Summary of the invention
Aiming at the problems existing in the prior art, the present invention provide a kind of 3D form colorable chemcor glass and itsPreparation method, safe, at low cost, easy to operate, to may be molded to softening point low after the colorant fused salt intermediate ion exchange of melting3D glass, have certain stressor layers compression depth and bearing stress, can be met after reprocessing people to product outsideThe appreciation demand of shape.
The present invention is to be achieved through the following technical solutions:
A kind of colorable chemcor glass of 3D molding, the component of the chemcor glass are wrapped by mass percentageIt includes, SiO255%~75%, Al2O37%~23%, B2O30~5%, Na2O 3%~25%, K2O 0~6%, P2O5 0~5%, ZnO 0~6%, MgO 0~3%, CaO 0.1%~3%, SnO20~4%.
Preferably, the SiO2Mass percent be 60%~65%.
Preferably, the Al2O3Mass percent be 12%~20%.
Preferably, the Na2The mass percent of O is 15%~22%.
Preferably, the Na2O+K2The mass percent and Al of O2O3Mass percent ratio be not more than 1.1.
Preferably, the mass percent of the ZnO is 0~3%.
Preferably, the mass percent of the CaO is 0.1%~0.5%.
A kind of 3D forms the preparation method of colorable chemcor glass, includes the following steps,
Step 1, by mass percentage, according to the component preparation raw material of glass, plate glass is shaped to after raw material is meltedGlass；The component of glass is 55%~75% SiO by mass percentage2, 7%~23% Al2O3, 0~5% B2O3,3%~25% Na2O, 0~6% K2O, 0~5% P2O5, 0~6% ZnO, 0~3% MgO, 0.1%~3%CaO, 0~4% SnO2；
Step 2, plate glass is subjected to the high temperature anneal according to technique, the plate glass after being annealed；
Step 3,1~6h of colorant fused salt intermediate ion exchange by the plate glass after annealing at 380~450 DEG C is obtained intoGlass after type coloring；The component of colorant fused salt is 30%~50% copper nitrate by mass percentage, 20%~35%Potassium nitrate and 20%~35% sodium nitrate；
Step 4, by molding coloring after glass be cooled to 80 DEG C from 400 DEG C in 1h, obtain 3D molding it is colorable fromSon exchange glass.
Further, the plate glass after annealing in step 3 is after the exchange of colorant fused salt intermediate ion, then at 380~450 DEG CPotassium nitrate and sodium nitrate high-temperature fusion liquid in carry out 0.5~2h of ion exchange, the glass after obtaining molding coloring, wherein nitreThe ratio of sour potassium is 90%~100%, and the ratio of sodium nitrate is 0~10%.
Further, step 2 first carries out cleaning treatment to surface of plate glass before high annealing.
Compared with prior art, the invention has the following beneficial technical effects:
3D of the present invention forms colorable chemcor glass, by by SiO2Concrete content be designed as qualityPercentage is 55%~75%, the glass of satisfactory chemical durability not only can be obtained in this way, but also glass can also be made to haveStandby suitable forming ability；The Al that mass percent is 7%~23%2O3Guaranteeing the case where glass has certain viscosity and material propertyUnder, the ion-exchange performance of glass is improved, obtainable maximum bearing stress and stressor layers compression depth are increased, it can alsoReduce the tendency towards devitrification of glass；The B that mass percent is 0~5%2O3The viscosity for not only reducing glass melting liquid, also serves asFluxing agent contributes to form the glass of low softening point, Al2O3The viscosity of glass melting liquid, Na can be improved2O and K2O can reduce glassThe viscosity of glass, if Na2O and K2The concentration of O is directed to Al2O3Concentration be balanced, 0~5% B2O3Concentration will not significantlyInfluence the high-temperature heat expansion coefficient of glassware；The P that mass percent is 0~5%2O5It is 3%~25% with mass percentNa2The K that O and mass percent are 0~6%2O is combined, and becomes loose in the structure for making glass and ion exchange reaches deeper depthIn the case where degree, the ion-exchange performance of glass can not only be promoted, and reduce the softening point of glass, obtain required surfaceCompression and stressor layers compression depth；The ZnO and quality that MgO that mass percent is 0~3%, mass percent are 0~6%The CaO that percentage is 0.1%~3% improves the melting behaviour of glass composition and the ion-exchange performance of glass, quality hundredDivide the SnO than being 0~4%2The clarification of glass can be achieved, therefore these components are by melting, high annealing and in colorantThe glass obtained after the exchange of fused salt intermediate ion can finally be shaped to the low 3D glass of softening point, deep with certain stress layer compressionDegree and bearing stress, can meet people to the appreciation demand of product shape after reprocessing.
3D of the present invention forms the preparation method of colorable chemcor glass, by being 55% by mass percent~75% SiO2, mass percent be 7%~23% Al2O3, mass percent be 0~5% B2O3, mass percent is3%~25% Na2O, the K that mass percent is 0~6%2O, the P that mass percent is 0~5%2O5, mass percent 0~6% ZnO, the MgO that mass percent is 0~3%, the SnO for the CaO and 0~4% that mass percent is 0.1%~3%2Melting may be molded to plate glass, then plate glass is carried out the high temperature anneal to remove thermal stress, finally in copper nitrate, nitreThe exchange of the salt bath intermediate ion of sour sodium and potassium nitrate, may be molded to the low 3D glass of softening point, have certain softening point, HTCTE, stressor layers compression depth and bearing stress；The preparation method of chemcor glass of the present invention, safe, at low cost, operationIt is convenient, people can be met after reprocessing to the appreciation demand of product shape.
Further, the plate glass after annealing is after the exchange of colorant fused salt intermediate ion, then in 380~450 DEG C of nitre0.5~2h of ion exchange is carried out in the high-temperature fusion liquid of sour potassium and sodium nitrate, can further improve the bearing stress of glass, is increasedStrength of glass is added.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention andIt is not to limit.
3D of the present invention forms colorable ion exchange alumina silicate glass, contains following composition by mass percentage, SiO255%~75%, Al2O37%~23%, B2O30~5%, Na2O 3%~25%, K2O 0~6%, P2O5 0~5%, ZnO 0~6%, MgO 0~3%, CaO 0.1%~3%, SnO20~4%.
The above-mentioned 3D of following discussion forms in colorable ion exchange alumina silicate glass the effect of each component and specificContent, content unit are mass percent.
SiO2: 55%~75%.
SiO2It is the neccessary composition for constituting glass skeleton.As SiO in glass2Concentration it is lower when, the change of gained glassIt is lower to learn durability, still, if SiO in glass2Excessive concentration, the forming ability of glass can be reduced, because of excessively high SiO2Concentration increases the difficulty of melten glass, this has detrimental effect to glass forming ability.Usual concentration is greater than 55% and is less than75% SiO2The molding of glass can be readily facilitated.In addition, content 65% is hereinafter, 60% or more can take into account melting, chemistryRequirement in terms of durability and mechanical strength.
Al2O3: 7%~23%.
Al2O3It is intermediate oxide, is used as glass network forming agent.Al2O3The viscosity that glass melting liquid can be improved, canThe tendency towards devitrification of glass is reduced, because it is mainly tetrahedral coordination in the glass melt formed by glass.Al2O3Pass throughIncrease the strain point of glass and increases diffusion of the alkali metal ion in the glass network to improve the ion exchangeable of the glassEnergy.Therefore, Al2O3Presence improve the dynamics of ion exchange process, and increase obtainable maximum bearing stress andStressor layers compression depth, wherein bearing stress can be abbreviated as CS, and stressor layers compression depth can be abbreviated as DOL.In order to obtain fromThe sub- dynamic (dynamical) improvement of exchange process, Al in glass2O3Concentration be typically larger than 7%, but if Al2O3Content is excessive, is just difficult toObtain the long glass of material property.Al2O3Content be 12%~20% glass melting liquid viscosity it is not too high, melting temperature is smallIn 1680 DEG C, it can assist the electric smelter of heating and platinum pipeline clarification system that can realize the melting and clarification of glass by natural gasEffect.
B2O3: 0~5%.
By B2O3It is added to glass to reduce the viscosity of glass melting liquid.Generally, by B2O3It can be used for shape as fluxing agentAt the glass with low softening point.But when in the presence of not by Al2O3The excess alkali metal oxide Na of complexing2O and K2When O,B2O3Presence significantly increase high-temperature heat expansion coefficient, high-temperature heat expansion coefficient can be abbreviated as HT CTE.But Al2O3It can mentionThe viscosity of high glass melting liquid, Na2O and K2O can reduce the viscosity of glass, if Na2O and K2The concentration of O is directed to Al2O3It is denseDegree is balanced, and 0~5% boron oxide concentration will not influence the HT CTE of glass significantly, so that obtaining has required propertyGlass.
Na2O:3%~25%.
Na is added in glass2O can promote the ion exchange of glass to strengthen, and reduce the melting temperature and liquidus curve temperature of glassDegree, to reduce the softening point of glass.Specifically, lesser Na in gained glass network+Ion can be with ion exchange salt bathIn biggish K+Ion swaps, if the Na in glass2O concentration is too low, gained stressor layers compression depth after ion exchangeIt is too low；But if Na in glass2The HT CTE of O excessive concentration, glass increases, 15%~22% Na2O is present in glassIn be optimal amount, other Na2The viscosity of glass can also be greatly reduced in O.
K2O:0~6%.
By K2O is added to glass to improve ion-exchange performance.It specifically, can be by K2O is added in glass to obtainThe bearing stress and stressor layers compression depth needed.In addition, R2O and Al2O3The ratio of concentration be typically less than or equal to 1.1,Middle R2O is Na2O and K2O。R2The sum of concentration of O is by Al2O3Concentration balance, this balance generates a variety of institutes in gained glassThe feature needed, specifically, Al2O3Using potassium ion and sodium ion come stable charging, if there are excessive in glass compositionAlkali metal, i.e. R2O:Al2O3It is greater than or waits 1.1, phase occurs for the boron in the excessive alkali metal of glass composition and the glass compositionInteraction, by boron from the tripartite of its standard, i.e., the configuration of triple coordinations is converted to tetrahedron, i.e. the construction of quadruple coordination, boron fromThe change that tripartite is coordinated to tetrahedral coordination increases the HT CTE of glass.Therefore, by by R2O and Al2O3Ratio keep it is smallIn or be equal to 1.1, prevent the boron ion in glass from taking tetrahedral coordination in glass, thus promote lower HT CTE.
P2O5: 0~5%.
P2O5Although the Network former of glass, due to there is a phosphorus oxygen double bond to be easily broken off in phosphorus oxygen tetrahedron, becauseThis its network is layer structure, and the bond distance of phosphorus oxygen key is greater than silicon oxygen bond, and the tetrahedral volume of phosphorus oxygen is also greater than silicon oxygen four sidesBody, therefore 0~5% P2O5Addition so that the structure of glass becomes loose, so that ion exchange reaches deeper depthDegree.
ZnO:0~6%, MgO:0~3%, CaO:0.1%~3%.
Oxides, divalent MO is added in glass, and wherein M is alkaline-earth metal or Zn, such as M can be Mg or Ca, these divalentOxide improves the melting behaviour of glass composition.In addition, addition MgO and ZnO further improves the ion-exchange performance of glass；Specifically, find given ion-exchange time and at a temperature of, addition MgO and ZnO usually increases bearing stress and answersPower layer compression depth, and do not increase the softening point of glass.In addition, in the softening point for not increasing glass when ZnO content is 3% or lessWhile can utmostly increase the bearing stress and stressor layers compression depth of glass.0.1%~3% CaO is added toGlass composition, which is typically facilitated, keeps enough bearing stresses and stressor layers compression depth after ion exchange reinforcing, whenBearing stress required for CaO content can keep for 0.5% or less while reducing synthesis cost and stress layer compressionDepth.
SnO2: 0~4%.
SnO2It is to be added to as clarifying agent in glass ingredient of the invention, content is 0~4%, can eliminate glassBubble in molten liquid.
The production process that 3D of the present invention forms colorable ion exchange alumina silicate glass is as follows,
Firstly, selection glass raw material, become the component of glass, prepared, be uniformly mixed, in glass-melting furnace intoRow melts, melting mode can be used the mode of all-electric melting furnace or the mode of flame combination electric boosting furnace form to obtain with a thickness of5mm plate glass below can specifically be carried out using float glass process and overflow downdraw.
Then, above-mentioned flat glass film surface first after cleaned processing, can be placed in high-temperature annealing furnace, according to techniqueThe high temperature anneal is carried out to remove thermal stress, then sheet glass is transferred in the colorant fused salt of melting rapidly, 380~450 DEG C of progress 1~6h of ion exchange form certain thickness bearing stress layer in glass surface, obtain required softening pointWith HT CTE, then in 380~450 DEG C of potassium nitrate and the high-temperature fusion liquid of sodium nitrate carry out 0.5~2h of ion exchange, to mentionThe CS of high glass, take out sheet glass, be placed in high-temperature annealing furnace, in 1h from 400 DEG C be cooled to 80 DEG C after reduce tensile stress increaseThe impact resistant strength of strong glass, takes out sheet glass, and the fused salt of sheet glass clean the surface obtains colorable glass finished-product.
According to batch of material listed by table 1, these oxides are mixed, melt and be shaped to glass finished-product, measure glass combinationProperty, that is, softening point of object, HT CTE, CS and DOL are shown in Table 2, wherein IOX1 indicates first time ion exchange, and IOX2 indicates theTwo-step ion-exchanging, A represent copper nitrate, and B represents sodium nitrate, and C represents potassium nitrate, when chemical strengthening, weigh in proportion respectively pointPure copper nitrate is analysed, sodium nitrate and potassium nitrate are put into 4 rustless steel containers of side wall Resistant heating and is heated to settingTemperature is kept the temperature after forming salt bath.
When specific operation,
The formula of eight embodiments and the formula of soda-lime glass are determined by oxide ratios listed by table 1 and comparative example, soWeigh a certain amount of quartz sand respectively according to the ratio of table 1 afterwards, the purity of quartz sand can for 99.8%, Fe content 100ppm withUnder, 100 mesh of granularity hereinafter, chemical pure alumina, the pure boric acid of chemistry, the pure sodium carbonate of chemistry, the pure potassium carbonate of chemistry, aluminium metaphosphate,Chemical pure zirconia magnesium, chemical pure zinc oxide, chemical carbonate-free lime and chemical pure zirconia tin are made into three parts of high alumina silicate glasses and matchClose material sample.A certain amount of quartz sand, the purity 99.8% of quartz sand, Fe content are weighed respectively in the ratio of 1 comparative example of table again100ppm hereinafter, 100 mesh of granularity hereinafter, chemical pure alumina, the pure sodium carbonate of chemistry, the pure potassium carbonate of chemistry, the pure calcium carbonate of chemistry,Chemical pure zirconia magnesium and chemical pure zirconia tin are made into soda-lime glass sample batch.
The soda-lime glass of the chemcor glass of the invention of table 1 and comparative example forms list
Above-mentioned batch is contained respectively in platinum pincers pot and is heated to 1650 DEG C in Muffle furnace and is melted and clarified 16After hour, it is cast into the glass plate of regulation shape in Stainless Molding Board, then annealed, ground and is polished, is respectively preparedWith a thickness of the plate glass of the different formulations of 5mm each 5, then above-mentioned each 5 of manufactured glass plate sample is immersed respectively and includesIt is strong that according to the temperature and time of setting chemistry twice is carried out in the high-temperature fusion liquid of the copper nitrate of colorant, potassium nitrate and sodium nitrateChange processing, wherein the ratio of first time be 30wt%~50wt% copper nitrate, the potassium nitrate of 20wt%~35wt% andThe sodium nitrate of 20wt%~35wt%, secondary ratio are the potassium nitrate of 90wt%~100wt% and the nitric acid of 0~10wt%Sodium.
Measure the bearing stress and stressor layers compression depth of the above sample respectively with FSM-6000 stress gauge, wherein surfaceCompression can be abbreviated as CS, and stressor layers compression depth can be abbreviated as DOL, according to CIE F2 light source and L*a*b* colour code rulerCarry out the degree of quantification color.
2 the embodiment of the present invention 1 of table to embodiment 3 and comparative example parameters and the results list
3 the embodiment of the present invention 4 of table to embodiment 8 parameters list
From test result table 2 and table 3 as can be seen that the softening point of glass is less than 800 after the reinforcing of high alumina silicate glassDEG C, it is 777~793 DEG C, high-temperature heat expansion coefficient is less than 30ppm/ DEG C, is 22.5~26.7ppm/ DEG C, has at least 714MPaBearing stress, at least 36.1 μm of the stressor layers compression depth in glass are extended to from the surface of glass, than common sodium calciumStrengthened glass has deeper stressor layers compression depth and bigger bearing stress, lower softening point and high-temperature heat expansion systemNumber.Glass composition has L*a*b* coordinate, L*, a*, and b* is the chromatic value for representing object color, that is, the color sky of the colorBetween coordinate, any color has unique coordinate value；Wherein L represents shading value, that is, Black-White, and a represents red green, b generationTable champac color, the color of high alumina silicate glass are blue.
The present invention passes through chemical strengthening and is shaped to the colorable alumina silicate glass of 3D shape, is impregnated using fused saltMethod, by the glass-impregnated through the high temperature anneal in the fused salt mixed by mantoquita and other a variety of salt, copper ion conductThe colorant of glass, the lesser sodium ion of radius in the biggish potassium ion displacement glass of radius in fused salt, at this point, in glass surfaceCertain compression is formed, copper ion is allow fast and effeciently to enter inside glass, pigmentable glass is obtained after annealing, moves backGlass after fire increases the bearing stress of glass through secondary hardening, and glass is made under the formula has low softening point and lowHigh-temperature heat expansion coefficient is easy to carry out three-dimensionally shaped.This glass finished-product with 3D shape and color is after reprocessingIt is used as the outer cover or crust component of consumer electronics such as mobile phone and plate.