CN107540211B - An alkali silica glass containing alumina and zirconia - Google Patents
An alkali silica glass containing alumina and zirconia Download PDFInfo
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- CN107540211B CN107540211B CN201711007123.8A CN201711007123A CN107540211B CN 107540211 B CN107540211 B CN 107540211B CN 201711007123 A CN201711007123 A CN 201711007123A CN 107540211 B CN107540211 B CN 107540211B
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000003513 alkali Substances 0.000 title abstract description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011521 glass Substances 0.000 abstract description 70
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 230000008521 reorganization Effects 0.000 abstract description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 230000006872 improvement Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 238000005496 tempering Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 238000003426 chemical strengthening reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种含有氧化铝和氧化锆的碱硅玻璃，按摩尔百分比计，包括：SiO2为45‑80％，R2O为10‑30％，ZrO2+Al2O3为10‑25％；其中：ZrO2:Al2O3的摩尔比为1:4，R2O:(Al2O3+ZrO2)的摩尔比为1.0‑1.2。本发明在碱硅玻璃中引入了Al2O3和ZrO2，有效实现玻璃结构的重组与再造；通过上述组分和配比，使玻璃的熔化特性、成型特性和工艺特性均能得到兼顾，且本发明的玻璃具有相对优良的力学性能，韧性好，抗冲击，耐划伤。The invention discloses an alkali-silica glass containing alumina and zirconia. In molar percentage, it comprises: SiO 2 is 45-80%, R 2 O is 10-30%, ZrO 2 +Al 2 O 3 is 10% ‑25%; wherein: the molar ratio of ZrO 2 :Al 2 O 3 is 1:4, and the molar ratio of R 2 O:(Al 2 O 3 +ZrO 2 ) is 1.0‑1.2. In the present invention, Al 2 O 3 and ZrO 2 are introduced into the alkali silica glass to effectively realize the reorganization and reconstruction of the glass structure; through the above components and proportions, the melting characteristics, forming characteristics and process characteristics of the glass can be taken into consideration, And the glass of the present invention has relatively excellent mechanical properties, good toughness, impact resistance and scratch resistance.
Description
技术领域technical field
本发明涉及玻璃技术领域，尤其涉及一种含有氧化铝和氧化锆的碱硅玻璃。The present invention relates to the technical field of glass, in particular to an alkali silica glass containing alumina and zirconia.
背景技术Background technique
碱硅玻璃(R2O-SiO2)是一种最为基础的二元玻璃体系，R2O为碱金属氧化物，具有较好的熔化特性，但是化学稳定性和力学强度不好，因此成为其致命弱点，即使采用复合碱金属氧化物(Li2O，Na2O，K2O)进行性能调节与改善，其性能提高也是相对有限。如果期望形成相对稳定的玻璃，一般要满足和控制R2O/SiO2的摩尔比<0.5，那么总体要求碱金属氧化物总量在碱硅玻璃总量中(R2O＝Li2O，Na2O，K2O)小于33mol％，才能符合成为玻璃的前提技术要求。Alkali silica glass (R 2 O-SiO 2 ) is the most basic binary glass system. R 2 O is an alkali metal oxide, which has good melting characteristics, but poor chemical stability and mechanical strength, so it becomes a Its Achilles heel is that even if composite alkali metal oxides (Li 2 O, Na 2 O, K 2 O) are used for performance adjustment and improvement, its performance improvement is relatively limited. If it is desired to form a relatively stable glass, it is generally necessary to meet and control the molar ratio of R 2 O/SiO 2 <0.5, then the total amount of alkali metal oxides is generally required to be in the total amount of alkali silica glass (R 2 O=Li 2 O, Only when Na 2 O, K 2 O) is less than 33 mol% can it meet the prerequisite technical requirements for becoming glass.
碱硅玻璃(R2O-SiO2)在三维空间的结构基本是层状结构，只有玻璃化学组成相对合理时，受玻璃黏度阻力影响可以阻止析晶发生。但是在实际生产过程中，即使化学组成选择是恰当的，因冷却速度相对不合理，也会出现两个不混溶液相(SiO2成份相，Na2O成份相)。The structure of alkali-silica glass (R 2 O-SiO 2 ) in three-dimensional space is basically a layered structure. Only when the chemical composition of the glass is relatively reasonable, the crystallization can be prevented by the influence of the glass viscosity resistance. However, in the actual production process, even if the chemical composition is selected properly, two immiscible solution phases (SiO 2 composition phase and Na 2 O composition phase) will appear due to the relatively unreasonable cooling rate.
为了改善碱硅玻璃(R2O-SiO2)性能，传统方法是添加碱土金属氧化物RO，RO为CaO、MgO等，使用最多的化学成份是CaO，形成R2O-CaO-SiO2玻璃系统，其中最为普遍使用的典型玻璃为Na2O-CaO-SiO2，该玻璃体系几乎占据当今玻璃产业90％以上的玻璃产品，包括平板玻璃、瓶罐玻璃、器皿玻璃、工艺玻璃等。在碱硅玻璃(R2O-SiO2)中加入CaO也是进一步改善玻璃性能，例如化学稳定性、玻璃稳定性、成型工艺特性。因为CaO依然为碱性氧化物，导致玻璃脆性相对较大，硬度不高，其力学特性相对较弱，不能取得相对优秀的耐磨性、抗划伤、抗冲击、弯折韧性。In order to improve the performance of alkali silica glass (R 2 O-SiO 2 ), the traditional method is to add alkaline earth metal oxide RO, RO is CaO, MgO, etc. The most used chemical component is CaO to form R 2 O-CaO-SiO 2 glass Among them, the most commonly used typical glass is Na 2 O-CaO-SiO 2 , which almost occupies more than 90% of glass products in today's glass industry, including flat glass, bottle glass, vessel glass, craft glass, etc. Adding CaO to alkali silica glass (R 2 O-SiO 2 ) also further improves glass properties, such as chemical stability, glass stability, and molding process characteristics. Because CaO is still an alkaline oxide, the glass is relatively brittle, the hardness is not high, and its mechanical properties are relatively weak, and it cannot achieve relatively excellent wear resistance, scratch resistance, impact resistance, and bending toughness.
发明内容SUMMARY OF THE INVENTION
针对上述问题中存在的不足之处，本发明提供一种含有氧化铝和氧化锆的碱硅玻璃。In view of the deficiencies in the above problems, the present invention provides an alkali silica glass containing alumina and zirconia.
为实现上述目的，本发明提供一种含有氧化铝和氧化锆的碱硅玻璃，按摩尔百分比计，包括：In order to achieve the above object, the present invention provides a kind of alkali silica glass containing alumina and zirconia, in molar percentage, comprising:
SiO2 45-80％；SiO 2 45-80%;
R2O 10-30％；R 2 O 10-30%;
ZrO2+Al2O3 10-25％；ZrO 2 +Al 2 O 3 10-25%;
其中：in:
ZrO2:Al2O3的摩尔比为1:4，R2O:(Al2O3+ZrO2)的摩尔比为1.0-1.2。The molar ratio of ZrO 2 :Al 2 O 3 is 1:4, and the molar ratio of R 2 O :(Al 2 O 3 +ZrO 2 ) is 1.0-1.2.
作为本发明的进一步改进，R2O包括Li2O、Na2O和K2O，Na2O占R2O摩尔总量的60-100％，K2O占R2O摩尔总量的0-30％，Li2O占R2O摩尔总量的0-15％。As a further improvement of the present invention, R 2 O includes Li 2 O, Na 2 O and K 2 O, Na 2 O accounts for 60-100% of the total mole of R 2 O, and K 2 O accounts for 60-100% of the total mole of R 2 O 0-30%, Li 2 O accounts for 0-15% of the total R 2 O moles.
作为本发明的进一步改进，所述SiO2的摩尔百分比为52-75％。As a further improvement of the present invention, the molar percentage of the SiO 2 is 52-75%.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
本发明在碱硅玻璃中引入了Al2O3和ZrO2，有效实现玻璃结构的重组与再造；通过上述组分和配比，使玻璃的熔化特性、成型特性和工艺特性均能得到兼顾，且本发明的玻璃具有相对优良的力学性能，韧性好，抗冲击，耐划伤。In the present invention, Al 2 O 3 and ZrO 2 are introduced into the alkali silica glass to effectively realize the reorganization and reconstruction of the glass structure; through the above components and proportions, the melting characteristics, forming characteristics and process characteristics of the glass can be taken into consideration, And the glass of the present invention has relatively excellent mechanical properties, good toughness, impact resistance and scratch resistance.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purposes, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the present invention. examples, but not all examples. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.
下面对本发明做进一步的详细描述：The present invention is described in further detail below:
玻璃的硬度和脆性严重制约玻璃应用与发展，目前，广泛使用的钠钙玻璃(Na2O-CaO-SiO2)在熔化制备方面相对较佳，可以满足熔化温度低，玻璃料性长，但是玻璃理化性能尚有不足，例如化学稳定性差，玻璃表面抗划伤、弯折韧性差、抗冲击强度低，这主要由钠钙玻璃中的碱土金属氧化物RO所导致，例如CaO、MgO、BaO、SrO等，这些碱土金属氧化物赋予玻璃很好的助熔特性，但是对氧原子作用力相对较弱，导致玻璃网络结构的疏松，呈现玻璃脆性增大的特性，在冲击作用下，易使玻璃表面的微小裂纹延展速率增大，玻璃更易破损。The hardness and brittleness of glass seriously restrict the application and development of glass. At present, the widely used soda-lime glass (Na 2 O-CaO-SiO 2 ) is relatively good in melting preparation, which can meet the requirements of low melting temperature and long frit, but The physical and chemical properties of glass are still insufficient, such as poor chemical stability, scratch resistance, poor bending toughness and low impact strength on the glass surface, which are mainly caused by the alkaline earth metal oxide RO in soda lime glass, such as CaO, MgO, BaO , SrO, etc. These alkaline earth metal oxides endow glass with good fluxing properties, but the force on oxygen atoms is relatively weak, resulting in loose glass network structure and increased glass brittleness. The propagation rate of micro-cracks on the glass surface increases, and the glass is more easily broken.
本发明为了抑制碱土金属氧化物(RO＝CaO、MgO、BaO、SrO)对钠钙玻璃的力学性能的影响，在玻璃组成设计方面，剔除碱土金属氧化物使用，以二元碱硅玻璃体系(R2O-SiO2)作为玻璃性能调节改造基础，利用氧化硅(SiO2)网络形成体作用，利用碱金属氧化物(R2O)作为网络外体，促进玻璃断网效率，有效实现玻璃熔化制备特性要求。In order to suppress the influence of alkaline earth metal oxides (RO=CaO, MgO, BaO, SrO) on the mechanical properties of soda-lime glass, the present invention eliminates the use of alkaline earth metal oxides in the design of glass composition, and uses binary alkali silica glass system ( R 2 O-SiO 2 ) is used as the basis for the adjustment and transformation of glass properties, using the role of silicon oxide (SiO 2 ) as a network former, and using alkali metal oxide (R 2 O) as the network outer body to promote the glass breaking efficiency and effectively realize the glass Melt preparation characteristic requirements.
本发明为了改善碱硅二元玻璃的力学性能相对不足，通过引入和使用氧化铝(Al2O3)和氧化锆(ZrO2)，完成玻璃结构重组与再造。In order to improve the relatively insufficient mechanical properties of the alkali-silicon binary glass, the present invention completes the structural reorganization and reconstruction of the glass by introducing and using alumina (Al 2 O 3 ) and zirconia (ZrO 2 ).
氧化铝(Al2O3)是中间体氧化物，作为氧化硅和碱金属氧化物的联络体，使二元碱硅玻璃网络结构紧密，减少和降低碱金属氧化物游离，促进玻璃化学稳定性提高。在氧化钠的协同作用下，当Na2O/Al2O3的摩尔比≤1时，可以促进氧化铝转化成网络形成体，玻璃结构的紧密性最佳，玻璃力学性能得到提高，尤其在玻璃脆性改善方面得到较大提升，弯折和冲击强度增大幅度50-80％，抑制和阻碍了微裂纹扩展，明显体现了玻璃韧性增强。Alumina (Al 2 O 3 ) is an intermediate oxide, which acts as a link between silicon oxide and alkali metal oxides, making the network structure of dibasic alkali silicate glass tight, reducing and reducing alkali metal oxide free, and promoting chemical stability of glass improve. Under the synergistic effect of sodium oxide, when the molar ratio of Na 2 O/Al 2 O 3 is less than or equal to 1, the conversion of alumina into a network can be promoted, the tightness of the glass structure is the best, and the mechanical properties of the glass are improved, especially in the The improvement of glass brittleness has been greatly improved, and the bending and impact strengths have increased by 50-80%, which inhibits and hinders the growth of micro-cracks, and clearly reflects the enhancement of glass toughness.
氧化锆(ZrO2)是一种体现阴离子特性的氧化物，锆离子是半径相对较大副族元素，在玻璃结构中基本很少参与玻璃网络联结，主要以阴离子团形式积聚，由于(ZrO2)具有很高的熔点2450℃，另外ZrO2自身硬度达到和接近氧化铝(Al2O3)，莫氏硬度达到8.5-9.0，是仅次于金刚石(莫氏硬度为10)的物质，因此促进和改善了玻璃表面抗划伤性提升，因为ZrO2在玻璃中的溶解度低，ZrO2在普通Na2O-CaO-SiO2玻璃中仅有3wt％，主要以阴离子团积聚方式存在；相对Al2O3可适当降低玻璃高温黏度，会诱导玻璃分相与析晶，致使玻璃失透，使玻璃态稳定性不好，即使没有达到析晶物质浓度条件，也会导致玻璃黏度提高、熔化温度提高、液相线温度提高，使玻璃生产制造变得异常困难，其相对实用性不佳。Zirconium oxide (ZrO 2 ) is an oxide with anionic properties. Zirconium ion is a subgroup element with a relatively large radius. ) has a very high melting point of 2450 ° C, in addition, the hardness of ZrO 2 reaches and is close to that of alumina (Al 2 O 3 ), and the Mohs hardness reaches 8.5-9.0, which is second only to diamond (Mohs hardness is 10). Therefore, Promote and improve the scratch resistance of glass surface, because ZrO 2 has low solubility in glass, ZrO 2 is only 3wt% in ordinary Na 2 O-CaO-SiO 2 glass, and mainly exists in the form of anion agglomeration; relatively Al 2 O 3 can appropriately reduce the high temperature viscosity of the glass, which will induce phase separation and crystallization of the glass, resulting in devitrification of the glass and poor stability of the glass state. The increase in temperature and the increase in liquidus temperature make glass production extremely difficult, and its relative practicability is not good.
本发明发现在二元碱硅玻璃体系(R2O-SiO2)中，氧化锆溶解度随着氧化铝含量存在相互依存关系，随着氧化铝增加，氧化锆溶解度逐步增加，这样摆脱玻璃力学增强采用单一依赖氧化铝的方式，借助于氧化铝和氧化锆双重作用，并且分别满足不同特性要求，氧化铝(Al2O3)提高韧性，氧化锆(ZrO2)提高耐划伤，这样玻璃的综合力学性能有了较好提升。氧化锆和氧化铝协同溶解度关系为：ZrO2/Al2O3的摩尔比＝1:4，且碱金属氧化物R2O/(Al2O3+ZrO2)的摩尔比＝1.0-1.2，另外ZrO2+Al2O3的摩尔总量占玻璃摩尔总量的10-25％；满足上述条件时，玻璃熔化特性、成型特性和工艺特性均能得到兼顾，并且可获得相对优良力学性能，韧性好、抗冲击、耐划伤的玻璃。依据上述规律组成的玻璃，其中碱金属氧化物R2O包括Li2O、Na2O和K2O，限于玻璃成份作用特性和经济性，优先使用氧化钠(Na2O)，其次是氧化钾(K2O)，再者是氧化锂(Li2O)，可以单独使用或复合使用，复合使用效果更佳，有利于混合碱效应，优选碱金属氧化物R2O的摩尔总量占玻璃摩尔总量的10-30％，其中Na2O占R2O摩尔总量的60-100％，K2O占R2O摩尔总量的0-30％，Li2O占R2O摩尔总量的0-15％。The present invention finds that in the dibasic alkali silica glass system (R 2 O-SiO 2 ), the solubility of zirconia is interdependent with the content of alumina. With the increase of alumina, the solubility of zirconia gradually increases, so as to get rid of the mechanical enhancement of glass In a single way of relying on alumina, with the help of the dual effects of alumina and zirconia, and respectively meeting different characteristic requirements, alumina (Al 2 O 3 ) improves toughness, and zirconia (ZrO 2 ) improves scratch resistance. The comprehensive mechanical properties have been improved. The synergistic solubility relationship between zirconia and alumina is: the molar ratio of ZrO 2 /Al 2 O 3 =1:4, and the molar ratio of alkali metal oxide R 2 O/(Al 2 O 3 +ZrO 2 )=1.0-1.2 In addition, the total molar amount of ZrO 2 +Al 2 O 3 accounts for 10-25% of the total glass molar amount; when the above conditions are met, the glass melting characteristics, forming characteristics and process characteristics can be taken into account, and relatively good mechanical properties can be obtained. , Glass with good toughness, impact resistance and scratch resistance. Glass composed according to the above rules, wherein the alkali metal oxides R 2 O include Li 2 O, Na 2 O and K 2 O. Limited to the function characteristics and economy of glass components, sodium oxide (Na 2 O) is preferentially used, followed by oxidation Potassium (K 2 O), and then lithium oxide (Li 2 O), can be used alone or in combination, and the combined use effect is better, which is conducive to the mixed alkali effect, preferably the total molar amount of alkali metal oxide R 2 O accounts for 10-30% of the total moles of glass, in which Na2O accounts for 60-100 % of the total moles of R2O , K2O accounts for 0-30 % of the total moles of R2O , and Li2O accounts for R2O 0-15% of the total molar amount.
SiO2是玻璃网络形成体，是形成硅酸盐玻璃必用的成份。为了满足玻璃理化和工艺性能要求，SiO2的摩尔总量占玻璃摩尔总量优选45-80％为佳，进一步优选52-75％。SiO 2 is a glass network former and is an essential component for forming silicate glass. In order to meet the requirements of glass physicochemical and technological properties, the total molar amount of SiO 2 is preferably 45-80% of the total glass molar amount, and more preferably 52-75%.
基于上述研究，本发明提供一种含有氧化铝和氧化锆的碱硅玻璃，按摩尔百分比计，包括：Based on the above research, the present invention provides an alkali silica glass containing alumina and zirconia, in molar percentage, comprising:
SiO2 45-80％；SiO 2 45-80%;
碱金属氧化物R2O 10-30％；Alkali metal oxide R 2 O 10-30%;
ZrO2+Al2O3 10-25％；ZrO 2 +Al 2 O 3 10-25%;
其中：in:
ZrO2:Al2O3的摩尔比为1:4，R2O:(Al2O3+ZrO2)的摩尔比为1.0-1.2；R2O包括Li2O、Na2O和K2O，Na2O占R2O摩尔总量的60-100％，K2O占R2O摩尔总量的0-30％，Li2O占R2O摩尔总量的0-15％。The molar ratio of ZrO 2 :Al 2 O 3 is 1:4, the molar ratio of R 2 O:(Al 2 O 3 +ZrO 2 ) is 1.0-1.2; R 2 O includes Li 2 O, Na 2 O and K 2 O, Na 2 O accounts for 60-100% of the total R 2 O moles, K 2 O accounts for 0-30% of the total R 2 O moles, and Li 2 O accounts for 0-15% of the total R 2 O moles.
优选的，SiO2的摩尔百分比为52-75％。Preferably, the molar percentage of SiO 2 is 52-75%.
本发明一种含有氧化铝和氧化锆的碱硅玻璃的制备方法为：A preparation method of the alkali silica glass containing alumina and zirconia of the present invention is:
按照上述配方称取各组分并混合，高温下熔化、澄清、均化、成型、退火，制得玻璃产品。According to the above formula, the components are weighed and mixed, melted at high temperature, clarified, homogenized, shaped and annealed to obtain a glass product.
本发明上述的玻璃作为物理钢化处理和化学强化处理的物质基础，为玻璃本体力学性能提升与改善创造技术条件，可为其应用领域实现拓展，例如高速交通(高铁、飞机)、新能源汽车、建筑幕墙玻璃、安全玻璃，甚至屏显保护玻璃。本发明所用的物理钢化是通常所用的玻璃软化点附近气流淬冷工艺，化学强化工艺采用的是低温法离子交换工艺，控制硝酸钾熔盐或复合硝酸盐熔盐(质量比，硝酸钾:硝酸钠的质量比为(70-95):(5-30))加热至低于玻璃应变点温度100℃左右，大约360-450℃之间，强化处理时间90-450min，可使玻璃表面压应力达到800-1200MPa，并且离子交换深度达到35-120μm，玻璃抗冲击强度可仅提升3-8倍，物理钢化大约提高3-5倍，化学钢化可以提高5-8倍，表面抗划伤性能提高30-50％，强化工艺对抗划伤性能提升的贡献率达60-70％。The above-mentioned glass of the present invention serves as the material basis for physical tempering treatment and chemical strengthening treatment, creates technical conditions for the improvement and improvement of the mechanical properties of the glass body, and can expand its application fields, such as high-speed transportation (high-speed rail, aircraft), new energy vehicles, Building curtain wall glass, safety glass, and even screen protection glass. The physical tempering used in the present invention is the commonly used gas flow quenching process near the softening point of the glass, and the chemical strengthening process adopts the low temperature ion exchange process, and controls potassium nitrate molten salt or composite nitrate molten salt (mass ratio, potassium nitrate: nitric acid) The mass ratio of sodium is (70-95):(5-30)) heated to about 100°C lower than the glass strain point temperature, about 360-450°C, and the strengthening treatment time is 90-450min, which can make the glass surface compressive stress. It can reach 800-1200MPa, and the ion exchange depth can reach 35-120μm. The impact strength of glass can only be increased by 3-8 times, the physical tempering can be increased by about 3-5 times, the chemical tempering can be increased by 5-8 times, and the surface scratch resistance can be improved. 30-50%, and the contribution rate of strengthening process to the improvement of scratch resistance is 60-70%.
本发明的具体实施例如表1、表2所示，表1和表2的单位均为mol％：Specific embodiments of the present invention are shown in Table 1 and Table 2, and the units in Table 1 and Table 2 are mol%:
表1Table 1
表2Table 2
本发明提供一种含有氧化铝和氧化锆的碱硅玻璃，以基础的二元碱硅玻璃(R2O-SiO2)力学性能改善为目的，采用力学增强成份Al2O3和ZrO2，进行玻璃结构空间的重组与再造，通过适当强化工艺处理，获得力学性能相对优秀的玻璃品种。The present invention provides an alkali-silica glass containing alumina and zirconia, aiming at improving the mechanical properties of the basic dibasic alkali-silica glass (R 2 O-SiO 2 ), using mechanical strengthening components Al 2 O 3 and ZrO 2 , Carry out the reorganization and reconstruction of the glass structure space, and obtain glass varieties with relatively excellent mechanical properties through appropriate strengthening process treatment.
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
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