WO2020177271A1 - Lithium-containing glass having low softening point - Google Patents

Lithium-containing glass having low softening point Download PDF

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WO2020177271A1
WO2020177271A1 PCT/CN2019/099256 CN2019099256W WO2020177271A1 WO 2020177271 A1 WO2020177271 A1 WO 2020177271A1 CN 2019099256 W CN2019099256 W CN 2019099256W WO 2020177271 A1 WO2020177271 A1 WO 2020177271A1
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glass
softening point
lithium
containing glass
sio
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PCT/CN2019/099256
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French (fr)
Chinese (zh)
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陈招娣
梁新辉
洪立昕
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科立视材料科技有限公司
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Publication of WO2020177271A1 publication Critical patent/WO2020177271A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C03B25/02—Annealing glass products in a discontinuous way
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00—Tempering or quenching glass products
    • C03B27/02—Tempering or quenching glass products using liquid
    • C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt

Definitions

  • the invention belongs to the field of glass materials, and specifically relates to a Li 2 O-Al 2 O 3 -SiO 2 -B 2 O 3 series glass with a softening point not higher than 820° C. and capable of ion exchange.
  • the chemical strengthening technology is a well-known technology, that is, the ions with a smaller radius on the glass surface and the ions with a larger radius in the molten salt are mutually replaced, so that the glass surface has a certain depth of compressive stress layer.
  • double stress layer glass has gradually appeared, such as Corning's fifth and sixth generation glass.
  • the present invention intends to provide a glass with a low softening point and improved ion exchange performance, that is, a strengthened glass that can obtain at least one stress layer through ion exchange, and the strengthened glass has a stress layer depth of at least 90 ⁇ m.
  • the glass obtained in the present invention has a relatively low softening point temperature and is suitable for 3D molding.
  • the purpose of the present invention is to provide a Li 2 O-Al 2 O 3 -SiO 2 -B 2 O 3 series glass with a low softening point and improved ion exchange performance against the deficiencies of the prior art.
  • the softening point temperature of the glass obtained in the present invention is not higher than 820°C, which is favorable for 3D molding.
  • the glass can be ion-exchanged in a single molten salt bath or a mixed molten bath, so that at least one lamination stress area is obtained on the surface of the glass, and the depth of the stress layer is at least 90 ⁇ m.
  • a low-softening point lithium-containing glass the composition of which includes SiO 2 55%-70%, Al 2 O 3 12%-20%, B 2 O 3 0.5%-5%, Na 2 O 10 %-16%, Li 2 O 1-5%, P 2 O 5 0.01%-10%.
  • composition of the glass also includes SnO 2 in a weight percentage of 0.05%-0.5%.
  • composition of the glass also includes 0%-0.8% K 2 O by weight.
  • the glass contains substantially no MgO.
  • the softening point of the glass is ⁇ 820°C. More preferably, the softening point is less than 800°C.
  • the glass can be ion exchanged for less than or equal to 5 hours in a single molten salt bath or a mixed salt bath at a temperature range of 380°C to 450°C, so that at least one lamination stress area is obtained on the glass surface, and the stress layer depth At least 90 ⁇ m or more.
  • the molten salt bath used is KNO 3 molten salt, NaNO 3 molten salt or a combination of both.
  • SiO 2 is the main formed body of the glass of the present invention, which is one of the essential components, and constitutes the main glass network structure.
  • the glass contains SiO 2 at a concentration of about 55-70 wt%, and enough SiO 2 gives the glass better chemical stability and mechanical properties. However, the molding performance of the glass will decrease with the increase of SiO 2 , so the SiO 2 concentration should be controlled below 70wt%.
  • Al 2 O 3 is one of the essential components of the glass of the present invention. Similar to SiO 2 , it can form a glass network structure, thereby improving glass stability and mechanical properties. Al 2 O 3 formed in glass has a larger volume of aluminum oxide tetrahedron than silicon oxide tetrahedron in glass, and the volume of the glass expands, thereby reducing the density of the glass; and it also provides exchange channels for the glass in the ion exchange process. It greatly improves the compression stress and the depth of the stress layer of the glass; at the same time, when the content of Al 2 O 3 and the content of SiO 2 and alkali metal in the glass reach a balanced state, the overflow molding characteristics of the glass can be improved.
  • Al 2 O 3 is an extremely refractory oxide, which can quickly increase the viscosity of the glass, which makes it more difficult to clarify and homogenize the glass, and the probability of the defect concentration in the glass increases sharply. Therefore, in the present invention, the concentration of Al 2 O 3 is limited to about 12 wt% to 20 wt%.
  • the present invention preferably restricts SiO 2 +Al 2 O 3 to 75 wt% or more.
  • P 2 O 5 is a component of the glass forming body. In order not to reduce the melting and molding characteristics of the glass too much, the concentration of P 2 O 5 is limited to less than 10 wt% in the present invention.
  • B 2 O 3 is a network forming body oxide, which can reduce the melt viscosity of glass, and research shows that it can effectively inhibit the decomposition of zircon. Therefore, the present invention adds more than 0.5 wt% of B 2 O 3 .
  • B 2 O 3 is not conducive to obtaining high compressive stress and high stress layer depth of the glass. Therefore, in the present invention, the concentration of B 2 O 3 is controlled to be less than 5 wt%.
  • Li 2 O is one of the ion exchange components.
  • the present invention proves through a large number of experiments that lithium-containing glass can quickly obtain a high compressive stress layer through the exchange of Li + and Na + in the glass in a sodium-containing molten salt at a suitable temperature. depth.
  • Li 2 O can reduce the viscosity characteristics of the glass quickly, especially when the high temperature viscosity is significantly reduced, which is beneficial to the melting and clarification of the glass, and provides the possibility for the high concentration of Al 2 O 3 in the glass.
  • the Li 2 O concentration in the present invention is not If the concentration of Li 2 O is too low, the exchange amount of Li + and Na + in the glass is insufficient, and it is difficult to obtain the depth of the high compressive stress layer; but the concentration of Li 2 O is too high, and the liquidus temperature increases with the viscosity of the glass. It is lowered, so that the glass becomes prone to devitrification. Therefore, the Li 2 O concentration in the present invention should not be higher than 5wt%.
  • Na 2 O is one of the essential components in glass. It provides a large amount of free oxygen source, destroys the glass silica network structure, greatly reduces the viscosity of the glass, and helps the glass to melt and clarify. At the same time, maintaining a relatively high concentration of Na 2 O in the glass provides the possibility of chemical strengthening of the glass. Therefore, the concentration of Na 2 O in the present invention is not less than about 10 wt%. However, if the Na 2 O concentration is too high, the mechanical properties and chemical stability of the glass will be deteriorated. Especially in high alumina concentration and phosphorus-containing silicate glass, Na 2 O tends to exchange with hydrogen ions in the water and dissolve into it.
  • the Na 2 O concentration on the glass surface can be maintained by the exchange of Li + and Na + in the sodium-containing molten salt, so that the glass surface maintains a high concentration of Na.
  • the concentration of Na ions required for the exchange of K + and Na + on the surface of the glass in the potassium-containing molten salt, so the Na 2 O concentration in the glass is preferably less than about 16 wt %.
  • the present invention keeps K 2 O at a low level, that is, without intentionally using raw materials to introduce K 2 O to make it The content is less than 1wt%.
  • the present invention preferably limits R 2 O/(Al 2 O 3 +B 2 O 3 ) to less than 1.2.
  • the glass of the present invention contains a chemical fining agent, in which the concentration of SnO 2 is controlled at about 0.05 to 0.5 wt%.
  • the glass product in the present invention generates a compressive stress and a compressive stress layer on the glass surface through ion exchange between small radius ions in the glass and large radius ions in the molten salt.
  • the compressive stress layer at least includes DOL1 formed by the exchange of sodium ions and potassium ions. Or one of DOL2 formed by the exchange of lithium ions and sodium ions.
  • the softening point temperature of the glass of the invention is not higher than 820°C, which is beneficial to 3D molding.
  • the glass can be ion-exchanged in a single molten salt bath or a mixed molten bath, so that at least one lamination stress area is obtained on the glass surface, and the depth of the stress layer is at least 90 ⁇ m.
  • the raw materials (quartz sand, alumina, soda ash, anhydrous borax, potassium nitrate, tin oxide, lithium carbonate, aluminum metaphosphate) are weighed and mixed according to the purity and moisture content.
  • Ion exchange of glass Prepare the annealed glass block into a glass flake with a thickness of about 0.7mm, and clean it with ultrasonic for use; after preheating the glass flake at 250°C ⁇ 300°C, soak it at 380°C ⁇ Soak in molten salt at 430°C for 20 to 120 minutes (the molten salt is potassium nitrate molten salt containing 20% to 50% by weight of sodium nitrate), then take out the glass flakes and soak in molten salt at 380 to 430°C for 10 to 90 minutes (The molten salt is a potassium nitrate molten salt with a sodium nitrate content of less than 20 wt%), the glass is taken out, and washed for testing.
  • Annealing point (°C): the temperature point when the glass viscosity is 10 13 poise, measured according to ASTM C-336 fiber elongation testing method;
  • E. CS1, DOL1 and CS2, DOL2 are the compressive stress value and the depth of the stress layer on the glass surface after ion exchange.
  • CS1 and DOL1 are produced by potassium and sodium ion exchange
  • CS2 and DOL2 are produced by sodium and lithium ion exchange.
  • the testing instrument is the Japan Orihara SLP-1000 surface stress meter.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

A lithium-containing glass having a low softening point comprises the following components in percentages by weight: SiO 2 55％-70％, Al 2O 3 12％-20％, B 2O 3 0.5％-5％, Na 2O 10％-16％, Li 2O 1-5％, and P 2O 5 0.01％-10％. The Li 2O-Al 2O 3-SiO 2-B 2O 3-based glass can perform ion exchange in a single molten salt bath or a mixed molten bath, such that a surface of the glass has at least one compressive stress region, and a stress layer thereof has a depth at least greater than 90μm.

Description

一种低软化点含锂玻璃A kind of low softening point lithium-containing glass 技术领域Technical field
本发明属于玻璃材料领域，具体涉及一种软化点不高于820℃且可进行离子交换的Li 2O-Al 2O 3-SiO 2-B 2O 3系玻璃。 The invention belongs to the field of glass materials, and specifically relates to a Li 2 O-Al 2 O 3 -SiO 2 -B 2 O 3 series glass with a softening point not higher than 820° C. and capable of ion exchange.
背景技术Background technique
伴随市场发展需求，业内人员不断的加强高性能玻璃配方的研发，并改善该玻璃的力学性能，其中很重要的一项就是改善玻璃的化学强化性能。化学强化技术属大众熟知技术，即玻璃表面半径较小的离子与熔盐中半径较大的离子进行相互置换，进而使得玻璃表面具有一定深度的压应力层。近年来，为了提升玻璃的耐摔性能，双应力层玻璃也逐渐出现，如康宁公司的第五代、第六代玻璃。Along with market development needs, industry personnel continue to strengthen the research and development of high-performance glass formulations and improve the mechanical properties of the glass, one of which is to improve the chemical strengthening properties of the glass. The chemical strengthening technology is a well-known technology, that is, the ions with a smaller radius on the glass surface and the ions with a larger radius in the molten salt are mutually replaced, so that the glass surface has a certain depth of compressive stress layer. In recent years, in order to improve the drop resistance of glass, double stress layer glass has gradually appeared, such as Corning's fifth and sixth generation glass.
发明概述Summary of the invention
技术问题technical problem
2016年～2017年，3D玻璃盖板开始走强，多家主流终端手机厂商纷纷采用，曲面玻璃一跃成为手机盖板高端机型的标配。为了更好的实现玻璃的3D形状，适当降低玻璃的软化点将有助于玻璃的生产成型。From 2016 to 2017, 3D glass cover began to strengthen, and many mainstream terminal mobile phone manufacturers adopted it. Curved glass has become the standard for high-end mobile phone cover models. In order to better realize the 3D shape of the glass, appropriately lowering the softening point of the glass will help the production and molding of the glass.
本发明意在提供一种低软化点且可改善离子交换性能的玻璃，即一种可通过离子交换获得至少一层应力层的强化玻璃，该强化玻璃具有的应力层深度至少90μm以上。同时，本发明所得玻璃具有相对较低的软化点温度，适合用于3D成型。The present invention intends to provide a glass with a low softening point and improved ion exchange performance, that is, a strengthened glass that can obtain at least one stress layer through ion exchange, and the strengthened glass has a stress layer depth of at least 90 μm. At the same time, the glass obtained in the present invention has a relatively low softening point temperature and is suitable for 3D molding.
问题的解决方案The solution to the problem
技术解决方案Technical solutions
本发明的目的在于针对现有技术的不足，提供一种具有低软化点且可改善离子交换性能的Li 2O-Al 2O 3-SiO 2-B 2O 3系玻璃。本发明所得玻璃的软化点温度不高于820℃，有利于3D成型。同时，所述玻璃可在单一熔盐浴或混合熔浴中进行离子交换，使玻璃表面获得至少一层压应力区域，且应力层深度至少在90μm以上 。 The purpose of the present invention is to provide a Li 2 O-Al 2 O 3 -SiO 2 -B 2 O 3 series glass with a low softening point and improved ion exchange performance against the deficiencies of the prior art. The softening point temperature of the glass obtained in the present invention is not higher than 820°C, which is favorable for 3D molding. At the same time, the glass can be ion-exchanged in a single molten salt bath or a mixed molten bath, so that at least one lamination stress area is obtained on the surface of the glass, and the depth of the stress layer is at least 90 μm.
为实现上述目的，本发明采用如下技术方案：In order to achieve the above objectives, the present invention adopts the following technical solutions:
一种低软化点含锂玻璃，其组成成分按重量百分数计包括：SiO 2 55％-70％、Al 2O 3 12％-20％、B 2O 3 0.5％-5％、Na 2O 10％-16％、Li 2O 1-5％，P 2O 5 0.01％-10％。 A low-softening point lithium-containing glass, the composition of which includes SiO 2 55%-70%, Al 2 O 3 12%-20%, B 2 O 3 0.5%-5%, Na 2 O 10 %-16%, Li 2 O 1-5%, P 2 O 5 0.01%-10%.
所述玻璃的组成成分中还包括重量百分数为0.05％-0.5％的SnO 2。 The composition of the glass also includes SnO 2 in a weight percentage of 0.05%-0.5%.
所述玻璃的组成成分中还包括重量百分数为0％-0.8％的K 2O。 The composition of the glass also includes 0%-0.8% K 2 O by weight.
所述玻璃中基本不含MgO。The glass contains substantially no MgO.
其中，SiO 2+Al 2O 3＞75％。 Among them, SiO 2 +Al 2 O 3 >75%.
R 2O/(Al 2O 3+B 2O 3)＜1.2，R 2O为Li 2O、Na 2O与K 2O之和。 R 2 O/(Al 2 O 3 +B 2 O 3 )<1.2, and R 2 O is the sum of Li 2 O, Na 2 O, and K 2 O.
所述玻璃的软化点≤820℃。更优的，软化点＜800℃。The softening point of the glass is ≤ 820°C. More preferably, the softening point is less than 800°C.
所述玻璃可在单一熔盐浴或混合盐熔浴中于380℃～450℃的温度范围下进行小于或等于5小时的离子交换，使玻璃表面获得至少一层压应力区域，且应力层深度至少在90μm以上。所用熔盐浴为KNO 3熔盐、NaNO 3熔盐或二者的组合。 The glass can be ion exchanged for less than or equal to 5 hours in a single molten salt bath or a mixed salt bath at a temperature range of 380°C to 450°C, so that at least one lamination stress area is obtained on the glass surface, and the stress layer depth At least 90μm or more. The molten salt bath used is KNO 3 molten salt, NaNO 3 molten salt or a combination of both.
SiO 2为本发明所述玻璃的主要成形体，其是必需成分之一，构成了玻璃网状主结构。玻璃中含浓度约55～70wt％的SiO 2，足够多的SiO 2赋予玻璃较佳化学稳定性、机械性能。但玻璃的成型性能会随着SiO 2的增加而降低，故SiO 2浓度应控制在低于70wt％。 SiO 2 is the main formed body of the glass of the present invention, which is one of the essential components, and constitutes the main glass network structure. The glass contains SiO 2 at a concentration of about 55-70 wt%, and enough SiO 2 gives the glass better chemical stability and mechanical properties. However, the molding performance of the glass will decrease with the increase of SiO 2 , so the SiO 2 concentration should be controlled below 70wt%.
Al 2O 3为本发明所述玻璃的必需成分之一，与SiO 2类似，其能构成玻璃网状结构，从而提高玻璃稳定性和机械性能。Al 2O 3在玻璃中形成的铝氧四面体比玻璃中的硅氧四面体体积要大，玻璃体积发生膨胀，从而降低玻璃的密度；且其还为玻璃在离子交换过程中提供交换通道，极大提高了玻璃压缩成应力和压缩成应力层深；同时，当玻璃中Al 2O 3含量和SiO 2及碱金属含量达到平衡状态时可以改善玻璃的溢流成型特性。但Al 2O 3属于极难熔氧化物，能快速提高玻璃粘度，致使玻璃澄清均化难度加大，玻璃中缺陷浓度几率急剧增加。故本发明中限定Al 2O 3的浓度约12wt％～20wt％。 Al 2 O 3 is one of the essential components of the glass of the present invention. Similar to SiO 2 , it can form a glass network structure, thereby improving glass stability and mechanical properties. Al 2 O 3 formed in glass has a larger volume of aluminum oxide tetrahedron than silicon oxide tetrahedron in glass, and the volume of the glass expands, thereby reducing the density of the glass; and it also provides exchange channels for the glass in the ion exchange process. It greatly improves the compression stress and the depth of the stress layer of the glass; at the same time, when the content of Al 2 O 3 and the content of SiO 2 and alkali metal in the glass reach a balanced state, the overflow molding characteristics of the glass can be improved. However, Al 2 O 3 is an extremely refractory oxide, which can quickly increase the viscosity of the glass, which makes it more difficult to clarify and homogenize the glass, and the probability of the defect concentration in the glass increases sharply. Therefore, in the present invention, the concentration of Al 2 O 3 is limited to about 12 wt% to 20 wt%.
为了保持玻璃的高强度本征特性，本发明优选的限制SiO 2+Al 2O 3在75wt％以上。 In order to maintain the high-strength intrinsic properties of the glass, the present invention preferably restricts SiO 2 +Al 2 O 3 to 75 wt% or more.
与SiO 2、Al 2O 3类似，P 2O 5属于玻璃形成体成分，为不过多的降低玻璃的熔化特性及成型特性，本发明中将P 2O 5浓度限制在10wt％以内。 Similar to SiO 2 and Al 2 O 3 , P 2 O 5 is a component of the glass forming body. In order not to reduce the melting and molding characteristics of the glass too much, the concentration of P 2 O 5 is limited to less than 10 wt% in the present invention.
B 2O 3属于网络形成体氧化物，可降低玻璃熔融粘度，并且研究表明其可有效的抑制锆石的分解，因此本发明加入高于0.5wt％的B 2O 3。但对于玻璃离子交换性能而言，B 2O 3不利于玻璃获取高压缩应力和高应力层深度，因此本发明中将B 2O 3浓度控制在小于5wt％。 B 2 O 3 is a network forming body oxide, which can reduce the melt viscosity of glass, and research shows that it can effectively inhibit the decomposition of zircon. Therefore, the present invention adds more than 0.5 wt% of B 2 O 3 . However, for glass ion exchange performance, B 2 O 3 is not conducive to obtaining high compressive stress and high stress layer depth of the glass. Therefore, in the present invention, the concentration of B 2 O 3 is controlled to be less than 5 wt%.
本发明中Li 2O属于离子交换成分之一，本发明通过大量实验证明含锂玻璃在含钠熔盐中、在合适温度下，可通过玻璃中Li +和Na +交换快速获得高压缩应力层深度。此外，Li 2O可使玻璃粘度特性快速下降，尤其是降低高温粘度明显，有利于玻璃熔化与澄清，为玻璃中高浓度的Al 2O 3浓度提供可能性，故本发明中Li 2O浓度不低于约1wt％，如Li 2O浓度过低，玻璃中Li +和Na +交换量不足，难以获得高压缩应力层深度；但Li 2O浓度过高，其液相线温度随着玻璃粘度而降低，从而使玻璃变得容易失透，因此，本发明中Li 2O浓度不应高于5wt％。 In the present invention, Li 2 O is one of the ion exchange components. The present invention proves through a large number of experiments that lithium-containing glass can quickly obtain a high compressive stress layer through the exchange of Li + and Na + in the glass in a sodium-containing molten salt at a suitable temperature. depth. In addition, Li 2 O can reduce the viscosity characteristics of the glass quickly, especially when the high temperature viscosity is significantly reduced, which is beneficial to the melting and clarification of the glass, and provides the possibility for the high concentration of Al 2 O 3 in the glass. Therefore, the Li 2 O concentration in the present invention is not If the concentration of Li 2 O is too low, the exchange amount of Li + and Na + in the glass is insufficient, and it is difficult to obtain the depth of the high compressive stress layer; but the concentration of Li 2 O is too high, and the liquidus temperature increases with the viscosity of the glass. It is lowered, so that the glass becomes prone to devitrification. Therefore, the Li 2 O concentration in the present invention should not be higher than 5wt%.
Na 2O为玻璃中必需成分之一，其提供大量游离氧来源，对玻璃硅氧网络结构体起破坏作用，大大降低玻璃的粘度，有助于玻璃熔化与澄清。同时，玻璃维持较高浓度的Na 2O为玻璃化学强化提供了可能。因此，本发明中Na 2O浓度不低于约10wt％。但Na 2O浓度过高，将使得玻璃机械性能和化学稳定性能劣化，尤其在高氧化铝浓度和含磷成分的硅酸玻璃中，Na 2O更容易倾向与水中的氢离子交换而溶入水中，加速玻璃表面化学性能变化；在含锂玻璃成分中，玻璃表面的Na 2O浓度可以通过含钠熔盐中Li +和Na +交换来维持，使玻璃表面维持高浓度的Na浓度，保证玻璃在含钾熔盐中玻璃表面中K +和Na +交换所需的Na离子浓度，因此玻璃中Na 2O浓度优选低于约16wt％。 Na 2 O is one of the essential components in glass. It provides a large amount of free oxygen source, destroys the glass silica network structure, greatly reduces the viscosity of the glass, and helps the glass to melt and clarify. At the same time, maintaining a relatively high concentration of Na 2 O in the glass provides the possibility of chemical strengthening of the glass. Therefore, the concentration of Na 2 O in the present invention is not less than about 10 wt%. However, if the Na 2 O concentration is too high, the mechanical properties and chemical stability of the glass will be deteriorated. Especially in high alumina concentration and phosphorus-containing silicate glass, Na 2 O tends to exchange with hydrogen ions in the water and dissolve into it. Water accelerates the change of the chemical properties of the glass surface; in the composition of lithium-containing glass, the Na 2 O concentration on the glass surface can be maintained by the exchange of Li + and Na + in the sodium-containing molten salt, so that the glass surface maintains a high concentration of Na. The concentration of Na ions required for the exchange of K + and Na + on the surface of the glass in the potassium-containing molten salt, so the Na 2 O concentration in the glass is preferably less than about 16 wt %.
少量K 2O的存在可以改善离子扩散率，但是K 2O对锆石分解温度具有不利影响，因此本发明将K 2O保持在低水平，即不刻意的使用原料引入K 2O，使得其含量小于1wt％。 The presence of a small amount of K 2 O can improve ion diffusivity, but K 2 O has an adverse effect on the decomposition temperature of zircon. Therefore, the present invention keeps K 2 O at a low level, that is, without intentionally using raw materials to introduce K 2 O to make it The content is less than 1wt%.
为了夯实玻璃网络结构，本发明优选的将R 2O/(Al 2O 3+B 2O 3)限制在小于1.2以内。 In order to consolidate the glass network structure, the present invention preferably limits R 2 O/(Al 2 O 3 +B 2 O 3 ) to less than 1.2.
除上述的氧化物之外，本发明的玻璃中含化学澄清剂，其中SnO 2浓度控制在约0.05～0.5wt％。 In addition to the above-mentioned oxides, the glass of the present invention contains a chemical fining agent, in which the concentration of SnO 2 is controlled at about 0.05 to 0.5 wt%.
本发明中玻璃制品通过玻璃中小半径离子与熔盐中大半径离子进行离子交换从而在玻璃表面产生压缩应力和压缩应力层，所述压缩应力层至少包含由钠离子与钾离子交换形成的DOL1、或由锂离子与钠离子交换形成的DOL2中的一种。发明的有益效果The glass product in the present invention generates a compressive stress and a compressive stress layer on the glass surface through ion exchange between small radius ions in the glass and large radius ions in the molten salt. The compressive stress layer at least includes DOL1 formed by the exchange of sodium ions and potassium ions. Or one of DOL2 formed by the exchange of lithium ions and sodium ions. The beneficial effects of the invention
有益效果Beneficial effect
本发明玻璃的软化点温度不高于820℃，有利于3D成型。同时，所述玻璃可在单一熔盐浴或混合熔浴中进行离子交换，使玻璃表面获得至少一层压应力区域，且应力层深度至少在90μm以上。The softening point temperature of the glass of the invention is not higher than 820°C, which is beneficial to 3D molding. At the same time, the glass can be ion-exchanged in a single molten salt bath or a mixed molten bath, so that at least one lamination stress area is obtained on the glass surface, and the depth of the stress layer is at least 90 μm.
发明实施例Invention embodiment
本发明的实施方式Embodiments of the invention
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。In order to make the content of the present invention easier to understand, the technical solutions of the present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to this.
实施例Example
1.按表1所示成分组成将各原料(石英砂、氧化铝、纯碱、无水硼砂、硝酸钾、氧化锡、碳酸锂、偏磷酸铝)依据纯度与水分含量进行配合后称重混合，以获得均匀的配合料；然后将配合料转移至约800ml铂坩埚中，将铂坩埚置入硅钼棒高温炉炉内，逐渐升温至1650℃，持温3～8小时，通过搅拌加速玻璃气泡排出和使玻璃均化消除。在熔融后，将熔融液倒入至耐热不锈钢模具进行成型，然后取出玻璃块并移入箱式退火炉内，于600℃进行约2小时的热处理，随后以小于1℃/分的速率降至550℃，之后自然冷却至室温(为取得更加稳定的测量结果，应选择化学级的配合原料)。1. According to the composition shown in Table 1, the raw materials (quartz sand, alumina, soda ash, anhydrous borax, potassium nitrate, tin oxide, lithium carbonate, aluminum metaphosphate) are weighed and mixed according to the purity and moisture content. To obtain a uniform batch material; then transfer the batch material to about 800ml platinum crucible, put the platinum crucible into the silicon-molybdenum rod high-temperature furnace, gradually increase the temperature to 1650℃, hold the temperature for 3-8 hours, and accelerate the glass bubbles by stirring Discharge and homogenize the glass. After melting, pour the molten liquid into the heat-resistant stainless steel mold for molding, then take out the glass block and move it into the box annealing furnace, heat treatment at 600 ℃ for about 2 hours, and then reduce to less than 1 ℃ / min 550°C, and then naturally cool to room temperature (in order to obtain more stable measurement results, chemical-grade materials should be selected).
2.玻璃的离子交换：将退火后的玻璃块制备成厚度约0.7mm的玻璃薄片，采用超声波进行清洗备用；将玻璃薄片于250℃～300℃预热处理后，将其浸泡在380℃～430℃熔盐中浸泡20～120分钟(所述熔盐是含有20wt％～50wt％硝酸钠的硝酸钾熔盐)，再将玻璃薄片取出，于380～430℃熔盐中浸泡10～90分钟(所述熔盐是硝酸钠含量低于20wt％的硝酸钾熔盐)，将玻璃取出，清洗待测试。2. Ion exchange of glass: Prepare the annealed glass block into a glass flake with a thickness of about 0.7mm, and clean it with ultrasonic for use; after preheating the glass flake at 250℃～300℃, soak it at 380℃～ Soak in molten salt at 430°C for 20 to 120 minutes (the molten salt is potassium nitrate molten salt containing 20% to 50% by weight of sodium nitrate), then take out the glass flakes and soak in molten salt at 380 to 430°C for 10 to 90 minutes (The molten salt is a potassium nitrate molten salt with a sodium nitrate content of less than 20 wt%), the glass is taken out, and washed for testing.
玻璃样品的物理性质如表1所示。其定义及解释如下所示：The physical properties of the glass samples are shown in Table 1. Its definition and explanation are as follows:
A.软化点(℃)：玻璃粘度为10 7.6泊时的温度点，根据ASTM C-338纤维伸长检测方法测量； A. Softening point (℃): the temperature point when the glass viscosity is 10 7.6 poise, measured according to ASTM C-338 fiber elongation testing method;
B.退火点(℃)：玻璃粘度为10 13泊时的温度点，根据ASTM C-336纤维伸长检测方法测量； B. Annealing point (℃): the temperature point when the glass viscosity is 10 13 poise, measured according to ASTM C-336 fiber elongation testing method;
C.应变点(℃)：玻璃粘度为10 14.5泊时的温度点，根据ASTM C-336纤维伸长检测方法测量； C. Strain point (℃): the temperature point when the glass viscosity is 10 14.5 poise, measured according to ASTM C-336 fiber elongation testing method;
D.维氏硬度：经离子交换处理后，玻璃的维氏硬度值，载荷200g，加载时间15秒。D. Vickers hardness: after ion exchange treatment, the Vickers hardness value of the glass, load 200g, load time 15 seconds.
E.CS1、DOL1和CS2、DOL2为经离子交换后玻璃表面的压应力值和应力层深度。其中CS1、DOL1为钾钠离子交换产生的，CS2、DOL2为钠锂离子交换产生。测试仪器为日本折原SLP-1000表面应力仪。E. CS1, DOL1 and CS2, DOL2 are the compressive stress value and the depth of the stress layer on the glass surface after ion exchange. Among them, CS1 and DOL1 are produced by potassium and sodium ion exchange, and CS2 and DOL2 are produced by sodium and lithium ion exchange. The testing instrument is the Japan Orihara SLP-1000 surface stress meter.
表1实施例1-8的玻璃配方及性能测试Table 1 Glass formula and performance test of Examples 1-8
Figure PCTCN2019099256-appb-000001
Figure PCTCN2019099256-appb-000001
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。The foregoing descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made in accordance with the scope of the patent application of the present invention shall fall within the scope of the present invention.

Claims (8)

  1. 一种低软化点含锂玻璃，其特征在于：其组成成分按重量百分数计包括：SiO 255％-70％、Al 2O 312％-20％、B 2O 30.5％-5％、Na 2O10％-16％、Li 2O1-5％，P 2O 50.01％-10％。 A low softening point lithium-containing glass, which is characterized in that its composition includes SiO 2 55%-70%, Al 2 O 3 12%-20%, B 2 O 3 0.5%-5%, Na 2 O 10%-16%, Li 2 O1-5%, P 2 O 5 0.01%-10%.
  2. 如权利要求1所述的低软化点含锂玻璃，其特征在于：所述玻璃的组成成分中还包括重量百分数为0％-0.8％的K 2O。 The low softening point lithium-containing glass according to claim 1, wherein the composition of the glass further includes 0%-0.8% K 2 O by weight.
  3. 如权利要求1所述的低软化点含锂玻璃，其特征在于：所述玻璃中基本不含MgO。The low softening point lithium-containing glass according to claim 1, wherein the glass contains substantially no MgO.
  4. 如权利要求1所述的低软化点含锂玻璃，其特征在于：所述玻璃的组成成分中还包括重量百分数为0.05％-0.5％的SnO 2。 The low softening point lithium-containing glass according to claim 1, wherein the composition of the glass further includes SnO 2 in a weight percentage of 0.05% to 0.5%.
  5. 如权利要求1-4所述的任意一种低软化点含锂玻璃，其特征在于：组成中SiO 2+Al 2O 3＞75％。 The low-softening point lithium-containing glass according to any one of claims 1 to 4, characterized in that: SiO 2 + Al 2 O 3 in the composition> 75%.
  6. 如权利要求1-4所述的任意一种低软化点含锂玻璃，其特征在于：组成中R 2O/(Al 2O 3+B 2O 3)＜1.2，R 2O为Li 2O、Na 2O与K 2O之和。 The low softening point lithium-containing glass according to any one of claims 1 to 4, characterized in that: in the composition, R 2 O/(Al 2 O 3 +B 2 O 3 )<1.2, R 2 O is Li 2 O , The sum of Na 2 O and K 2 O.
  7. 如权利要求1-4所述的低软化点含锂玻璃，其特征在于：所述玻璃的软化点≤820℃。The low softening point lithium-containing glass according to claims 1-4, wherein the softening point of the glass is ≤ 820°C.
  8. 如权利要求1-4所述的低软化点含锂玻璃，其特征在于：所述玻璃在单一熔盐浴或混合盐熔浴中进行离子交换后，具有90μm以上的应力层深度。The low-softening point lithium-containing glass according to claims 1-4, wherein the glass has a stress layer depth of 90 μm or more after ion exchange in a single molten salt bath or a mixed salt bath.
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