CN105859125A - Ultrathin glass with high hardness and high strength and preparation method thereof - Google Patents
Ultrathin glass with high hardness and high strength and preparation method thereof Download PDFInfo
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- CN105859125A CN105859125A CN201610209072.6A CN201610209072A CN105859125A CN 105859125 A CN105859125 A CN 105859125A CN 201610209072 A CN201610209072 A CN 201610209072A CN 105859125 A CN105859125 A CN 105859125A
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- thin glass
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- strength ultra
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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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- 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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
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Abstract
The invention belongs to the technical field of glass production, and relates to a formula and preparation method for producing ultrathin glass by an overflow method. The ultrathin glass with high hardness and high strength is characterized by comprising the components in mass percent: 70-78wt% of SiO2, 1-3wt% of Al2O3, 9-13wt% of Na2O, 6-10wt% of CaO, 2-5wt% of MgO, 0.5-3.5wt% of SrO and 0-1wt% of K2O. The preparation method can improve the hardness and strength of glass to achieve the scratch-proof and pressure resistant characteristics of the product.
Description
Technical field
The invention belongs to field of glass production technology, relate to a kind of press over system that is applicable to and produce formula and the preparation method of ultra-thin glass,
A kind of preparation method of the high-strength ultra-thin glass of high rigidity.
Background technology
Along with development and the demand in ultra-thin glass market, the range of application of current ultra-thin glass is quite varied, relates to industry-by-industry
And field.Such as, LCDs, camera head, solar cell substrate, mobile phone and universe solar cell substrate
Deng.
The research being abroad directed to ultra-thin glass is more much earlier than domestic.Present Domestic is the most for ultra-thin glass research, but its property
Can especially in terms of physical and mechanical properties ratio external Corning, Gorilla and Xensation etc. compare, also exist one
Fixed gap.The fragmentation of ultra-thin glass, lose and the problem such as cut also happens occasionally, to such an extent as to most ultra-thin glass
The requirement of product is met by import.So China is in the urgent need to having independent intellectual property right and ultra-thin glass of good performance.
In the glass ingredient mentioned in prior art, alkali content is higher, reduces the mechanical performance of glass.Chinese patent is " ultra-thin floating
Method glass " (publication No.: CN1712375A) formulate according to the particular/special requirement of performance, effect and the ultra-thin glass of various components,
But its Vickers hardness and bending strength are the highest.
Chinese patent " a kind of high strength slim glass and preparation method thereof " (publication No.: CN103722816) is at glass basis
Surface has the film plating layer of stress with at least one of which, mainly uses and improves intensity by the way of plated film rather than carry
The intensity of high glass itself.
Chinese patent " a kind of low-density and high-strength touch screen cover-plate glass " (publication No.: CN104211299A) adds necessarily
The LiO of amount2And B2O3, deducted the alkali and alkaline earth metal ions oxide that ionic radius is bigger, reduced the density of cover-plate glass
With its intensity of raising.But the intensity before its non-tempering is relatively low.
The present invention passes through CaO and Na2The mass fraction ratio design of O, selects the basic components of optimization；Ensure alkali on its basis
The physical and mechanical properties that earth metal total content one timing utilizes " mixed alkali effect " of alkaline earth oxide to improve ultra-thin glass reaches
Requirement to ultra-thin glass product.
Summary of the invention
It is an object of the invention to the development for current ultra-thin glass market and demand, adjusted by glass ingredient, it is provided that Yi Zhonggao
Hardness high strength slim glass and preparation method thereof, can improve hardness and the intensity of glass, to have reached the scratch-resistant pressure of product
Feature.
For achieving the above object, the technical solution used in the present invention is: a kind of hard high-strength ultra-thin glass, it is characterised in that
In described glass, the mass percent of each component is respectively: SiO2: 70～78wt%, Al2O3: 1～3wt%, Na2O:9～13wt%,
CaO:6～10wt%, MgO:2～5wt%, SrO:0.5～3.5wt%, K2O:0～1wt%.
In described glass, the mass percent of each component is respectively: SiO2: 72.5～73wt%, Al2O3: 1.6～1.8wt%,
Na2O:11.5～11.7wt%, CaO:7.5～8.1wt%, MgO:4.1～4.5wt%, SrO:0.5～1.5wt%, K2O:0.7～0.9wt%.
SiO2Preferably mass percent is: 71～74wt%.
Al2O3Preferably mass percent is: 1.5～2wt%.
Na2The preferred mass percent of O is: 10～12.5wt%.
The preferred mass percent of CaO is: 7.0～9.8wt%.
The preferred mass percent of MgO is: 3～5wt%.
The preferred mass percent of SrO is: 0.5～3wt%.
K2The preferred mass percent of O is: 0.5～1wt%.
SiO2It is important glass former oxide, forms irregular continuous net with the construction unit of silicon-oxy tetrahedron [SiO4]
Network, becomes the skeleton of glass.Its content affects endurance and the mechanical strength of glass, can produce the density of glass
Raw impact.Content is the highest, and chemical resistance and the mechanical strength of glass are the highest.On the other hand, put forward full-bodied tendency owing to having,
Content is the highest, increases the high temperature viscosity of glass, makes glass be difficult to melt.SiO of the present invention2Content is between 70～78wt%, preferably
It is between 71～74wt%.
Al2O3It it is the neccessary composition improving chemical durability of glass.But as Na in glass2O and Al2O3Mol ratio more than 1 time,
Form aluminum-oxygen tetrahedron and form continuous print structural network with silicon-oxy tetrahedron, and mol ratio is less than 1, then form octahedron, for
Network outer body and be in the hole of silica structure net.Most glass all introduce the Al of 1～3.5wt%2O3.Al of the present invention2O3
Content is between 1～3wt%, preferably 1.5～2wt%.
MgO is the network modifying oxide of glass, often MgO is replaced part CaO in glass, and the hardness speed of glass can be made to become
Slowly, forming of glass performance is improved.And a certain amount of MgO, chemical stability and the mechanical strength of glass can be improved.The present invention
Content of MgO is between 2～5wt%, between preferably 3～5wt%.
K2O is also the network modifying oxide of glass.K+The addition of ion, not only reduces the viscosity of glass, and can improve
The transparency of glass and gloss.K of the present invention2The content of O is between 0～1wt%, between preferably 0.5～1wt%.
Na2O, CaO and SrO are all the network modifying oxides of glass.It can reduce the viscosity of glass, promotes the fusing of glass
And clarification, but Na2O can reduce the heat stability of glass, chemical stability and mechanical strength.When CaO is higher, glass can be made
Tendency increases, and easily makes glass embrittlement, Na2When O content is higher, the mechanical performance of glass can be reduced.In same main group, SrO
More weak relative to MgO and CaO of character.When introduction volume is less, jointly can act on main group oxide with other two kinds
Improve the mechanical performance of glass, but when substituted amount is too much, the mechanical performance of glass can greatly reduce.So selecting to introduce
The Na of CaO, 10～the 12.5wt% of 7.0～9.8wt%2The SrO of O and 0.5～3wt%.
Under conditions of " mixed alkali effect " of alkaline earth oxide refers to that the total content of alkaline earth oxide is constant, by one alkali
Soil metal oxide replaces another or two kinds, and its performance change curve is not straight line change, but in specific position
Extreme value occurs.
The preparation method of above-mentioned a kind of hard high-strength ultra-thin glass, it is characterised in that comprise the steps:
1) the choosing of raw material: by the mass percent of component each in glass respectively: SiO2: 70～78wt%, Al2O3: 1～3wt%,
Na2O:9～13wt%, CaO:6～10wt%, MgO:2～5wt%, SrO:0.5～3.5wt%, K2O:0～1wt%, the raw material chosen is equal
It is the analytical pure of Chemical Reagent Co., Ltd., Sinopharm Group's production, wherein SiO2、Al2O3、Na2O, CaO, MgO, SrO and
K2O is introduced by silicon dioxide, aluminium oxide, sodium carbonate, calcium carbonate, basic magnesium carbonate, strontium carbonate, potassium carbonate respectively；
2) raw material after weighing is sufficiently mixed uniformly, obtains compound；
3) again compound is put in crucible, at 1500～1600 DEG C, be incubated 1.5～2.5h, then by fast for the vitreous humour that melts
Rapid-result type, obtains glass sample；The stress in glass sample, wherein annealing process system: annealing temperature is eliminated by annealing
600～650 DEG C and annealing time 2～3h；
4) utilize inner circle cutting machine to cut into the glass sample after annealing thin glass that thickness is 0.5～1mm；Wherein, thin glass
Preparation method: being bonded on ready target by glass sample, the program being fixed on cutting machine and setting cutting machine is (thick
Degree is 0.5～1mm), the equipment of being then turned on cuts；
5) acid corrosion method-etch method is used to obtain hard high-strength ultra-thin glass in above-mentioned thin glass.Wherein, etch method
Refer to that the corrosion treatmentCorrosion Science that the surface of high-quality glass carries out 30～35min makes its lower thickness, then utilize supersound washing 1.5～2h
The Impurity removal of glass surface, the high-temperature heating that glass finally carries out 1000～1200 DEG C makes it naturally shakeout；Used
Acid solution is the HF acid solution of the 3～5wt% of 30ml.
The invention has the beneficial effects as follows: by CaO and Na2The mass fraction ratio design of O, selects the basic components of optimization；?
Ensure on the basis of it that alkaline-earth metal total content one timing utilizes " mixed alkali effect " of alkaline earth oxide, increase the hard of ultra-thin glass
Degree and intensity.After the technical program adjusts the content of above two oxide, alkaline earth oxide total content on its basis
One timing introduces MgO and CaO of SrO Substitute For Partial, modest viscosity and be prone to fusing during glass high temperature, thus reduces fuel etc.
Consumption, decrease the pollution to environment；Product has relatively low density, and density is 2.47～2.50g/cm3Between；Through one it is
After row physical method processes, its microhardness is up to 673.4Kfg/mm2And bending strength reaches more than 120MPa, and
Scratch-resistant pressure, it is entirely capable of reaching the serviceability requirement of ultra-thin glass product.
Accompanying drawing explanation
Fig. 1 is the H103 resin figure of the 300-800nm of comparative example 1-6.
Fig. 2 is the H103 resin figure of the 300-800nm of embodiments of the invention 7-12.
Fig. 3 is the H103 resin figure of the 300-800nm of embodiments of the invention 13-15.
Detailed description of the invention
A kind of hard high-strength ultra-thin glass, it is important that the percent mass score of each constituent in the formula of above-mentioned glass
It is not: SiO2: 70～78wt%, Al2O3: 1～3wt%, Na2O:9～13wt%, CaO:6～10wt%, MgO:2～5wt%, SrO:0.5～3.5%,
K2O:0～1wt%.
The preparation method of above-mentioned a kind of hard high-strength ultra-thin glass, comprises the steps:
1) the choosing of raw material: by the mass percent of component each in glass respectively: SiO2: 70～78wt%, Al2O3: 1～3wt%,
Na2O:9～13wt%, CaO:6～10wt%, MgO:2～5wt%, SrO:0.5～3.5wt%, K2O:0～1wt%, the raw material chosen is equal
It is the analytical pure of Chemical Reagent Co., Ltd., Sinopharm Group's production, wherein SiO2、Al2O3、Na2O, CaO, MgO, SrO and
K2O is introduced by silicon dioxide, aluminium oxide, sodium carbonate, calcium carbonate, basic magnesium carbonate, strontium carbonate, potassium carbonate respectively；
2) raw material after weighing is sufficiently mixed uniformly, obtains compound；
3) again compound is put in crucible, at 1500～1600 DEG C, be incubated 1.5～2.5h, then by fast for the vitreous humour that melts
Rapid-result type, obtains glass sample；The stress in glass sample, wherein annealing process system: annealing temperature is eliminated by annealing
600～650 DEG C and annealing time 2～3h；
4) utilize inner circle cutting machine to cut into the glass sample after annealing thin glass that thickness is 0.5～1mm；Wherein, thin glass
Preparation method: being bonded on ready target by glass sample, the program being fixed on cutting machine and setting cutting machine is (thick
Degree is 0.5～1mm), the equipment of being then turned on cuts；
5) acid corrosion method-etch method is used to obtain hard high-strength ultra-thin glass in above-mentioned thin glass；Wherein, acid corrosion
Method-etch method refers to that the corrosion treatmentCorrosion Science that the surface of high-quality glass carries out 30～35min makes its lower thickness, then utilizes ultrasonic washing
Washing 1.5～2h makes it naturally shakeout the Impurity removal of glass surface, the high-temperature heating that glass finally carries out 1000～1200 DEG C；
The acid solution used is the HF acid solution of the 3～5wt% of 30ml.
The hard high-strength ultra-thin glass obtained is carried out key property test, wherein contain density, transmitance, micro-firmly
Degree and intensity etc..
Table 1 shows proportioning and the key property test result of comparative example 1-6.Table 2 shows the embodiment of the present invention
The proportioning of 7-12 and key property test result.
Table 1 (comparative example 1-6)
Table 2 (embodiment of the present invention 7-12)
By table 1, table 2 it can be seen that utilize in inventive formulation and first adjust CaO and Na with method of substitution2The mass fraction ratio of O；
Under conditions of ensureing that on the basis of its optimization formula alkaline earth oxide total content is certain, introduce SrO and replace part MgO and CaO
Utilize " mixed alkali effect " of alkaline earth oxide；Both common effects can increase hardness and the intensity of glass, and its density exists
2.47～2.50g/cm3, microhardness reach 673.4Kfg/mm2, bending strength reach more than 120MPa, and scratch-resistant pressure,
It is entirely capable of reaching the serviceability requirement of ultra-thin glass product.
Table 3 (embodiment of the present invention 13-15)
As can be seen from Table 3, utilize in inventive formulation and first adjust CaO and Na with method of substitution2The mass fraction ratio of O；At it
Under conditions of ensureing on the basis of optimization formula that alkaline earth oxide total content is certain, introduce SrO replacement part MgO and CaO comes
Utilize " mixed alkali effect " of alkaline earth oxide；Both common effects can increase hardness and the intensity of glass.
The bound of each raw material of the present invention, interval value, and the bound of technological parameter (such as temperature, time etc.), interval
Value can realize the present invention, embodiment numerous to list herein.
Claims (11)
1. a hard high-strength ultra-thin glass, it is characterised in that in described glass, the mass percent of each component is respectively:
SiO2: 70～78wt%, Al2O3: 1～3wt%, Na2O:9～13wt%, CaO:6～10wt%, MgO:2～5wt%, SrO:0.5～3.5wt%,
K2O:0～1wt%.
A kind of hard high-strength ultra-thin glass the most according to claim 1, it is characterised in that each component in described glass
Mass percent respectively: SiO2: 72.5～73wt%, Al2O3: 1.6～1.8wt%, Na2O:11.5～11.7wt%,
CaO:7.5～8.1wt%, MgO:4.1～4.5wt%, SrO:0.5～1.5wt%, K2O:0.7～0.9wt%.
A kind of hard high-strength ultra-thin glass the most according to claim 1, it is characterised in that SiO2Preferably quality hundred
Mark is: 71～74wt%.
A kind of hard high-strength ultra-thin glass the most according to claim 1, it is characterised in that Al2O3Preferably quality hundred
Mark is: 1.5～2wt%.
A kind of hard high-strength ultra-thin glass the most according to claim 1, it is characterised in that Na2The preferred quality of O hundred
Mark is: 10～12.5wt%.
A kind of hard high-strength ultra-thin glass the most according to claim 1, it is characterised in that the preferred quality of CaO
Percent is: 7.0～9.8wt%.
A kind of hard high-strength ultra-thin glass the most according to claim 1, it is characterised in that the preferred quality of MgO hundred
Mark is: 3～5wt%.
A kind of hard high-strength ultra-thin glass the most according to claim 1, it is characterised in that the preferred quality of SrO hundred
Mark is: 0.5～3wt%.
A kind of hard high-strength ultra-thin glass the most according to claim 1, it is characterised in that K2The preferred quality of O
Percent is: 0.5～1wt%.
The preparation method of a kind of hard high-strength ultra-thin glass the most as claimed in claim 1, it is characterised in that include as follows
Step:
1) the choosing of raw material: by the mass percent of component each in glass respectively: SiO2: 70～78wt%, Al2O3: 1～3wt%,
Na2O:9～13wt%, CaO:6～10wt%, MgO:2～5wt%, SrO:0.5～3.5wt%, K2O:0～1wt%, the raw material chosen；
Wherein SiO2、Al2O3、Na2O, CaO, MgO, SrO and K2O respectively by silicon dioxide, aluminium oxide, sodium carbonate, calcium carbonate,
Basic magnesium carbonate, strontium carbonate, potassium carbonate introduce；
2) raw material after weighing is sufficiently mixed uniformly, obtains compound；
3) again compound is put in crucible, at 1500～1600 DEG C, be incubated 1.5～2.5h, then by fast for the vitreous humour that melts
Rapid-result type, obtains glass sample；The stress in glass sample, wherein annealing process system: annealing temperature is eliminated by annealing
600～650 DEG C and annealing time 2～3h；
4) glass sample after annealing is cut into the thin glass that thickness is 0.5～1mm；
5) use acid corrosion method-etch method to process in above-mentioned thin glass, obtain hard high-strength ultra-thin glass.
The preparation method of 11. a kind of hard high-strength ultra-thin glass according to claim 10, it is characterised in that: described
Acid corrosion method-etch method process refers to that the corrosion treatmentCorrosion Science that the surface of thin glass carries out 30～35min makes its lower thickness, then profit
Make it certainly the Impurity removal of glass surface, the high-temperature heating that glass finally carries out 1000～1200 DEG C with supersound washing 1.5～2h
So shakeout；The acid solution used is the HF acid solution of the 3～5wt% of 30ml.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610209072.6A CN105859125B (en) | 2016-04-06 | 2016-04-06 | A kind of hard high-strength ultra-thin glass and preparation method thereof |
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| CN105859125B CN105859125B (en) | 2019-04-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423001A (en) * | 2019-07-29 | 2019-11-08 | 信义电子玻璃（芜湖）有限公司 | A kind of electronic glass and its application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56145132A (en) * | 1980-04-14 | 1981-11-11 | Nippon Electric Glass Co Ltd | Glass composition |
| CN101410333A (en) * | 2006-03-27 | 2009-04-15 | 旭硝子株式会社 | Glass-making process |
| CN102056855A (en) * | 2008-06-09 | 2011-05-11 | 皮尔金顿集团有限公司 | Glass plate for a solar unit, and glass composition |
-
2016
- 2016-04-06 CN CN201610209072.6A patent/CN105859125B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56145132A (en) * | 1980-04-14 | 1981-11-11 | Nippon Electric Glass Co Ltd | Glass composition |
| CN101410333A (en) * | 2006-03-27 | 2009-04-15 | 旭硝子株式会社 | Glass-making process |
| CN102056855A (en) * | 2008-06-09 | 2011-05-11 | 皮尔金顿集团有限公司 | Glass plate for a solar unit, and glass composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423001A (en) * | 2019-07-29 | 2019-11-08 | 信义电子玻璃（芜湖）有限公司 | A kind of electronic glass and its application |
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