Table 1
Continued 1
Can be seen that alumina silicate glass provided by the present invention by the result of table 1 has good heat endurance, energy
Enough have higher annealing point temperature and relatively low fusion temperature and forming temperature concurrently, be unlikely to deform, be not easy to soften.Specifically, aluminium
Silicate glass is 10 in viscosity13Corresponding annealing point temperature can not only reach more than 750 DEG C during pool, and be in viscosity
Corresponding temperature is less than 1650 DEG C during 200 pool, and when viscosity is 35000 pool, corresponding temperature is less than 1300 DEG C.So as to add
The practicality of alumina silicate glass.
The alumina silicate glass corresponding temperature and viscosity when viscosity is 35000 pool are 1013During pool corresponding temperature it
Between difference be less than 490 DEG C, there is relatively low forming temperature, so as to shorten the length of production line, reduce energy consumption and making
Cost, beneficial to industrialized production.
The alumina silicate glass still has higher mechanical strength, its density is less than 2.70g/cm after being thinned3；50
~350 DEG C of thermal coefficient of expansion is less than 39 × 10-7/℃；Young's modulus is more than 80GPa；Surface tension under 1250 DEG C of high temperature is low
In 380mN/m.
In addition, the alumina silicate glass has suitable chemical resistance, it is under 10%HF sour (20 DEG C/20min)
Resistance to chemical corrosion be 4.0~6.0mg/cm2, so as to be effectively improved the yield of product, beneficial to industrialized production.
On the premise of poisonous and harmful fining agent, the sulfate, nitrate, tin oxide and the oxygen that select integral molar quantity to be not more than 1%
Change at least one of stannous and be used as fining agent, the effect well clarified can be reached, in the present invention, the alumino-silicate glass
Glass bubble diameter in per kilogram glass substrate is invisible more than 0.1mm bubbles number.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited thereto.In the skill of the present invention
In art concept, technical scheme can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and these simple variants and combination should equally be considered as content disclosed in this invention, belong to
Protection scope of the present invention.
Claims (13)
1. a kind of alumina silicate glass, it is characterised in that on the basis of the integral molar quantity of the alumina silicate glass, with oxide
Meter, the alumina silicate glass contain：
2. alumina silicate glass according to claim 1, it is characterised in that SiO2Molar content be 64~67.5%.
3. alumina silicate glass according to claim 1, it is characterised in that Al2O3Molar content be 12~14.5%.
4. alumina silicate glass according to claim 1, it is characterised in that B2O3Molar content be 1~3.5%, preferably
For 1.51~2.99%.
5. alumina silicate glass according to claim 1, it is characterised in that MgO molar content is 6~14%, preferably
It is more preferably 7~12% for 6.5~13.5%, more preferably 7.5~9.5%.
6. alumina silicate glass according to claim 1, it is characterised in that CaO molar content is 1~8.5%.
7. alumina silicate glass according to claim 1, it is characterised in that SrO molar content is 3.5~8.5%, excellent
Elect 4~8% as, be more preferably 4.3~7.5%, more preferably 4.6~7%.
8. alumina silicate glass according to claim 1, it is characterised in that ZnO molar content is 0.05~0.7%.
9. alumina silicate glass according to claim 1, it is characterised in that MoO3Molar content be 0.005~0.3%.
10. alumina silicate glass according to claim 1, it is characterised in that the alumina silicate glass also contains fining agent；
Preferably, the fining agent is at least one of barium sulfate, barium nitrate, strontium nitrate, tin oxide and stannous oxide；
Preferably, on the basis of the integral molar quantity of sillico aluminate glass, the mole of the fining agent is not more than 1%, is preferably
0.08~0.5%, more preferably 0.1~0.4%.
11. alumina silicate glass according to claim 1, it is characterised in that the density of the alumina silicate glass is less than
2.70g/cm3, preferably 2.5~2.65g/cm3；50~350 DEG C of thermal coefficient of expansion is less than 39 × 10-7/ DEG C, preferably 30~
39×10-7/℃；Young's modulus is more than 80GPa, preferably 81~90GPa；1250 DEG C of high temperature surface tension are less than 380mN/m, excellent
Elect 320~380mN/m as；
Preferably, corresponding temperature is less than 1650 DEG C, preferably 1500~1650 DEG C when viscosity is 200 pool；Viscosity is 35000 pools
When corresponding temperature be less than 1300 DEG C, preferably 1100~1300 DEG C；Viscosity is 1013Corresponding annealing point temperature is 750 during pool
More than DEG C, preferably 750~830 DEG C；
Preferably, corresponding temperature and viscosity are 10 when viscosity is 35000 pool13Difference during pool between corresponding annealing point temperature
Less than 490 DEG C, preferably smaller than 470 DEG C, 460 DEG C, most preferably 370~460 DEG C are further preferably no larger than；In 10%HF acid (20
DEG C/20min) under chemical resistance be 4.0~6.0mg/cm2；Bubble diameter is more than 0.1mm bubble in per kilogram glass substrate
Number is invisible.
12. a kind of method for preparing the alumina silicate glass in claim 1-11 described in any one, this method include：By original
Material mixing is to obtain compound, and by the compound melt-processed, stirring discharges bubble and is homogenized glass metal, is then moved back
Fire processing and cold work.
13. the base material that the alumina silicate glass in claim 1-11 described in any one shows and illuminated as plane is answered
With.
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| CN201710683419.5A CN107382054A (en) | 2017-08-10 | 2017-08-10 | Alumina silicate glass and its preparation method and application |
| CN201810898378.6A CN109020195B (en) | 2017-08-10 | 2018-08-08 | Aluminosilicate glass and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114716143A (en) * | 2022-04-13 | 2022-07-08 | 青岛融合装备科技有限公司 | Alkali-free boroaluminosilicate glass for liquid crystal glass substrate |
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| CN109775984B (en) * | 2019-03-08 | 2022-02-08 | 东旭光电科技股份有限公司 | Glass composition, aluminosilicate glass, and preparation method and application thereof |
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| DE19939789A1 (en) * | 1999-08-21 | 2001-02-22 | Schott Glas | Alkali-free aluminoborosilicate glasses and their uses |
| DE102005019958B4 (en) * | 2005-04-29 | 2010-02-18 | Schott Ag | Flash light source with glass envelope |
| US7709406B2 (en) * | 2007-07-31 | 2010-05-04 | Corning Incorporation | Glass compositions compatible with downdraw processing and methods of making and using thereof |
| CN106495468A (en) * | 2016-10-11 | 2017-03-15 | 武汉理工大学 | A kind of ultra-thin glass of low surface tension and preparation method thereof |
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| CN114716143A (en) * | 2022-04-13 | 2022-07-08 | 青岛融合装备科技有限公司 | Alkali-free boroaluminosilicate glass for liquid crystal glass substrate |
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