阅读说明：本技术 一种抗划伤和抗外界冲击力的离子交换玻璃及其制备方法 (A kind of scratch resistance and the chemcor glass of resistance to external shocks power and preparation method thereof ) 是由 牛桃霞 彭引平 于 2019-08-27 设计创作，主要内容包括：本发明一种抗划伤和抗外界冲击力的离子交换玻璃及其制备方法,所述玻璃的组分按质量百分比计包括,SiO<Sub>2</Sub>54％～70％,Al<Sub>2</Sub>O<Sub>3</Sub>10％～23％,Li<Sub>2</Sub>O 0～5％,Na<Sub>2</Sub>O 5％～17％,K<Sub>2</Sub>O 0～8％,MgO 1％～10％,CaO 0～4％,ZrO<Sub>2</Sub>1％～5％,SnO<Sub>2</Sub>0.3％～1％,CeO<Sub>2</Sub>0.2％～1.5％；所述制备方法包括步骤1,按质量百分比计,依照上述玻璃的组分配制原料,将原料熔化和澄清后成型为玻璃；步骤2,将玻璃进行化学强化处理,得到抗划伤和抗外界冲击力的离子交换玻璃；该玻璃比钠钙玻璃具有更强的抗冲击强度和抗表面刮擦能力,对电子产品的保护能力更好。(A kind of scratch resistance of the present invention and the chemcor glass of resistance to external shocks power and preparation method thereof, the component of the glass includes SiO by mass percentage 2 54%~70%, Al 2 O 3 10%~23%, Li 2 O 0~5%, Na 2 O 5%~17%, K 2 O 0~8%, MgO 1%~10%, CaO 0~4%, ZrO 2 1%~5%, SnO 2 0.3%~1%, CeO 2 0.2%~1.5%；The preparation method includes step 1, by mass percentage, according to the component preparation raw material of above-mentioned glass, will be shaped to glass after melting sources and clarification；Step 2, glass is subjected to chemical intensification treatment, obtains the chemcor glass of scratch resistance and resistance to external shocks power；The glass than soda-lime glass there is stronger impact strength and resistance to surface to scrape ability, more preferable to the protective capability of electronic product.)

1. the chemcor glass of a kind of scratch resistance and resistance to external shocks power, which is characterized in that the group of the chemcor glass Divide includes SiO by mass percentage₂54%~70%, Al₂O₃10%~23%, Li₂O 0~5%, Na₂O 5%~ 17%, K₂O 0~8%, MgO 1%~10%, CaO 0~4%, ZrO₂1%~5%, SnO₂0.3%~1%, CeO₂ 0.2%~1.5%.

2. the chemcor glass of a kind of scratch resistance and resistance to external shocks power according to claim 1, which is characterized in that institute The SiO stated₂Mass percent be 56%~68%.

3. the chemcor glass of a kind of scratch resistance and resistance to external shocks power according to claim 1, which is characterized in that institute The Al stated₂O₃Mass percent be 12%~20%.

4. the chemcor glass of a kind of scratch resistance and resistance to external shocks power according to claim 1, which is characterized in that institute The Na stated₂The mass percent of O is 8%~14%.

5. the chemcor glass of a kind of scratch resistance and resistance to external shocks power according to claim 1, which is characterized in that institute The K stated₂The mass percent of O is 2%~6%.

6. the chemcor glass of a kind of scratch resistance and resistance to external shocks power according to claim 1, which is characterized in that institute The sum of mass percent of the CaO and MgO that state is 5%~11%.

7. the chemcor glass of a kind of scratch resistance and resistance to external shocks power according to claim 1, which is characterized in that institute The ZrO stated₂、CeO₂And SnO₂The sum of mass percent be 2%~7%.

8. the preparation method of a kind of scratch resistance and the chemcor glass of resistance to external shocks power, which is characterized in that including following step Suddenly,

Step 1, by mass percentage, according to the component preparation raw material of glass, glass will be shaped to after melting sources and clarification； The component of glass is SiO by mass percentage₂54%~70%, Al₂O₃10%~23%, Li₂O 0~5%, Na₂O 5% ~17%, K₂O 0~8%, MgO 1%~10%, CaO 0~4%, ZrO₂1%~5%, SnO₂0.3%~1%, CeO₂ 0.2%~1.5%；

Step 2, glass is subjected to chemical intensification treatment, obtains the chemcor glass of scratch resistance and resistance to external shocks power, it is described Chemical intensification treatment includes single strong or complex intensifying, wherein

Dan Qiang is carried out in the molten liquid of potassium nitrate, and temperature is 380~420 DEG C, and the time is 300~360min；

Complex intensifying carries out in the molten liquid of potassium nitrate and sodium nitrate, and the temperature of the first step is 380~420 DEG C, enhanced time For 100~130min, the mass percent of sodium nitrate is 20%~40%, and the mass percent of potassium nitrate is 60%~80%； The temperature of second step is 380~420 DEG C, and enhanced time is 30~60min, and the mass percent of sodium nitrate is 5%~15%, nitre The mass percent of sour potassium is 85%~95%.

9. the preparation method of a kind of scratch resistance according to claim 8 and the chemcor glass of resistance to external shocks power, It is characterized in that, the thickness of glass is 1~5mm.

10. a kind of scratch resistance that the preparation method as described in any one of claim 8~9 obtains and resistance to external shocks power Chemcor glass.

Technical field

The present invention relates to glassmaking art, the ion exchange glass of specially a kind of scratch resistance and resistance to external shocks power Glass and preparation method thereof.

Background technique

With the development of modern display science and technology, liquid crystal display, ATM protection screen, touch screen, mobile phone and information inquiry The flat panel display products such as machine, which emerge in multitude, to be widely used in our daily life, but the scratch resistance of these display products Foreign impacts ability is all poor with resisting.

Some electronical display products be frequently encountered such as sharppointed article the various severe use environments of delineation and some For destruction.It write, delineated on a display screen in addition, touch screen often has finger, electronic pen, signature pen even key And there is damaged and surface scratching, influence to show product in the risky operation such as impact, this screen that will lead to electronical display product Display effect, or even injure their service life.Therefore the screen surface of these display products is badly in need of a kind of hardness and machine The good glass material of tool intensity.

Summary of the invention

Aiming at the problems existing in the prior art, the present invention provides the ion exchange of a kind of scratch resistance and resistance to external shocks power Glass and preparation method thereof, easy to operate, at low cost, resulting glass machinery intensity is high, wear-resistant, impact resistance, chemical stabilization Property it is good, there is stronger impact strength and resistance to surface to scrape ability, to the protective capability of electronic product than common sodium calcium glass Glass is more preferable.

The present invention is to be achieved through the following technical solutions:

The component of a kind of chemcor glass of scratch resistance and resistance to external shocks power, the chemcor glass presses quality hundred Dividing than meter includes SiO₂54%~70%, Al₂O₃10%~23%, Li₂O 0~5%, Na₂O 5%~17%, K₂O 0~ 8%, MgO 1%~10%, CaO 0~4%, ZrO₂1%~5%, SnO₂0.3%~1%, CeO₂0.2%~1.5%.

Preferably, the SiO₂Mass percent be 56%~68%.

Preferably, the Al₂O₃Mass percent be 12%~20%.

Preferably, the Na₂The mass percent of O is 8%~14%.

Preferably, the K₂The mass percent of O is 2%~6%.

Preferably, the sum of mass percent of the CaO and MgO is 5%~11%.

Preferably, the ZrO₂、CeO₂And SnO₂The sum of mass percent be 2%~7%.

The preparation method of a kind of scratch resistance and the chemcor glass of resistance to external shocks power, includes the following steps,

Step 1, by mass percentage, according to the component preparation raw material of glass, will be shaped to after melting sources and clarification Glass；The component of glass is SiO by mass percentage₂54%~70%, Al₂O₃10%~23%, Li₂O 0~5%, Na₂O 5%~17%, K₂O 0~8%, MgO 1%~10%, CaO 0~4%, ZrO₂1%~5%, SnO₂0.3%~ 1%, CeO₂0.2%~1.5%；

Step 2, glass is subjected to chemical intensification treatment, obtains the chemcor glass of scratch resistance and resistance to external shocks power, The chemical intensification treatment includes single strong or complex intensifying, wherein

Dan Qiang is carried out in the molten liquid of potassium nitrate, and temperature is 380~420 DEG C, and the time is 300~360min；

Complex intensifying carries out in the molten liquid of potassium nitrate and sodium nitrate, and the temperature of the first step is 380~420 DEG C, strengthens Time is 100~130min, and the mass percent of sodium nitrate is 20%~40%, the mass percent of potassium nitrate is 60%~ 80%；The temperature of second step is 380~420 DEG C, and enhanced time is 30~60min, the mass percent of sodium nitrate is 5%~ 15%, the mass percent of potassium nitrate is 85%~95%.

Further, the thickness of glass is 1~5mm.

A kind of ion exchange of the scratch resistance that the preparation method as described in above-mentioned any one obtains and resistance to external shocks power Glass.

Compared with prior art, the invention has the following beneficial technical effects:

Chemcor glass of the present invention, by by SiO₂Concrete content be designed as mass percent be 54%~ 70%, mechanical strength, chemical stability and the thermal stability of the glass formed after not only can improving, and can also keep away Exempt from glass melting and clarification is difficult；The Al that mass percent is 10%~23%₂O₃The crystallization of the glass formed after can reducing Tendency improves glass hard (HRC65Yi Shang) and mechanical strength；Li₂O is extraordinary fluxing agent, the Li that mass percent is 0~5%₂In O Li⁺It can complete well and Na in fused salt⁺Exchange, without destroying glass network structure, so that the machine of the glass formed later Tool performance is declined, and production cost is higher；The Na that mass percent is 5%~17%₂O and mass percent are 0~8% K₂The glass viscosity that the introducing of O is formed after advantageously reducing reduces melting temperature, lesser Na in glass network⁺Ion can be with Biggish K in ion exchange salt bath⁺Ion swaps, and obtains required chemcor glass；Mass percent is 0~4% CaO and mass percent be 1%~10% MgO introduce after while reducing frit temperature, glass can be improved Mechanical strength；The ZrO that mass percent is 1%~5%₂The chemical durability of glass formed after can not only improving increases Add glass surface hardness, resist the extension that glass forms crackle and crackle, so that glass is more resistant to scratching and fall, and will not Improve the fusion temperature of glass；The SnO that mass percent is 0.3%~1%₂It is 0.2%~1.5% with mass percent CeO₂Clarification is mainly played in the preparation process of glass；In addition, ZrO₂、SnO₂And CeO₂Being added simultaneously can be improved glass Chemical-resistant stability, therefore the sodium calcium fortification that these components are more common in the chemcor glass obtained after chemical strengthening Glass has deeper ion exchange depth and bigger bearing stress, flexural strength and hardness, thus has stronger Impact strength and resistance to surface scrape ability, more preferable than common soda-lime glass to the protective capability of electronic product.

The preparation method of chemcor glass of the present invention passes through the SiO for being 54%~70% by mass percent₂, The Al that mass percent is 10%~23%₂O₃, mass percent be 0~5% Li₂O, mass percent are 5%~17% Na₂O, the K that mass percent is 0~8%₂O, the MgO that mass percent is 1%~10%, mass percent are 0~4% CaO, the ZrO that mass percent is 1%~5%₂, mass percent be 0.3%~1% SnO₂With 0.2%~1.5% CeO₂It is shaped to glass after fusing and clarification, then glass is subjected to single strong or complex intensifying, scratch resistance and anti-extraneous punching can be obtained The chemcor glass of power is hit, the more common sodium calcium fortification glass of the glass, with deeper ion exchange depth and bigger Bearing stress, flexural strength and hardness, thus there is stronger impact strength and resistance to surface to scrape ability, electronics is produced The protective capability of product is more preferable than common soda-lime glass.

The chemcor glass of scratch resistance and resistance to external shocks power of the invention, can following process be screen protection glass, Have the advantages that high mechanical strength, wear-resistant, impact resistance, chemical stability are good, to the protective capability of electronic product than common sodium Lime glass is more preferable, can effectively prevent the impact of display product surface and scratch damage, while can also extend the use of product Service life enhances using effect.

Specific embodiment

Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and It is not to limit.

Scratch resistance of the present invention and the chemcor glass of resistance to external shocks power are alumina silicate glass, by mass percentage Wt% meter includes SiO₂54%~70%, Al₂O₃10%~23%, Li₂O 0~5%, Na₂O 5%~17%, K₂O 0~ 8%, MgO 1%~10%, CaO 0~4%, ZrO₂1%~5%, SnO₂0.3%~1%, CeO₂0.2%~1.5%.

The specific content and effect of each component in the above-mentioned alumina silicate glass of following discussion, that is, limit each ingredient Content range the reasons why, unit is mass percent.

SiO₂: 54%~70%.

SiO₂It is important glass former oxide, the structure of oxygen-octahedron forms irregular contiguous network, Constitute the skeleton of glass.If SiO₂Content is lower, and the chemical resistance after forming glass can reduce, and have crystallization trend, SiO₂ Content height the mechanical strength, chemical stability and thermal stability of glass, but too high levels can be improved, will cause glass melting It is difficult with clarification, glass viscosity increase is also resulted in, needs to control its content in suitable range.Therefore SiO₂Content be 54%~70%, work as SiO₂Content be 56%~68% when can be in mechanical strength, the chemical stability for greatly improving glass With avoid glass melting and clarification difficult while thermal stability well.

Al₂O₃: 10%~23%.

Al₂O₃It is intermediate oxide, participates in glass network and formed, plays network and generate body, while glass can be reduced Tendency towards devitrification, improve glass hard (HRC65Yi Shang) and mechanical strength, but too high levels will lead to glass viscosity increase, specifically, if Its content is greater than 23%, will increase the crystallization tendency and viscosity of glass.Work as Al₂O₃Content be 12%~20% when can be big Width improves glass hard (HRC65Yi Shang) and mechanical strength.

Li₂O:0~5%, Na₂O:5%~17% and K₂O:0~8%.

Li₂O is network modifying oxide, is extraordinary fluxing agent in glass fusion process, in first step ion exchange Process completes the Li in very important glass in first step chemical strengthening process⁺With Na in fused salt⁺Exchange, but it is excessively high Li₂O can destroy glass network structure, so that the mechanical performance of glass is declined, and production cost is higher.Therefore Li₂O Content be preferably 5% or less.K₂O and Na₂O is also network modifying oxide, oxygen-octahedron can be made to be formed by net after introducing Network relaxation and fracture, advantageously reduce glass viscosity, reduce melting temperature, therefore can be used as fluxing agent.In glassware Add Na₂O can promote the ion exchange of glassware to strengthen, specifically, lesser Na in gained glass network⁺Ion can With K biggish in ion exchange salt bath⁺Ion swaps.Work as Na₂When the content of O is 8%~14%, glass can be significantly reduced Glass viscosity and melting temperature, while the ion exchange for being obviously promoted glassware is strengthened.Work as K₂When the content of O is 2%~6%, Also glass viscosity and melting temperature can be significantly reduced.

CaO:0~4% and MgO:1%~10%.

CaO and MgO can also make oxygen-octahedron be formed by network relaxation and fracture after introducing, advantageously reduce melting temperature Degree, and the effect in terms of mechanical strength of the CaO and MgO for improving glass is better than alkali metal oxide.The content of CaO is preferred It is 2~4%.The content of MgO is preferably 2~6%, not only may be used when the sum of mass percent of CaO and MgO is 5%~11% To significantly reduce melting temperature, the mechanical strength of glass can also be obviously improved.

ZrO₂: 1%~5%.

ZrO₂It is intermediate oxide, can be improved chemical durability of glass, increases glass surface hardness, and glass can be resisted Glass forms the extension of crackle and crackle, so that glass is more resistant to scratching and fall, but ZrO₂Too high levels when, not only can Increase the crystallization tendency of glass, and the fusion temperature of glass can be improved, therefore ZrO₂Content be 1%~5%, preferably contain Amount is 1.5%~4%.

SnO₂: 0.3%~1%.

SnO₂Clarification, SnO are mainly played in the preparation process of glass₂Content be 0.3%~1%.

CeO₂: 0.2%~1.5%.

CeO₂Also play clarification in the preparation process of glass, content is 0.2%~1.5% to eliminate glass melting Bubble in liquid, preferably 0.4%~1.2% can also achieve the effect that completely remove bubble while saving raw material.

ZrO₂、SnO₂And CeO₂Simultaneously using the chemical-resistant stability that can be improved glass, the sum of mass percent is preferred It is 2%~7%.In addition, SnO₂And CeO₂Simultaneously using the appearance color that can improve glass, because of CeO₂Content is higher, ultraviolet Line absorption enhancing, and absorb cut-off end and elapsed to visible light, cause occur apparent yellow in glass, therefore utilize SnO₂Generation For part CeO₂The transmitance of glass can be improved.

The production process that the present invention promotes the chemcor glass of scratch resistance and resistance to external shocks power is as follows,

Firstly, in batch mixer after mixing being put according to dosage and the weighing that above-mentioned glass formula calculates corresponding raw material Enter in platinum crucible, and 4~10h is melted and clarified in 1550~1750 DEG C of high temperature furnace, using under float glass process or overflow Daraf(reciprocal of farad) forms to obtain the glass with a thickness of 1.0~5mm, needs dicing according to processing later, such sheet glass is easily changed It learns and strengthens, the hardness on its surface and impact strength is made to increase；

Then, above-mentioned manufactured sheet glass sample is immersed into the high-temperature fusion liquid of potassium nitrate or the height of potassium nitrate and sodium nitrate Chemical intensification treatment is carried out according to the temperature and time of setting in warm molten liquid, wherein the high-temperature fusion liquid of potassium nitrate is corresponding single By force, the high-temperature fusion liquid of potassium nitrate and sodium nitrate corresponds to complex intensifying；The temperature of Dan Qiang be 380~420 DEG C, the time be 300~ 360min；In complex intensifying, the temperature of the first step is 380~420 DEG C, and enhanced time is 100~130min, the ratio of sodium nitrate For 20wt%~40wt%, the ratio of potassium nitrate is 60wt%~80wt%；The temperature of second step is 380~420 DEG C, when reinforcing Between be 30~60min, the ratio of sodium nitrate is 5wt%~15wt%, and the ratio of potassium nitrate is 85wt%~95wt%.It can obtain Obtain the chemcor glass of scratch resistance and resistance to external shocks power.

According to raw materials and consumption listed by table 1, these oxides are mixed, melt and be shaped to glass finished-product, measurement should Property, that is, Vickers hardness, bending strength, shock resistance energy, bearing stress (i.e. CS) and the stressor layers compression depth of glass are (i.e. DOL), wherein IOX1 indicates first time ion exchange, and IOX2 indicates second of ion exchange, and A represents sodium nitrate, and B represents nitric acid Potassium when chemical strengthening, weighs analytically pure sodium nitrate and potassium nitrate in proportion respectively and is put into annealing furnace and is heated to setting Temperature is kept the temperature after forming salt bath, vickers hardness test be using digital display microhardness tester, using Vickers indenter, load 200g, Action time is 10s；Bending strength test uses four-point bending method of testing, i.e. 4PB method；Shock resistance energy test is using falling sphere Shock machine uses impact ball weight for 227g, and the thickness of glass of test is 1mm；CS and DOL uses FSM-6000 stress gauge It is measured.

The ingredient and performance of table 1 the embodiment of the present invention 1~3 and comparative example

Comparative example

Firstly, selecting raw material by glass ingredient listed by table 1, its ingredient is set to meet the glass composition of comparative example, wherein quartz The purity of sand is 99.8%, Fe content 100ppm hereinafter, 100 mesh of granularity is hereinafter, other glass raw materials are that chemistry is pure；It will be above-mentioned Batch is contained in platinum crucible, and 6h is melted and clarified in 1680 DEG C of high temperature furnace, then in Stainless Molding Board It is cast into the glass plate of regulation shape, then annealed, ground and is polished, is respectively prepared the glass with a thickness of 1mm, then by glass Glass sample, which immerses in the high-temperature fusion liquid of potassium nitrate, carries out chemical intensification treatment according to the temperature and time of comparative example.It is shown in table 1 The basic performance of the glass, Vickers hardness 560MPa, bending strength 572MPa, shock resistance energy 1.98J, CS 654MPa are shown With 20 μm of DOL.