CN110002744A - A kind of high impact properties glass and preparation method thereof - Google Patents
A kind of high impact properties glass and preparation method thereof Download PDFInfo
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- CN110002744A CN110002744A CN201910364865.9A CN201910364865A CN110002744A CN 110002744 A CN110002744 A CN 110002744A CN 201910364865 A CN201910364865 A CN 201910364865A CN 110002744 A CN110002744 A CN 110002744A
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- alkali metal
- high impact
- metal ion
- impact properties
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- 239000011521 glass Substances 0.000 title claims abstract description 276
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 80
- 238000007906 compression Methods 0.000 claims abstract description 36
- 230000006835 compression Effects 0.000 claims abstract description 36
- 238000012360 testing method Methods 0.000 claims abstract description 30
- 238000005452 bending Methods 0.000 claims abstract description 26
- 238000009826 distribution Methods 0.000 claims abstract description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 61
- 230000003014 reinforcing effect Effects 0.000 claims description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 229910052681 coesite Inorganic materials 0.000 claims description 27
- 229910052906 cristobalite Inorganic materials 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 229910052682 stishovite Inorganic materials 0.000 claims description 27
- 229910052905 tridymite Inorganic materials 0.000 claims description 27
- 229910052593 corundum Inorganic materials 0.000 claims description 26
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 26
- 239000012530 fluid Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229930002839 ionone Natural products 0.000 claims 2
- 150000002499 ionone derivatives Chemical class 0.000 claims 2
- 239000004744 fabric Substances 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract description 10
- 239000010410 layer Substances 0.000 description 25
- 238000005342 ion exchange Methods 0.000 description 21
- 239000000523 sample Substances 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 17
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000003426 chemical strengthening reaction Methods 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000006058 strengthened glass Substances 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000002787 reinforcement Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000005354 aluminosilicate glass Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- -1 alkali metal cation Chemical class 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000003116 impacting effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—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
Abstract
The invention discloses a kind of high impact properties glass, wherein, along high impact properties thickness of glass direction, there are two types of high impact-resistant glass tools or the above alkali metal ion, when 0 < x≤2t/5, distribution on each alkali metal ion concentration through-thickness is all satisfied relational expression: y=aln (x)+b, wherein t is the thickness of the high impact properties glass；X is the distance between certain point and glass surface, and unit is μm；Y is a kind of concentration of alkali metal ion of the point, and unit is quality %；A, b is arbitrary constant, and the numerical value of a and b are determined by the type of alkali metal.The invention further relates to a kind of preparation method and applications of high impact properties glass.High impact properties glass according to the present invention and preparation method thereof, the bending strength that the surface compression stress of the high impact properties glass of offer is high, stress layer depth is big, 4 anti-bending tests measure is bigger, resistible impact energy is big, and shock resistance other machinery is had excellent performance.
Description
Technical field
The present invention relates to liquid-crystalline glasses technical fields, and in particular to a kind of high impact properties glass and preparation method thereof.
Background technique
Currently, being applied to mobile phone, computer, smartwatch and other are various with the mobile device screens such as touch screen panel
The cover-plate glass of protection, usually requiring that has preferably physical property and higher mechanical performance, such as high mechanical strength, high Young
Modulus, high chemical temperatures and lightening etc. so that mobile device avoid in use due to impacting, falling, scraping,
Screen caused by the extraneous factors such as extruding damages.
The physical property and mechanical performance for promoting glass such as change the composition of glass, adjustment is melted and molded there are many method
Technique, post-production technique (being such as thinned, polishing, tempering, coating, plated film), in the prior art mainly from two aspects, one
It is the structure composition for changing glass itself, adjusts glass formula, such as soda-lime glass is substituted with high aluminosilicate glass, first is that using the later period
Processing technology glass is strengthened again, such as chemical strengthening.
High aluminosilicate glass on the market is after chemical strengthening now, bearing stress (CS) can achieve 500MPa with
On, stress layer depth (DOL) can achieve 25 μm or more, and the bending strength (P) that 4 anti-bending tests measure is arrived in 300MPa
Between 400MPa, falling sphere experiment and complete machine drop test in, resistible impact energy can reach 100Nmm~
120N·mm.It is significantly promoted although having compared with common soda lime glass various aspects of performance, for the ultra-thin of present mobile device
Superpower cover board requirement has a certain gap, especially for needing to resist impact energy in the falling sphere of 200Nmm or more and whole
When machine falls, the common high aluminosilicate glass after conventional chemical is strengthened can not meet requirement.
Summary of the invention
It can not meet asking for actual demand to solve above-mentioned conventional chemical strengthened glass impact resistance in the prior art
Topic, the present invention provide the bending strength that a kind of surface compression stress is high, stress layer depth is big, 4 anti-bending tests measure it is big, can
The big high impact properties glass of the impact energy of resistance, specific technical solution are as follows:
The present invention provides a kind of high impact properties glass, wherein
Along high impact properties thickness of glass direction, high impact-resistant glass tool there are two types of or the above alkali metal from
Son,
When 0 < x≤2t/5, the distribution on each alkali metal ion concentration through-thickness is all satisfied relational expression: y=aln
(x)+b,
Wherein, t is the thickness of the high impact properties glass；X is the distance between certain point and glass surface, and unit is
μm；Y is a kind of concentration of alkali metal ion of the point, and unit is quality %；A, b is arbitrary constant, and the numerical value of a and b are by alkali gold
The type of category determines.
Further, the high impact properties glass with a thickness of 0.2mm≤t≤2.0mm.
Further, the distribution on the maximum alkali metal ion concentration through-thickness of ionic radius meets relational expression: y=
a11n(x)+b1, a1< 0, b1> 0；Distribution on the smallest alkali metal ion concentration through-thickness of ionic radius meets relationship
Formula: y=a2ln(x)+b2, a2> 0, b2> 0.
Further, the high impact properties glass, surface compression stress CS is in 700MPa or more, preferably
750MPa；Its compression stress layer depth DOL is at 70 μm or more, preferably at 80 μm or more；The bending resistance that its 4 anti-bending tests measure
Intensity P is in 500MPa or more, preferably in 520MPa or more；Its resistible impact energy Ep preferably exists in 280Nmm or more
300Nmm or more.
Further, the high impact properties glass is by carrying out the original glass plate being prepared by glass composition
Intensive treatment and obtain；It is indicated with mass percent, the glass composition contains: SiO2: 56.8%~63%, Al2O3:
13.5%~21.5%, MgO:1.1%~8.5%, Na2O:10%~22% and K2O, and K2O/Na2The ratio of O is less than
0.5；Preferably, containing Na2O:11%~18%, and K2O/Na2The ratio of O is less than 0.45；Preferably, contain:
SiO2: 58%~61.5%, Al2O3: 13.5%~20%, MgO:3.5%~7%, Na2O:12%~15%；Further preferably
Contain on ground: SiO2: 59.5%~61.5%, Al2O3: 13.5%~17.5%, MgO:3.5%~6.8%, Na2O:
12.5%~14.5%.
Further, the high impact properties glass is by successively carrying out having source strength for the first time to the glass composition
Change, passive reinforcing, second active reinforcing and be made.
Further, the distributing homogeneity δ in the original glass plate, on every kind of alkali metal ion concentration through-thickness
It is all satisfied δ≤0.05, preferably δ≤0.04.
On the other hand, the present invention provides a kind of glass composition for being used to prepare high impact properties glass, wherein
It is indicated, is contained with mass percent: SiO2: 56.8%~63%, Al2O3: 13.5%~21.5%, MgO:
1.1%~8.5%, Na2O:10%~22% and K2O, and K2O/Na2The ratio of O is less than 0.5；Preferably, contain:
Na2O:11%~18%, and K2O/Na2The ratio of O is less than 0.45.Preferably, contain: SiO2: 58%~61.5%,
Al2O3: 13.5%~20%, MgO:3.5%~7%, Na2O:12%~15%；It is further preferred that it contains: SiO2:
59.5%~61.5%, Al2O3: 13.5%~17.5%, MgO:3.5%~6.8%, Na2O:12.5%~14.5%；By institute
It states in the original glass plate that glass composition is prepared, the distributing homogeneity on every kind of alkali metal ion concentration through-thickness
δ is all satisfied δ≤0.05, preferably δ≤0.04.
Another aspect, the present invention provide a kind of preparation method of foregoing high impact properties glass, wherein it is wrapped
It includes, following processing is successively carried out to the original glass plate made of glass composition:
Surface and/or edge pretreatment；
The pre-heat treatment；
Active intensive treatment for the first time, wherein including being put into the glass plate after above-mentioned the pre-heat treatment with the first main alkali
Active intensive treatment is carried out in the forced fluid of metal ion；
Passive intensive treatment；
Second of active intensive treatment, wherein including being put into the glass plate after above-mentioned passive intensive treatment with second
Active intensive treatment is carried out in the forced fluid of main alkali metal ion；
The glass composition, is indicated with mass percent, is contained: SiO2: 56.8%~63%, Al2O3: 13.5%~
21.5%, MgO:1.1%~8.5%, Na2O:10%~22% and K2O, and K2O/Na2The ratio of O is less than 0.5；
The original glass plate thickness t meets 0.2mm≤t≤2.0mm, every kind of alkali metal ion on its thickness direction
Distributing homogeneity is all satisfied δ and meets δ≤0.05, preferably δ≤0.04.
Further, in the preparation method, the preheating temperature of the pre-heat treatment is 370 DEG C~410 DEG C, preferably 380
DEG C~400 DEG C, more preferable 380 DEG C~390 DEG C.
Further, in the preparation method,
In the first time active intensive treatment step, the forced fluid also contain in addition to the first main alkali metal ion it
Outer one or more of secondary alkali metal ions, wherein the ionic radius of the first main alkali metal ion is greater than the glass
The big alkali metal ion of composition Ionic Radius time, the pair alkali metal ion total content are less than 5000ppm, preferably smaller than
4000ppm, more preferable 3000ppm；
The temperature of the first time active intensive treatment is not less than 350 DEG C, and the glass composition strain point temperature
Low at least 60 DEG C；Preferably, the temperature of active intensive treatment is not less than 380 DEG C for the first time, and the glass composition strains
Point temperature is at least 80 DEG C low；
The time of the first time active intensive treatment is 4h~10h, preferably 5h~8h, more preferable 5h~6h.
Further, the temperature of the passive intensive treatment be 380 DEG C~480 DEG C, preferably 400 DEG C~480 DEG C, more preferably
440 DEG C~450 DEG C, most preferably 450 DEG C；
The time of the passive intensive treatment is 10min~120min, preferably 60min~120min, more preferable 100min
~120min.
Further, in second of active intensive treatment step, the forced fluid also contains in addition to the second main alkali
One or more of secondary alkali metal ions except metal ion, wherein the ionic radius of the second main alkali metal ion is big
In the big alkali metal ion of the glass composition Ionic Radius time, the pair alkali metal ion total content is less than 4000ppm,
Preferably smaller than 3500ppm, more preferably less than 3000ppm；
The temperature of second of active intensive treatment is not less than 360 DEG C, and the glass composition strain point temperature
Low at least 100 DEG C；Preferably, the temperature of second of active intensive treatment is not less than 390 DEG C, and the glass composition strains
Point temperature is at least 120 DEG C or more low；
The time of the second active intensive treatment is 0.15h~2h, preferably 0.5h~1.5h, more preferable 0.5h~
1h。
Further, the preparation method, further includes:
After carrying out above-mentioned second of active intensive treatment step to the glass, passive intensive treatment and second are repeated
The step of active intensive treatment.
It is used for mobile terminal device in preparation in another aspect, the present invention also provides foregoing high impact properties glass,
It is preferred that the application in the protection glass process of mobile phone, computer, smartwatch.
The effect of invention
High impact properties glass according to the present invention, surface compression stress is high, stress layer depth is big, 4 bending resistances
The bending strength measured is big, resistible impact energy is big, so that shock resistance is substantially better than conventional chemical and strengthens glass
Glass.High impact properties glass of the invention is that original glass is prepared in the glass composition with constituent content of the present invention
Glass plate, then by the original glass plate pass sequentially through it is active for the first time strengthen, the multistage of passive reinforcing and second active reinforcing
Intensive treatment and obtain.The first time active reinforcing obtains biggish surface compression stress and stress layer depth；The nothing
Source strength step obtains bigger stress layer depth, this phase table face pressure stress under compression can be lowered；It is described to have source strength for the second time
Change, and increases surface compression stress.High surface compression stress and stress layer depth can be obtained simultaneously by multistage intensive treatment
Degree is obtained for the glass plate that particular glass composition of the invention is prepared by specific chemical strengthening method of the invention
To strengthened glass shock resistance be substantially better than the standby obtained glass plate of other glass compositions through strengthening resulting reinforcing glass
Glass.
Detailed description of the invention
Alkali metal ion Na in the original glass plate of Fig. 1 one specific embodiment of the present invention+Concentration is in a thickness direction
The curve graph of distribution.
Alkali metal ion K in the original glass plate of Fig. 2 one specific embodiment of the present invention+Concentration is in a thickness direction
The curve graph of distribution.
Fig. 3~Fig. 9 embodiment of the present invention A1 "~A7 " is active by second of the passive reinforcing-of active reinforcing-for the first time
Alkali metal ion Na after reinforcing+And K+Concentration distribution trend figure in a thickness direction.
High impact properties glass schematic diagram Figure 10 of the invention, t are thickness of glass, and x is inside glass certain point and distance
The distance between the closer glass surface of point.
Specific embodiment
It makes an explanation below in conjunction with attached drawing to exemplary embodiment of the invention, including each of embodiment of the present invention
Kind details should think them only exemplary to help understanding.Therefore, those of ordinary skill in the art should recognize
It arrives, embodiment described herein can be made various changes and modifications, without departing from scope and spirit of the present invention.
Term in invention
Surface compression stress (CS) refers to when carrying out the chemical strengthening of glass, glass is placed in forced fluid, glass is made
Radius lesser cation in surface layer is exchanged with the biggish cation of radius in forced fluid, is finally formed in two outer surfaces of glass
Compressive stress layers form compression stress in surface of ordinary glass, and the glass by reinforcing offsets surface when bearing external force first
Compression stress, to improve bearing capacity, reinforcing glass itself anti-wind pressure, cold and heat, impact etc..
Compression stress layer depth (DOL), refers to glass during chemical strengthening, the biggish sun of the radius in forced fluid
The depth that ion is exchanged with the lesser cation of the radius in glass.
4 anti-bending tests of glass, refer to and glass are placed on two stress points of certain distance, in the upper of stress point
Side is there are two putting to glass to apply pressure, and being had altogether up and down there are four point is the point of application and stress point respectively, which is referred to as glass
4 anti-bending tests of glass.
Bending strength (P) refers to and resists the not broken ability of bending by the glass that 4 anti-bending tests of glass measure.Extremely
Unit area load value when glassbreak is the bending strength of glass.
Resistible impact energy (Ep) refers in the impact test of glass, glass is impacted, until glassbreak,
Energy possessed by impacting at this time.
Distributing homogeneity (δ) on alkali metal ion concentration through-thickness refers to every kind of alkali metal ion concentration in thickness
The concentration deviation on direction is spent, is indicated with ion concentration standard deviation.
Active reinforcing refers to that the glass can provide the reinforcing that ion exchange is carried out with alkali metal ion in glass in the external world
The reinforcing carried out in liquid makes alkali gold in the alkali metal ion and the relatively large forced fluid of diameter in the relatively small glass of diameter
Ion carries out ion exchange, so that glass surface is had stronger compression stress, achievees the effect that strengthen glass.
Passive reinforcing refers to the reinforcing swapped without the extraneous alkali metal ion with glass, and glass is by active
After reinforcing, there are concentration differences for the alkali metal ion concentration of glass section, will can make after glass heating in active reinforced portion
Alkali metal ion into glass continues to spread to inside glass, causes the surface compression stressor layers of glass to deepen, middle cardiac stress
Constantly decline, achievees the purpose that reinforcing, the shock resistance of glass can be substantially improved.
In a specific embodiment, the present invention provides a kind of high impact properties glass, wherein along the high impact-resistant
Property thickness of glass direction on, high impact-resistant glass tool there are two types of or the above alkali metal ion, when 0 < x≤2t/5, each alkali
Distribution on concentration of metal ions through-thickness is all satisfied relational expression: y=aln (x)+b, wherein t is the high impact properties
The thickness of glass；X is certain point with apart from the distance between the closer glass surface of point, and unit is μm, as shown in Figure 10；y
For a kind of concentration of alkali metal ion of the point, unit is quality %；A, b is arbitrary constant, and the numerical value of a and b are by alkali metal
Type determines.
In a specific embodiment, the glass surface compression stress CS of high impact properties glass of the invention exists
700MPa or more, compression stress layer depth DOL at 70 μm or more, the bending strength P that 4 anti-bending tests measure 500MPa with
On, resistible impact energy Ep has in 280Nmm or more compared with high impact resistance and excellent other machinery performance.
In one preferred embodiment, the glass surface compression stress CS of high impact properties glass of the invention exists
750MPa or more, compression stress layer depth DOL at 80 μm or more, the bending strength P that 4 anti-bending tests measure 520MPa with
On, resistible impact energy Ep has higher shock resistance and excellent other machinery in 300Nmm or more
Energy.
Due to more to inside glass ion exchange more dynamics it is smaller, and the center tensile stress CT that is generated after reinforcing of glass with
There are non-error function relationships by surface compression stress CS, stress layer depth DOL and thickness t, and when tensile stress CT in center is more than glass
When the glass brittleness limit, glass will appear self-destruction risk, therefore CT is embodied in the relationship of x and thickness t no more than its brittleness limit
On, 0 < x≤t/2, comprehensive ion exchanges the influence to the amplification effect of glass properties and to center tensile stress CT, therefore in this hair
In bright above embodiment, 0 < x≤2t/5 is selected.In one preferred embodiment, 0 < x≤t/3.
In a specific embodiment, in high impact properties glass of the invention, the maximum alkali metal of ionic radius from
Distribution on sub- concentration through-thickness meets relational expression: y=a11n(x)+b1, a1< 0, b1> 0；The smallest alkali of ionic radius
Distribution on concentration of metal ions through-thickness meets relational expression: y=a2ln(x)+b2, a2> 0, b2> 0.
In a specific embodiment, high impact properties glass of the invention is to made of glass composition
Original glass plate successively carry out it is active for the first time strengthen, passive reinforcing, second active reinforcing and be made.
The process that original glass plate is prepared in the present invention is not particularly limited, and is not limited to casting method, centrifugal process, is floated
Method, press over system, glass tube down-drawing etc..
In a specific embodiment, preparation is melted using laboratory in the original glass plate, has no effect on original
Implementation of the glass plate in production.
In a specific embodiment, the specific preparation process of the original glass plate is as follows:
Conversion output charger sheet is carried out first, in accordance with each group distribution ratio in material side, it is former to weigh each corresponding compound by charger sheet
Expect and be mixed, mixture after mixing evenly is poured into platinum crucible and be put into high temperature furnace, carries out at high temperature
Fusing, fusion temperature are 1500 DEG C to 1650 DEG C, ultimately form glass metal.The glass metal of melting is cast in and is preheated to 550 DEG C
Into 700 DEG C of metal dies, glass is put into togerther annealing furnace annealing cooling, annealing temperature 630 together with metal die
DEG C to 650 DEG C, soaking time is 30~60 minutes at this temperature, then is naturally cooling to 120 DEG C to 80 DEG C, is cut after cooling
Polishing is cut, original glass plate of the invention is obtained.
In a specific embodiment, every kind of alkali metal ion concentration through-thickness in original glass plate of the invention
On distributing homogeneity δ be all satisfied δ≤0.05, preferably δ≤0.04.
To obtain this higher high impact resistance glass of resistible impact energy Ep of the invention, above embodiment
Distributing homogeneity δ in original glass plate on alkali metal ion concentration through-thickness is defined, original glass is conducive to
Plate when carrying out subsequent intensive treatment, alkali metal on through-thickness outside each level alkali metal ion and relatively each level from
Ion exchange between son more evenly, it is more efficient, to provide preferably primary attribute to ion exchange, while also to have for the second time
Distribution after the intensive treatment of source on alkali metal ion concentration through-thickness meets y=aln (x)+b relationship and provides basic guarantee.
The present invention also provides a kind of glass compositions for being used to prepare high impact properties glass, wherein
Preferably, it indicates by weight percent, the glass composition contains SiO2: 56.8~63%；Preferably,
Contain SiO2: 58~61.5%；It is highly preferred that it contains SiO2: 59.5%~61.5%；Most preferably, containing SiO2:
59.5%~61.2%；
Preferably, it indicates by weight percent, the glass composition contains Al2O3: 13.5%~21.5%；More preferably
Ground contains Al2O3: 13.5%~20%；It is highly preferred that it contains Al2O3: 13.5%~17.5%, most preferably, contain
There is Al2O3: 15.5%~16.8%；
Preferably, it indicates by weight percent, the glass composition contains MgO:1.1%~8.5%；Preferably,
It contains MgO:3.5%~7%；It is highly preferred that it contains MgO:3.5%~6.8%；
Preferably, it indicates by weight percent, the glass composition contains Na2O:10%~22%；Preferably,
Contain Na2O:11%~18%；It is highly preferred that it contains Na2O:12%~15% most preferably contains Na2O:12.5%
~14.5%；
Preferably, it indicates by weight percent, K2O/Na2The ratio of O is less than 0.5；It is highly preferred that K2O/Na2The ratio of O
Less than 0.45；
Preferably, it indicates by weight percent, the glass composition contains: SiO2: 56.8%~63%, Al2O3:
13.5%~21.5%, MgO:1.1%~8.5%, Na2O:10%~22% and K2O, and K2O/Na2The ratio of O is less than
0.5；
More selection of land indicates that the glass composition contains: SiO by weight percent2: 58%~61.5%, Al2O3:
13.5%~20%, MgO:3.5%~7%, Na2O:12%~15% and K2O, and K2O/Na2The ratio of O is less than 0.45.
Ingredient, ion-exchange temperature and the time of glass composition, schedule of reinforcement and to strengthen number be to influence ion exchange
The content of the principal element of intensity, the ingredient of glass composition and each ingredient has opposite impacts on ion exchange.In the following, first
First the composition of glass composition of the invention is illustrated, the mass percent on the basis of oxide is used to indicate each component
Content.
SiO2Silicon oxygen three-dimensional framework is constituted in glass, with oxygen-octahedron (SiO in glass structure2)4-As basic
Mechanism unit exists, and on the one hand assigns the good chemical stability of glass, thermal stability is transparent, higher softening temperature, firmly
Degree and mechanical strength, on the other hand with (AlO3)5-Aluminium silicon oxyanion group is formed, knot can be provided in the chemical intensification treatment in later period
Structure support.Such as SiO2Content is low, it may appear that thermal expansion coefficient of glass becomes larger, marresistance is deteriorated, glass transition temperature declines
Situation, while will affect later period chemical intensification treatment effect；Such as SiO2Content is high, then other components content is opposite in glass drops
It is low, in addition to SiO2Bring viscosity itself increases, glass is difficult to outside the factor melted, other performances of glass are due to other components
Variation occurs can not performance of expected change, it will usually reduce glass properties.To SiO in component2Content is limited to 56.8%~63%, both
It can assign glass good assertive evidence characteristic, and preferable supporting role can be played to later period chemical process.Work as SiO2Content is insufficient
When 56.8%, stability, glass and hardness is low or weatherability is low, preferably 58% or more, more preferably 59.5% or more.
SiO2When content is more than 63%, the viscosity of glass increases, meltbility decline, preferably 61.5% hereinafter, more preferably existing
61.2% or less.
Al2O3Because of Al3+Ligancy is not fixed or 4 or 6, with aluminum-oxygen tetrahedron (AlO in structural network4)4-With alumina eight
Face body (AlO6)8-In the presence of, and in alkali metal oxide R2In the presence of O or alkaline earth oxide RO, with (AlO3)5-
In the presence of due to (AlO3)5-Volume is about 41cm3/ mol, than (SiO2)4-Volume 27.24cm3/ mol is big, therefore works as Al2O3Content increases
Added-time, vitreum organization network space enlargement are conducive to ion diffusion exchange, improve ion-exchange speed.Al simultaneously2O3Have
Stable and anti-crystallization effect, high temperature viscosity of glass will increase when content is higher.Al in component2O3Content is preferably 13.5%~
21.5%, so that glass has preferable ion-exchange capacity, while high temperature viscosity is unlikely to excessive and is unable to meet production.When
Al2O3When less than 13.5%, ion-exchange speed is low, preferably 15% or more.Al2O3When more than 21.5%, the viscosity of glass
It increases, the melting of homogeneous becomes difficult.Preferably 20% hereinafter, more preferably 17.5% hereinafter, more preferably 16.8% with
Under.
MgO is the weaker ingredient of effect for declining ion-exchange speed, it is necessary at least containing 1.1% or more MgO.
When MgO is less than 1.1%, meltbility decline.Preferably 3.5% or more.When MgO is more than 8.5%, ion-exchange speed is low.Compared with
It is 7% well hereinafter, more preferably below 6.8%.
Na2O and K2O has fluxing action, while being the direct participant of chemical strengthening intermediate ion exchange, and chemistry is by force
The characterization person of stress intensity after change.Mainly by the biggish alkali metal cation displacement glass of extraneous ionic radius in ion exchange
The lesser alkali metal cation of Ionic Radius promotes glass to form compression stress at glass surface and stressor layers
Intensity.
Na in glass2On the one hand O promotes glass melting efficiency, on the other hand in the chemical intensification treatment in later period due to net
Na in network structure+More, ion exchange can be preferably participated in, keeps chemical strengthening effect more preferable, Na2When O is less than 10%, it is difficult to
Required surface compression stressor layers are formed by ion exchange.Preferably 11% or more, more preferably 12% or more, preferably
12.5% or more.Meanwhile Na2O content cannot be excessively high, such as more than 22%, glass will appear thermal expansion coefficient become larger, weatherability
The performances degradation trends such as variation, in addition, being limited to the balance limitation of glass each component total content, General N a2O content has upper limit value,
Preferably 18% hereinafter, more preferably 15% hereinafter, preferably below 14.5%.
K2O is the transparency and gloss that can increase glass, improves the ingredient of the meltbility of glass, and is for improving
Ion-exchange speed in chemical strengthening obtains the ingredient of required CS and DOL, is required.K2O is not above Na2O contains
Amount, usual K2O/Na2O is less than 0.5, and preferably smaller than 0.45, control K2O/Al2O3Mass values, then can be achieved at the same time higher
Liquid phase viscosity and higher ion-exchange performance, obtain the protection glass of shock resistance stress characteristics that performance advanced optimizes
Plate.
The present invention provides a kind of method for preparing high impact properties glass, and the preparation method includes: to by glass combination
Original glass plate made of object carries out following processing: surface and/or edge pretreatment；The pre-heat treatment；For the first time at active reinforcing
Reason, wherein carried out at active reinforcing including being put into the original glass plate in the forced fluid with the first main alkali metal ion
Reason；Passive intensive treatment；Second of active intensive treatment, wherein including being put into the original glass plate with the second main alkali
Active intensive treatment is carried out in the forced fluid of metal ion；And it may be selected after the passive reinforcing repeated again second
The reinforcing step of secondary active reinforcing；Wherein, the glass composition is indicated with oxide mass percentage, is contained: SiO2:
56.8%~63%, Al2O3: 13.5%~21.5%, MgO:1.1%~8.5%, Na2O:10%~22% and K2O, and
K2O/Na2The ratio of O is less than 0.5；The glass composition thickness t meets 0.2mm≤t≤2.0mm, along its thickness direction
Alkali metal ion distributing homogeneity meets δ and meets δ≤0.05.
Surface or/and edge pre-treatment step in above embodiment are carried out to original glass plate, are to remove or subtracting
The microdefects such as few glass surface and micro-crack, pit, the Micro scratching of edge, reduce the glass carry out it is active or without source strength
It usually can be used conventional at microdefect since the risk of glass breaking is concentrated and expanded or directly contribute to stress when change
CNC carving machine carries out.
First time active reinforcing step in above embodiment is carried out to the glass plate after the pre-heat treatment, it is therefore an objective to pass through
Technique defined by active reinforcing allows the glass strengthening the more exchange ions of rear surface enrichment, while inside can reach
The deeper time of the stage ion exchange, the i.e. stage obtain bigger compression stress layer depth DOL.
Passive reinforcing step in above embodiment is carried out to the glass plate of active reinforcing of above-mentioned first time, is to pass through
The energy that the external world assigns spreads the exchange ion of the glass surface enrichment to inside glass, and internal exchange ion is to more
Inside diffusion, to reach enhancing DOL purpose.Simultaneously because surface exchange ion is internally spread, without external world's exchange ion
Supplement, surface exchange ion is fewer and fewer, i.e. stage CS can be lower and lower.
Second of active reinforcing step is carried out to the glass plate after above-mentioned passive intensive treatment again, is for by extraneous ion
Source swaps ion to the glass surface and inside and is supplemented, and reaches enhancing surface C S purpose.
The reinforcing step that second of active reinforcing after the passive reinforcing repeated may be selected, with above-mentioned corresponding step
Purpose is the same, and effect can be better after reinforcing, but cost will increase, therefore selectivity carries out as needed.
In a specific embodiment, the preparation method of the high impact properties glass, wherein the pre-heat treatment
Preheating temperature is 370 DEG C~410 DEG C, preferably 380 DEG C~400 DEG C, more preferable 380 DEG C~390 DEG C.
In a specific embodiment, the preparation method of the high impact properties glass, wherein have in the first time
In source strength processing step, the forced fluid also contains one or more of secondary alkali gold other than the first main alkali metal ion
Belong to ion, wherein it is big that the ionic radius of the first main alkali metal ion is greater than the glass composition Ionic Radius time
Alkali metal ion, the pair alkali metal ion total content are less than 5000ppm, preferably smaller than 4000ppm, more preferable 3000ppm；Institute
The temperature of active intensive treatment for the first time is stated at 350 DEG C or more, and the glass composition strain point temperature is at least 60 DEG C low；
Preferably, the temperature of first time active intensive treatment is at 380 DEG C or more, and the glass composition strain point temperature is low at least
80℃；The time of active intensive treatment is 4h~10h, preferably 5h~8h, more preferable 5h~6h for the first time.At the passive reinforcing
The temperature of reason be 380 DEG C~480 DEG C, preferably 400 DEG C~480 DEG C, more preferable 440 DEG C~450 DEG C, most preferably 450 DEG C；The nothing
The time of source intensive treatment is 10min~120min, preferably 60min~120min, more preferable 100min~120min.Described
In second of active intensive treatment step, the forced fluid also contains one or more of other than the second main alkali metal ion
Secondary alkali metal ion, wherein the ionic radius of the second main alkali metal ion is greater than the glass composition intermediate ion half
The big alkali metal ion of diameter time, the pair alkali metal ion total content is less than 4000ppm, preferably smaller than 3500ppm, more preferably small
In 3000ppm；The temperature of second of active intensive treatment is at 360 DEG C or more, and the glass composition strain point temperature
Spend low at least 100 DEG C；Preferably, the temperature of second of active intensive treatment is at 390 DEG C or more, and the glass composition is answered
Height temperature is at least 120 DEG C or more low；The time of the second active intensive treatment is 0.15h~2h, preferably 0.5h~
1.5h, more preferable 0.5h~1h.
In a specific embodiment, the strain point of glass temperature is 500 DEG C~600 DEG C, and the first time is active
The temperature of intensive treatment is less than 460 DEG C, and specially 400 DEG C~450 DEG C, preferably 400 DEG C~430 DEG C, more preferable 405 DEG C~410
℃。
In a specific embodiment, the temperature of second of active intensive treatment is less than 460 DEG C, specially 400
DEG C~440 DEG C, preferably 410 DEG C~420 DEG C, more preferable 415 DEG C；
In one preferred embodiment, the preparation method of high impact properties glass of the invention, the first main alkali metal
Main alkali metal ion in ion forced fluid is usually K+Ion, secondary alkali metal ion are usually Na+Ion or/and Li+Ion,
The sum of secondary alkali metal ion concentration is less than 5000ppm.
In one preferred embodiment, the preparation method of high impact properties glass of the invention, the second main alkali metal
Main alkali metal ion in ion forced fluid is usually K+Ion, secondary alkali metal ion are usually Na+Ion or/and Li+Ion,
The sum of secondary alkali metal ion concentration is less than 4000ppm.
It is mobile for mobile phone, computer, smartwatch etc. in preparation that the present invention also provides a kind of above-mentioned high impact properties glass
Application in the protection glass process of equipment.
In addition, in the present invention, the distributing homogeneity δ in glass composition on alkali metal ion concentration through-thickness,
Alkali metal ion concentration value on test thickness direction can be used, measured according to the deviation of its concentration Distribution value, usually marked with it
Quasi- difference characterizes.The mode of thinning method test alkali metal ion concentration can be used in the present invention.Specifically, can be subtracted with 2 μm/layer
The thin glass, successively test corresponds to alkali metal ion concentration value after being thinned every time, then finds out the mark of alkali metal ion concentration value
It is quasi- poor.Thinned mode can be physics and be thinned, and be also possible to chemical reduction, and Japanese Shimadzu can be used in test alkali metal ion concentration
MXF-2400X ray fluorescence spectrometer.Furthermore EPMA electron probe microanalyzer can also be used and directly test the direction thickness t
Upper alkali metal ion concentration distribution mode.
Other test items in the present invention can be used such as the test of surface compression stress CS and compression stress layer depth DOL
Surface stress instrument, such as former FSM-6000LE of Japan's folding；The omnipotent of model QJ-211S can be used in test warping resistance performance 4PB
Experimental machine；The controlled drop machine of mobile phone that model GP-2112 can be used in test impact energy carries out.It should be understood that
Above-mentioned test mode and test equipment only characterize a kind of means of technical solution of the present invention and technical effect, it also can be used
His test mode and test equipment, have no effect on final result.
High impact properties glass of the invention is that will there is the glass composition of constituent content of the present invention to be prepared
Original glass plate, then the original glass plate is passed sequentially through into active reinforcing for the first time, passive reinforcing and second of active reinforcing
Multistage intensive treatment and obtain, finally obtained strengthened glass surface compression stress is high, stress layer depth is big, 4 bending resistances are surveyed
The bending strength that examination measures is big, resistible impact energy is big, and shock resistance is substantially better than conventional chemical strengthened glass.
Embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention are not
It is limited to this.
A1~A10 is thickness, the correlated performance of the glass composition of the different formulations prepared using floating process in the following table 1
And each component content.Wherein, A1~A7 is the glass composition prepared using material side of the invention, and A8~A10 is using existing
Glass composition prepared by the common material side in technology.
Table 1
The preparation of original glass plate
It is matched respectively according to the component ratio of A1~A10 in table 1, meanwhile, mixed raw material is packed into hermetic bag, close
It is mixed in envelope, then pours into platinum crucible and melt, melted, melten glass liquid is cast in metal die, by glass
Glass is put into togerther in annealing furnace together with metal mold carries out fine annealing cooling, and annealing temperature is 630 DEG C, when keeping the temperature at this temperature
Between be 30 minutes, then be naturally cooling to 70 DEG C, glass blocks after cooling be subjected to cutting and polishing, is obtained with a thickness of the saturating of 0.7mm
Bright original glass plate.
Then, original glass plate is pre-processed, it is small by the way that 145mm × 73mm × 0.7mm is made after cutting, grinding
Sample.Its edge is checked with microscope again, guarantees that edge chipping size is not more than 30 μm.
It is as shown in Figure 1, Figure 2 to measure distribution of the alkali metal ion on the direction thickness t in each original glass plate.
Embodiment A1 "~A7 "
Using intensifying method of the invention, i.e., active reinforcing-for the first time is passive strengthens-second active reinforcing.
Several progress of the glass sample that A1~A7 glass composition after taking above-mentioned corner and surface preparation is prepared
Above-mentioned pretreated sample is specifically put into pre-heating device Muffle furnace and preheats by intensive treatment of the invention, preheating
System are as follows: initial room-temperature -- 0.5h to 385 DEG C of heating -- heat preservation 0.5h.
Active intensive treatment for the first time is carried out to the sample after preheating.Specifically, the sample taken out from preheating chamber is fast
Speed is put into Na+Ion concentration is in 5000ppm KNO below3In forced fluid, preferably Na+Ion concentration is 3000ppm；Forced fluid temperature
410 DEG C of degree setting；Enhanced time is 6h.Same batch of sample uses same technique.
Sample after the active reinforcing of above-mentioned first time is subjected to passive intensive treatment, specifically, after above-mentioned active reinforcing
Sample be put into Muffle furnace, be warming up to 450 DEG C；Heat preservation 50 minutes takes out sample after being naturally cooling to 100 DEG C or less.It is passive
Processing makes surface compression stress elimination.
Above-mentioned passive treated sample is subjected to second of active intensive treatment, specifically, by passive treated sample
Product are quickly put into NaNO3Content is the KNO of 2000ppm3In alkali metal ion forced fluid, forced fluid temperature setting is 415 DEG C；By force
The change time is 1h.Same batch of sample uses same technique.
After second of active reinforcing, obtained glass is denoted as embodiment A1 "~A7 ", and it is finally obtained to test each embodiment
Surface compression stress, compression stress layer depth, shock resistance and warping resistance performance, are denoted as CS2、DOL2、Ep2And P2, test
As a result such as table 2.
Table 2
Comparative example
Comparative example A 1 '~A10 '
Firstly, the glass sample for taking A1~A10 glass composition after above-mentioned corner and surface preparation to be prepared, is adopted
With conventional chemical intensive treatment, i.e., primary active intensive treatment.
Preheated specifically, sample is put into pre-heating device Muffle furnace, pre-fire system are as follows: initial room-temperature -- heating
0.5h to 380 DEG C -- heat preservation 0.5h.Then the sample taken out from preheating chamber is quickly put into Na+Ion concentration is in 5000ppm
KNO below3Chemical strengthening is carried out in forced fluid；410 DEG C of forced fluid temperature setting；Enhanced time is 330 minutes.
Glass after primary active intensive treatment is denoted as comparative example A 1 '~A10 ', measures comparative example A 1 '~A10 ' in chemistry
The bending resistance of surface compression stress, compression stress layer depth, resistible impact energy and 4 anti-bending tests after reinforcing is strong
Degree, is denoted as CS1、DOL1、Ep1And P1.Test result such as table 3, compression stress layer depth, the resistible impact energy of each comparative example
It measures lower.
Table 3
Comparative example A 8 "~A10 "
Several progress of the glass sample that A8~A10 glass composition after taking above-mentioned corner and surface preparation is prepared
Intensive treatment of the invention, i.e., identical as embodiment A1 "~A7 " enhanced processing method, active reinforcing-is without source strength for the first time
Change-second active reinforcing.The glass obtained after second of active reinforcing is denoted as comparative example A 8 "~A10 ", tests each comparison
The finally obtained surface compression stress of example, compression stress layer depth, shock resistance and warping resistance performance, test result such as table 2.
By table 2,3 it is recognized that while the comparative example product A1 ' of the more conventional reinforcement process production of the CS of each embodiment A1 "~A7 "
~A7 ' is slightly relatively low, but embodiment A1 "~A7 " DOL amplification is larger, is embodied in intuitive performance, and shock resistance Ep is substantially
It is promoted.
Contrast table 2, table 3 can also show that the original glass plate being prepared using the material side A1~A7 of the present invention is carried out normal
After rule are strengthened, the original glass plate that CS, DOL, P and Ep of the strengthened glass being prepared are higher than the preparation of the material side A8~A10 is adopted
With CS, DOL, P and Ep of the strengthened glass being prepared after conventional strengthen；In addition, using the glass of the material side A1~A7 of the present invention
Composition, by passive CS, DOL, P and the Ep for strengthening-second active reinforcement process and being prepared of active reinforcing-for the first time
Strengthen-second active reinforcement process preparation using active reinforcing-for the first time is passive higher than the glass composition of the material side A8~A10
CS, DOL, P and Ep of obtained strengthened glass.
For embodiment A1 "~A7 " and comparative example A 1 '~A10 ', comparative example A 8 "~A10 ", sample segment is taken respectively, it will
Reduction processing is carried out after sample clean, is successively thinned with 2 μm/layer frequency, and each attenuated layer Na is measured+And K+Content.Find out Na+And K+Content with thickness thinning the regularity of distribution, to derive Na+And K+The distribution situation of content through-thickness.
Fig. 3~Fig. 9 shows that it is real for being prepared after active reinforcing, passive reinforcing, second of active reinforcement process
Alkali metal ion concentration through-thickness distribution situation in an A1 "~A7 " is applied, distribution trend is all satisfied y=aln (x)+b,
In, Na+A > 0 in distribution, b > 0, K+A < 0 in distribution, b > 0；And the Na in embodiment A1 "~A7 "+The preferred model of ion concentration
Enclosing is≤120 μm, K+Ion concentration preferred scope is≤130 μm；
Although embodiment of the present invention is described in conjunction with attached drawing above, the invention is not limited to above-mentioned
Specific embodiments and applications field, above-mentioned specific embodiment are only schematical, directiveness, rather than restricted
's.Those skilled in the art are under the enlightenment of this specification and in the range for not departing from the claims in the present invention and being protected
In the case where, a variety of forms can also be made, these belong to the column of protection of the invention.
Claims (15)
1. a kind of high impact properties glass, wherein
Along high impact properties thickness of glass direction, there are two types of high impact-resistant glass tools or the above alkali metal ion,
When 0 < x≤2t/5, the distribution on each alkali metal ion concentration through-thickness is all satisfied relational expression: y=aln (x)+
B,
Wherein, t is the thickness of the high impact properties glass；X is the distance between certain point and glass surface, and unit is μm；y
For a kind of concentration of alkali metal ion of the point, unit is quality %；A, b is arbitrary constant, and the numerical value of a and b are by alkali metal
Type determines.
2. high impact properties glass according to claim 1, wherein the high impact properties glass with a thickness of 0.2mm
≤t≤2.0mm。
3. high impact properties glass according to claim 1 or 2, wherein
Distribution on the maximum alkali metal ion concentration through-thickness of ionic radius meets relational expression: y=a11n(x)+b1, a1
< 0, b1> 0；
Distribution on the smallest alkali metal ion concentration through-thickness of ionic radius meets relational expression: y=a2ln(x)+b2, a2
> 0, b2> 0.
4. high impact properties glass described in any one of claim 1 to 3, wherein
Its surface compression stress CS is in 700MPa or more, preferably 750MPa；
Its compression stress layer depth DOL is at 70 μm or more, preferably at 80 μm or more；
The bending strength P that its 4 anti-bending tests measure is in 500MPa or more, preferably in 520 MPa or more；
Its resistible impact energy Ep is in 280Nmm or more, preferably in 300 Nmm or more.
5. high impact properties glass according to any one of claims 1 to 4, wherein
The high impact properties glass is obtained and carrying out intensive treatment to the original glass plate being prepared by glass composition
It arrives；
It is indicated with mass percent, the glass composition contains: SiO2: 56.8%~63%, Al2O3: 13.5%~
21.5%, MgO:1.1%~8.5%, Na2O:10%~22% and K2O, and K2O/Na2The ratio of O is less than 0.5；It is preferred that
Ground contains Na2O:11%~18%, and K2O/Na2The ratio of O is less than 0.45；Preferably, contain: SiO2: 58%~
61.5%, Al2O3: 13.5%~20%, MgO:3.5%~7%, Na2O:12%~15%；It is further preferred that it contains:
SiO2: 59.5%~61.5%, Al2O3: 13.5%~17.5%, MgO:3.5%~6.8%, Na2O:12.5%~14.5%.
6. high impact properties glass according to claim 5, wherein the high impact properties glass passes through to the glass
Composition successively carry out it is active for the first time strengthen, passive reinforcing, second active reinforcing and be made.
7. high impact properties glass according to claim 5 or 6, wherein in the original glass plate, every kind of alkali metal from
Distributing homogeneity δ on sub- concentration through-thickness is all satisfied δ≤0.05, preferably δ≤0.04.
8. a kind of glass composition for being used to prepare high impact properties glass, wherein
It is indicated, is contained with mass percent: SiO2: 56.8%~63%, Al2O3: 13.5%~21.5%, MgO:1.1%~
8.5%, Na2O:10%~22% and K2O, and K2O/Na2The ratio of O is less than 0.5；Preferably, contain: Na2O:11%~
18%, and K2O/Na2The ratio of O is less than 0.45.Preferably, contain: SiO2: 58%~61.5%, Al2O3: 13.5%~
20%, MgO:3.5%~7%, Na2O:12%~15%；It is further preferred that it contains: SiO2: 59.5%~61.5%,
Al2O3: 13.5%~17.5%, MgO:3.5%~6.8%, Na2O:12.5%~14.5%；
Point in the original glass plate be prepared by the glass composition, on every kind of alkali metal ion concentration through-thickness
Cloth uniformity δ is all satisfied δ≤0.05, preferably δ≤0.04.
9. a kind of preparation method of such as high impact properties glass according to any one of claims 1 to 7, wherein it includes, right
The original glass plate made of glass composition successively carries out following processing:
Surface and/or edge pretreatment；
The pre-heat treatment；
Active intensive treatment for the first time, wherein including being put into the glass plate after the above-mentioned the pre-heat treatment with the first main alkali
Active intensive treatment is carried out in the forced fluid of metal ion；
Passive intensive treatment；
Second of active intensive treatment, wherein including being put into the above-mentioned glass plate after passive reinforcing with the second main alkali gold
Belong in the forced fluid of ion and carries out active intensive treatment；
The glass composition, is indicated with mass percent, is contained: SiO2: 56.8%~63%, Al2O3: 13.5%~
21.5%, MgO:1.1%~8.5%, Na2O:10%~22% and K2O, and K2O/Na2The ratio of O is less than 0.5；
The original glass plate thickness t meets 0.2mm≤t≤2.0mm, every kind of alkali metal ion distribution on its thickness direction
Uniformity is all satisfied δ and meets δ≤0.05, preferably δ≤0.04.
10. the preparation method of high impact properties glass according to claim 9, wherein the preheating temperature of the pre-heat treatment
Degree is 370 DEG C~410 DEG C, preferably 380 DEG C~400 DEG C, more preferable 380 DEG C~390 DEG C.
11. the preparation method of high impact properties glass according to claim 9 or 10, wherein
In the first time active intensive treatment step, the forced fluid also contains other than the first main alkali metal ion
One or more of secondary alkali metal ion, wherein the ionic radius of the first main alkali metal ion is greater than the glass combination
The big alkali metal ion of object Ionic Radius time, the pair alkali metal ion total content are less than 5000ppm, preferably smaller than
4000ppm, more preferable 3000ppm；
The temperature of the first time active intensive treatment be not less than 350 DEG C, and the glass composition strain point temperature down to
It is 60 DEG C few；Preferably, the temperature of active intensive treatment is not less than 380 DEG C, and the glass composition strain point temperature for the first time
Spend low at least 80 DEG C；
The time of the first time active intensive treatment is 4h~10h, preferably 5h~8h, more preferable 5h~6h.
12. the preparation method of high impact properties glass according to any one of claim 9~11, wherein
The temperature of the passive intensive treatment be 380 DEG C~480 DEG C, preferably 400 DEG C~480 DEG C, more preferable 440 DEG C~450 DEG C,
Most preferably 450 DEG C；
The time of the passive intensive treatment be 10min~120min, preferably 60min~120min, more preferable 100min~
120min。
13. the preparation method of high impact properties glass according to any one of claim 9~12, wherein
In second of active intensive treatment step, the forced fluid also contains other than the second main alkali metal ion
One or more of secondary alkali metal ion, wherein the ionic radius of the second main alkali metal ion is greater than the glass combination
The big alkali metal ion of object Ionic Radius time, the pair alkali metal ion total content are less than 4000ppm, preferably smaller than
3500ppm, more preferably less than 3000ppm；
The temperature of the second active intensive treatment is not less than 360 DEG C, and the glass composition strain point temperature down to
It is 100 DEG C few；Preferably, the temperature of second of active intensive treatment is not less than 390 DEG C, and the glass composition strain point temperature
Spend low at least 120 DEG C or more；
The time of second of active intensive treatment is 0.15h~2h, preferably 0.5h~1.5h, more preferable 0.5h~1h.
14. the preparation method of high impact properties glass according to any one of claim 9~13, wherein further include:
After carrying out above-mentioned second of active intensive treatment step to the glass, repeats passive intensive treatment and second active
The step of intensive treatment.
15. as high impact properties glass according to any one of claims 1 to 7 is used for mobile terminal device in preparation, preferably
Application of the protection of mobile phone, computer, smartwatch in glass process.
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| CN110937824A (en) * | 2019-12-05 | 2020-03-31 | 四川旭虹光电科技有限公司 | Chemically strengthened glass and preparation method and application thereof |
| CN112939472A (en) * | 2019-12-11 | 2021-06-11 | 四川旭虹光电科技有限公司 | Microcrystalline glass and preparation method and application thereof |
| CN114149175A (en) * | 2021-12-27 | 2022-03-08 | 四川虹科创新科技有限公司 | Window protective glass panel and impact-resistant reinforced window protective glass panel |
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