A kind of glass compositionss, alumina silicate glass and its preparation method and applicationTechnical field
The present invention relates to field of glass production technology, in particular it relates to a kind of glass compositionss, alumina silicate glass andIts preparation method and application.
Background technology
With the development of modern display science and technology, electronical display product emerges in multitude within nearest 10 years, and advanced flat pannel display is producedProduct emerge in an endless stream, such as: mobile phone, handheld device, LCD TV, liquid crystal display (as notebook liquid crystal display), ATM,Billboard media machine, Multi-media information inquiry machine etc..
At present, the either small-size product such as mobile phone, pda, mp4, digital camera, or pos machine, industrial computer, oneThe large scale products such as body machine, game play machine, all apply touching technique, and particularly incell, ogs becomes the master touching productStream, the requirement to corresponding cover-plate glass is higher, needs glass lightening, has higher intensity, scratch resistant scratch-resistant, anti-impact simultaneouslyHit performance.For thickness below 1mm ultra-thin glass, need to through chemical enhanced process, after ion exchange, in glass fromThe less na of sub- radius+By the big k of the ionic radius in chemical tempering liquid+Displacement, forms compressive stress layer in glass surface, thusPlay enhanced effect.Therefore, in frit side's aspect, improve strength of glass, scratch resistant scratch-resistant and shock resistance is important classOne of topic.
Content of the invention
The invention aims to solution above-mentioned technical problem, provide a kind of glass compositionss, alumina silicate glassAnd its preparation method and application.The chemically reactive strengthening of alumina silicate glass of the present invention, intensity is high, scratch resistant scratch-resistant, and has excellentShock resistance.
To achieve these goals, in a first aspect, the invention provides a kind of glass compositionss, with the weight of said compositionOn the basis of amount, in terms of oxide, said composition contains the sio of 58-67wt%2, the la of 0.1-2wt%2o3, 12-16wt%al2o3, the na of 8-15wt%2The li of o, 0-2wt%2The sro of cao, 0.5-2wt% of mgo, 0.1-2wt% of o, 2-5wt%,The b of 0.1-2wt%2o3, the tio of 0-1wt%2Zro with 0.01-2wt%2.
Preferably, described compositionss also contain clarifier, and described clarifier is na2so4、nano3And ceo2Mixture,On the basis of the weight of said composition, the content of described clarifier is 0.5-2wt%, more preferably 0.8-1.5wt%；
Preferably, na2so4、nano3And ceo2Weight than for 1.5-9:1:1-16, more preferably 1.6-5:1:2.5-7.
Preferably, on the basis of the weight of said composition, in terms of oxide, la2o3Content be 0.5-1wt%.
Preferably, on the basis of the weight of said composition, in terms of oxide, b2o3Content be 1.3-1.6wt%.
Preferably, on the basis of the weight of said composition, in terms of oxide, zro2Content be 0.8-1wt%.
Preferably, on the basis of the weight of said composition, in terms of oxide, li2The content of o is 0.8-1.2wt%.
Preferably, on the basis of the weight of said composition, in terms of oxide, sio2Content be 60-64wt%.
Preferably, on the basis of the weight of said composition, in terms of oxide, al2o3Content be 14-16wt%.
Preferably, on the basis of the weight of said composition, in terms of oxide, na2The content of o is 10-14wt%.
Preferably, on the basis of the weight of said composition, in terms of oxide, the content of mgo is 3-4.6wt%.
Preferably, on the basis of the weight of said composition, in terms of oxide, the content of cao is 0.8-1.8wt%.
Preferably, on the basis of the weight of said composition, in terms of oxide, the content of sro is 0.7-1.2wt%.
Preferably, on the basis of the weight of said composition, in terms of oxide, tio2Content be 0.3-0.5wt%.
Second aspect, the invention provides a kind of method preparing alumina silicate glass, the method is included institute of the present inventionThe glass stated compositionss carry out melt process, forming processes, annealing and machining processes successively.
Preferably, the product that the method also includes machining processes are obtained carries out chemical intensification treatment.
The third aspect, the invention provides the alumina silicate glass that said method prepares.
Preferably, the elastic modelling quantity of described alumina silicate glass is higher than 70gpa, and density is less than 2.45g/cm3, 30-380 DEG CIn the range of thermal coefficient of expansion be less than 87 × 10-7/℃.
Preferably, the Vickers hardness of the alumina silicate glass that chemical intensification treatment obtains is more than 870mpa, and shock resistance can be bigIn 4j.
Preferably, the strain point of described alumina silicate glass is higher than 550 DEG C, and annealing point is higher than 600 DEG C, and softening point is higher than820℃.
Preferably, described alumina silicate glass is 10 in viscosity4During dpa s, corresponding temperature is 1000-1150 DEG C,Viscosity is 102During dpa s, corresponding temperature is not more than 1620 DEG C.
Preferably, the compression stress that the glass surface that described chemical intensification treatment obtains is formed, in more than 850mpa, enters oneStep is preferably 870-920mpa；Compression stress layer depth more than 55 μm, more preferably 57-60 μm.
Fourth aspect, the invention provides glass compositionss of the present invention or alumina silicate glass touch in preparationApplication in panel type display part, the preferably application in preparing the touch screen cover-plate glass of flat board or Flexible Displays product,It is further preferred that described flat board or Flexible Displays product be mobile phone, handheld device, digital camera, mp4, liquid crystal display,At least one in ATM, billboard media machine, Multi-media information inquiry machine, pos machine and industrial computer.
The glass compositionss of the present invention, are a kind of frit side with good chemical strengthening effect, belong to aluminum silicateSalt glass system is it is adaptable to the various Conventional glassmaking methods such as float glass process, press over system, glass tube down-drawing are used for producing thickness > 0.1mmThe plate glass or thickness flexible glass less than 0.1mm.It is hard that the glass preparing has higher surface after chemical enhancedDegree, scratch resistant scratch-resistant, excellent wearability and shock resistance, can meet the performance requirement to touch screen cover-plate glass for the market.
A preferred embodiment of the invention, the sio containing certain content in glass compositionss2、la2o3、al2o3、na2o、li2o、mgo、cao、sro、b2o3、tio2、zro2、na2so4、nano3And ceo2, using this glass compositionsThe glass preparing, elastic modelling quantity is higher than 70gpa, and density is less than 2.45g/cm3, thermal coefficient of expansion in the range of 30-380 DEG CLess than 87 × 10-7/ DEG C, the Vickers hardness of the alumina silicate glass that chemical intensification treatment obtains is more than 870mpa, and shock resistance can be bigIn 4j, strain point is higher than 550 DEG C, and annealing point is higher than 600 DEG C, and softening point is higher than 820 DEG C, is 10 in viscosity4Correspond to during dpa sTemperature be 1000-1150 DEG C, viscosity be 102During dpa s, corresponding temperature is not more than 1620 DEG C, and chemical intensification treatment obtainsThe compression stress that the glass surface arriving is formed is at more than 850mpa (preferably 870-920mpa)；Compression stress layer depth is at 55 μmAbove (preferably 57-60 μm).
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concreteEmbodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
Herein the end points of disclosed scope and any value are not limited to this accurate scope or value, these scopes orValue should be understood to comprise the value close to these scopes or value.For numerical range, between the endpoint value of each scope, respectivelyBetween the endpoint value of individual scope and single point value, and can be obtained one or more between single point value with combination with one anotherNew numerical range, these numerical rangies should be considered herein specifically to disclose.
In a first aspect, the invention provides a kind of glass compositionss, on the basis of the weight of said composition, with oxideMeter, said composition contains the sio of 58-67wt%2, the la of 0.1-2wt%2o3, the al of 12-16wt%2o3, 8-15wt%na2The li of o, 0-2wt%2The b of sro, 0.1-2wt% of cao, 0.5-2wt% of mgo, 0.1-2wt% of o, 2-5wt%2o3、The tio of 0-1wt%2Zro with 0.01-2wt%2.
In the glass compositionss of the present invention, under preferable case, compositionss also contain clarifier, and described clarifier isna2so4、nano3And ceo2Mixture, on the basis of the weight of said composition, the content of described clarifier is 0.5-2wt%,More preferably 0.8-1.5wt%.
Wherein, using aforementioned compound clarifier (na2so4+nano3+ceo2), clear in floating process sulfate, nitrateOn the basis of clear, introduce cerium oxide, only do not clarify the effect of de-soak moreover it is possible to increase substantially the quality of glass, increaseGlass transparent degree, improves strength of glass and resistance to water.
Preferably, na2so4、nano3And ceo2Weight than for 1.5-9:1:1-16, more preferably 1.6-5:1:2.5-7.
In the glass compositionss of the present invention, introduce the la of 0.1-2wt%2o3, the intensity of glass and hard can not only be improvedDegree, also helps glass clarifying, improves the transparency of glass.Preferably, on the basis of the weight of said composition, with oxideMeter, la2o3Content be 0.5-1wt%.
In the glass compositionss of the present invention, introduce the b of 0.1-2wt%2o3, not only there is the effect fluxed, can also simultaneouslyImprove chemical stability, provide good condition for subsequent chemistry intensive treatment.Preferably, with the weight of said composition as baseStandard, in terms of oxide, b2o3Content be 1.3-1.6wt%.
In the glass compositionss of the present invention, introduce the zro of 0.01-2wt%2, by increasing capacitance it is possible to increase the intensity of glass and wear-resistingProperty, and al2o3、zro2It is used in combination, it is possible to increase sodium, potassium ion exchange velocity and depth, the strengthening effect of reinforcing glass.Preferably,On the basis of the weight of said composition, in terms of oxide, zro2Content be 0.8-1wt%.
In the glass compositionss of the present invention, introduce the li of 0-2wt%2O, can accelerate the less na of glass Ionic Radius+By the k that chemical tempering liquid Ionic Radius are larger+Displacement, the compression stress of the compressive stress layers on reinforcing glass surface, improveScratch-proofness.Preferably, on the basis of the weight of said composition, in terms of oxide, li2The content of o is 0.8-1.2wt%.
In the glass compositionss of the present invention, under preferable case, on the basis of the weight of said composition, in terms of oxide,sio2Content be 60-64wt%.
In the glass compositionss of the present invention, under preferable case, on the basis of the weight of said composition, in terms of oxide,al2o3Content be 14-16wt%.
In the glass compositionss of the present invention, under preferable case, on the basis of the weight of said composition, in terms of oxide,na2The content of o is 10-14wt%.
In the glass compositionss of the present invention, under preferable case, on the basis of the weight of said composition, in terms of oxide,The content of mgo is 3-4.6wt%.
In the glass compositionss of the present invention, under preferable case, on the basis of the weight of said composition, in terms of oxide,The content of cao is 0.8-1.8wt%.
In the glass compositionss of the present invention, under preferable case, on the basis of the weight of said composition, in terms of oxide,The content of sro is 0.7-1.2wt%
In the glass compositionss of the present invention, under preferable case, on the basis of the weight of said composition, in terms of oxide,tio2Content be 0.3-0.5wt%.
It will be understood by those skilled in the art that in the glass compositionss of the present invention, the sio that compositionss contain2、la2o3、al2o3、na2o、li2o、mgo、cao、sro、b2o3、tio2、zro2And ceo2, refer to that said composition contains chemical combination containing siThing, compound containing la, compound containing al, compound containing na, compound containing li, compound containing mg, compound containing ca, chemical combination containing srThing, compound containing b, compound containing ti, compound containing zr and compound containing ce, carbonate such as containing aforementioned each element, nitrate,Sulfate, oxide etc., and the content of the aforementioned each component referring to is all in terms of the oxide of each element, the carbon of specific each elementHydrochlorate, nitrate, sulfate, being chosen as it is known to those skilled in the art that will not be described here of oxide.
In the glass compositionss of the present invention, when preparing alumina silicate glass using it, why enable to glass toolThere is excellent combination property, be mainly attributed in compositionss cooperating between each group is divided, especially sio2、la2o3、al2o3、na2o、li2o、mgo、cao、sro、b2o3、tio2、zro2、na2so4、nano3And ceo2Between mating reaction, more particularly beforeState certain content each group divide between cooperate.
Second aspect, the invention provides a kind of alumina silicate glass, on the basis of the weight of described glass, described glassSio containing 58-67wt%2, the la of 0.1-2wt%2o3, the al of 12-16wt%2o3, the na of 8-15wt%2O, 0-2wt%'sli2The b of sro, 0.1-2wt% of cao, 0.5-2wt% of mgo, 0.1-2wt% of o, 2-5wt%2o3, the tio of 0-1wt%2Zro with 0.01-2wt%2.
Preferably, also contain clarifier in alumina silicate glass, described clarifier is na2so4、nano3And ceo2MixingThing, on the basis of the weight of this glass, the content of described clarifier is 0.5-2wt%, more preferably 0.8-1.5wt%.
It is further preferred that na2so4、nano3And ceo2Weight than for 1.5-9:1:1-16, still more preferably for1.6-5:1:2.5-7.
Preferably, in alumina silicate glass, on the basis of the weight of glass, la2o3Content be 0.5-1wt%.
Preferably, in alumina silicate glass, on the basis of the weight of glass, b2o3Content be 1.3-1.6wt%.
Preferably, in alumina silicate glass, on the basis of the weight of glass, zro2Content be 0.8-1wt%.
Preferably, in alumina silicate glass, on the basis of the weight of glass, li2The content of o is 0.8-1.2wt%.
Preferably, in alumina silicate glass, on the basis of the weight of glass, sio2Content be 60-64wt%.
Preferably, in alumina silicate glass, on the basis of the weight of glass, al2o3Content be 14-16wt%.
Preferably, in alumina silicate glass, on the basis of the weight of glass, na2The content of o is 10-14wt%.
Preferably, in alumina silicate glass, on the basis of the weight of glass, the content of mgo is 3-4.6wt%.
Preferably, in alumina silicate glass, on the basis of the weight of glass, the content of cao is 0.8-1.8wt%.
Preferably, in alumina silicate glass, on the basis of the weight of glass, the content of sro is 0.7-1.2wt%.
Preferably, in alumina silicate glass, on the basis of the weight of glass, tio2Content be 0.3-0.5wt%.
The third aspect, the invention provides a kind of method preparing alumina silicate glass, the method is included institute of the present inventionThe glass stated compositionss carry out melt process, forming processes, annealing and machining processes successively.
In the method for the present invention, the concrete restriction for glass compositionss refers to aforementioned corresponding contents description, hereRepeat no more.
Process of the present invention it is preferred in the case of, the condition of melt process includes: temperature is 1580 DEG C -1650 DEG C, the timeFor 8-12h.In addition, those skilled in the art can determine specific melt temperature and melting time according to practical situation, this isAs it is known to those skilled in the art that will not be described here.
Process of the present invention it is preferred in the case of, the condition of annealing includes: temperature is 600-620 DEG C, and the time is more than0.5h.In addition, those skilled in the art can determine specific annealing temperature and annealing time according to practical situation, this is abilityKnown to field technique personnel, will not be described here.
In the method for the present invention, for machining processes, there is no particular limitation, can be common various in this areaMachining mode, for example, can be that the product obtaining annealing carries out cutting, grinds, polishes.
In order to improve the combination property of glass further, under preferable case, the method also includes machining processes are obtainedTo product carry out chemical intensification treatment.It is further preferred that the method for chemical intensification treatment includes: machining processes are obtainedTo product be placed in 400-460 DEG C of melting kno3Middle process at least 0.1h (as 3-8h).Those skilled in the art can basisPractical situation determines the temperature and time of specific chemical intensification treatment, and this is well known to those skilled in the art, and here is no longerRepeat.After afore mentioned chemical intensive treatment, glass surface stress can be at least up to 850mpa, ion exchange within a short period of timeDepth is more than 55 μm, and glass surface forms compressive stress layer, and the higher intensity of compressive stress layer imparting glass, surface are scratch resistant scratch-resistant.
Fourth aspect, the invention provides the alumina silicate glass that said method prepares.
Under preferable case, the elastic modelling quantity of described alumina silicate glass is higher than 70gpa, and density is less than 2.45g/cm3, 30-Thermal coefficient of expansion in the range of 380 DEG C is less than 87 × 10-7/℃.
Under preferable case, the Vickers hardness of the alumina silicate glass that chemical intensification treatment obtains is more than 870mpa, shock resistance4j can be more than.
Under preferable case, the strain point of described alumina silicate glass is higher than 550 DEG C, and annealing point is higher than 600 DEG C, and softening point is highIn 820 DEG C.
Under preferable case, described alumina silicate glass is 10 in viscosity4During dpa s, corresponding temperature is 1000-1150DEG C, it is 10 in viscosity2During dpa s, corresponding temperature is not more than 1620 DEG C.
Under preferable case, the compression stress that glass surface that described chemical intensification treatment obtains is formed in more than 850mpa,More preferably 870-920mpa；Compression stress layer depth more than 55 μm, more preferably 57-60 μm.
5th aspect, the invention provides glass compositionss of the present invention or alumina silicate glass touch in preparationApplication in panel type display part, the preferably application in preparing the touch screen cover-plate glass of flat board or Flexible Displays product,It is further preferred that described flat board or Flexible Displays product be mobile phone, handheld device, digital camera, mp4, liquid crystal display,At least one in ATM, billboard media machine, Multi-media information inquiry machine, pos machine and industrial computer.
Embodiment
Hereinafter will be described the present invention by embodiment.In following examples, if no special instructions, usedEach material all can pass through commercially available, and if no special instructions, method used is the conventional method of this area.
In following examples and comparative example, measure glass density with reference to astm c-693, unit is g/cm3.
Use the thermal expansion coefficient of glass α of 30-380 DEG C of horizontal expander instrument mensure with reference to astm e-22830/380, with averageThe coefficient of expansion represents, unit is 10-7/℃.
Material mechanical test machine is used to measure glass Young's moduluss with reference to astm c-623, unit is gpa.
Vickers is used to measure glass Vickers hardness with reference to astm e-384, unit is mpa.
(viscosity is to measure the annealing point of glass with reference to astm c-336 using glass annealing point and strain point tester1013Temperature during dpa s) and strain point (viscosity be 1014.5Temperature during dpa s), unit be DEG C.
Reference astm c-338 measures the softening point of glass using glass softening point tester, and (viscosity is 107.6During dpa sTemperature), unit be DEG C.
Drum type brake rotation high-temperature viscosimeter is used to measure glass high temperature viscosity-temperature curve with reference to astm c-965, by fulcher(also referred to as vft formula) calculates viscosity is 104Corresponding temperature (as operating temperature t during dpa sw) and viscosity be 102dpa·Corresponding temperature (as melting point t during sm), unit be DEG C.
Measure glass surface compression stress (unit is mpa) and compression stress layer depth using fsm-6000le surface stress meterDegree (unit be μm).
Measure the shock resistance energy of glass according to standard astm d1709 using the falling sphere tester that impact ball weight is 227g(unit is j).
Embodiment 1-8
Weigh each component according to the glass composition shown in table 1, mix, compound is poured in platinum crucible, Ran HouHeat 10 hours in 1620 DEG C of high temperature furnace, and discharge bubble using platinum rod stirring.The vitreous humour melting is poured intoIn rustless steel cast iron grinding tool, it is configured to the both bulk glasses product specifying, then by glass 610 DEG C of annealing 1 in the lehrHour, close power supply furnace cooling to 25 DEG C.Glass is carried out cutting, grinds, polishes, by polishing obtain 50 × 50 ×The surface deionized water of the glass of 1mm puts into melting kno after cleaning up3Middle process certain time, then take out simultaneouslyIt is cooled to 25 DEG C, deionized water cleans up and dries, prepared glass finished-product.Respectively the various performances of each glass finished-product are enteredRow measures, and the results are shown in Table 1.
Table 1
Embodiment 9-11, comparative example 1-5
According to embodiment 5 method, except for the difference that, the performance of compound composition (corresponding glass composition) and the product obtaining is surveyedSurely the results are shown in Table 2.
Table 2
Embodiment 5 in table 1 is compared with the data of comparative example 1-4 in table 2 and understands, containing certain content in preparing glass chargela2o3、b2o3、zro2、li2During o, hardness, chemical enhanced characteristic and shock resistance of glass etc. can be improved further.
Embodiment 5 in table 1 is compared with the data of comparative example 5 in table 2 and understands, the specific composition of the present invention and the glass of contentThe glass that glass dispensing prepares, has significantly higher hardness, more excellent chemical enhanced characteristic and shock resistance etc., moreThe performance requirement to touch screen cover-plate glass for the suitable market.
Data in table 1-2 is compared and understands, the method for the present invention utilizes the sio containing certain content2、la2o3、al2o3、na2o、li2o、mgo、cao、sro、b2o3、tio2、zro2、na2so4、nano3And ceo2Glass compositionss prepareGlass, elastic modelling quantity is higher than 70gpa, and density is less than 2.45g/cm3, the thermal coefficient of expansion in the range of 30-380 DEG C is less than 87 × 10-7/ DEG C, the Vickers hardness of the glass that chemical intensification treatment obtains is more than 870mpa, and shock resistance can be more than 4j, and strain point is higher than 550DEG C, annealing point is higher than 600 DEG C, and softening point is higher than 820 DEG C, is 10 in viscosity4During dpa s, corresponding temperature is 1000-1150DEG C, it is 10 in viscosity2During dpa s, corresponding temperature is not more than 1620 DEG C, and the glass surface that chemical intensification treatment obtains is formedCompression stress is at more than 850mpa (preferably 870-920mpa)；Compression stress layer depth (preferably 57-60 μ more than 55 μmM), can give glass higher hardness, and be effectively prevented the impact of display product glass surface and scratch infringement.Base of the present inventionGlass in each component oxide coefficient of expansion combinatorial principle, refractory oxides combinatorial principle and ion exchange occupy-place Technology designThe glass of compositionss preparation, has excellent physicochemical property, can prepare touch screen cover-plate glass.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodimentDetail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, thisA little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lanceIn the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various canThe compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to thisThe thought of invention, it equally should be considered as content disclosed in this invention.