WO2020078075A1 - 一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃 - Google Patents
一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃 Download PDFInfo
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- WO2020078075A1 WO2020078075A1 PCT/CN2019/099257 CN2019099257W WO2020078075A1 WO 2020078075 A1 WO2020078075 A1 WO 2020078075A1 CN 2019099257 W CN2019099257 W CN 2019099257W WO 2020078075 A1 WO2020078075 A1 WO 2020078075A1
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- glass
- ion exchange
- strain point
- acid resistance
- zinc
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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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- 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
Definitions
- the invention relates to the technical field of glass materials, in particular to a zinc-phospho-aluminosilicate glass with high strain point, fast ion exchange and weak acid resistance.
- touch screen and display cover glass With the development and demand of the touch screen and display market, it has driven the rapid development and demand of touch screen and display cover glass. With the pursuit of the appearance and performance of mobile terminal devices such as smart phones, the cover glass gradually transitions from the traditional 2D shape to 2.5D and 3D shapes. This also puts more stringent requirements on the performance of the cover glass used for protecting the screen. However, the strength of ordinary silicate glass still can not meet the needs of daily use, such as multiple drops of mobile phones and collision with sharp objects, etc., will cause damage to the screen. The cover glass is required to have high fracture resistance, bending resistance and drop resistance.
- the ion exchange effect of the glass depends on the temperature and time of the ion exchange.
- the glass has stress relaxation phenomenon.
- the stress relaxation of glass can be reduced by reducing the temperature of ion exchange, thereby maintaining a high surface compressive stress value, but at the same time, the efficiency of ion exchange is reduced, resulting in too low a compressive stress layer. Therefore, it is difficult to achieve high surface compressive stress values And high compressive stress layer.
- glass is required to be processed into products with 2.5D and 3D curved shapes.
- the glass surface such as CNC process 2.5D glass and hot bending forming process 3D glass, the glass surface is inevitably damaged in the processing process And, there are many stains on the glass surface, such as cerium oxide and other polishing powder.
- the glass In order to remove the dirt on the glass surface, the glass is generally cleaned with a weak acidic cleaning agent, such as an oxalic acid solution with a pH of 2, so the glass surface is required to have a certain resistance to weak acid to avoid the glass surface from being damaged by the weak acid and causing visible scratches Damage, thereby reducing the transmittance of the glass and affecting the yield.
- a weak acidic cleaning agent such as an oxalic acid solution with a pH of 2 2
- the purpose of the present invention is to provide a zinc phosphorus aluminum silicate glass with high strain point, fast ion exchange and weak acid resistance, which has high surface compressive stress, high compressive stress layer and weak acid resistance.
- the present invention adopts the following technical solutions:
- the composition of the glass SiO 2 + Al 2 O 3 + P 2 O 3 ⁇ 80%, (Al 2 O 3 + P 2 O 5 ) / ZnO> 3, (MgO + ZnO + SrO + Al 2 O 3 ) / (Li 2 O + Na 2 O + K 2 O + B 2 O 3 ) ⁇ 1.5, the strain point temperature of the glass is ⁇ 600 °C, and the compressive stress layer is ⁇ 40 ⁇ m.
- the glass has weak acid resistance, and the unit area after soaking in 60 ° C oxalic acid solution for 6hrs Weight loss rate ⁇ 0.15mg / cm 3 .
- SiO 2 is the main glass forming body, which is one of the essential components and mainly constitutes the glass network main structure, which gives the glass better chemical stability, mechanical properties and forming properties.
- the SiO 2 component in the glass belongs to the main component attacked by acidic substances, and it can increase the strain point temperature of the glass, so the SiO 2 content is at least 56%, preferably, at least 59%, more preferably, at least 60%;
- high SiO 2 content will increase the melting temperature of the glass, resulting in the defect of a large number of small bubbles in the glass, and also reduce the surface compressive stress and compressive stress layer of the glass after ion exchange, so the SiO 2 content is at most 65%, preferably , At most 64%, more preferably at most 63%.
- Al 2 O 3 is one of the essential components of glass and belongs to the network intermediate composition.
- alkaline ions charge balance Al 3+ ions, so that most alumina tends to become glass aluminum oxide tetrahedron, forming a glass network main structure, thereby improving glass stability and mechanical properties.
- the aluminum-oxygen tetrahedron formed by Al 2 O 3 in glass is larger in volume than the silicon-oxygen tetrahedron.
- the volume of the glass expands, which reduces the density of the glass, provides an exchange channel for the glass during the ion exchange process, and improves the glass compression
- the stress layer is deep, and the glass with high Al 2 O 3 concentration has a high strain point temperature, so that the glass maintains a high compression stress after glass ion exchange, and the Al 2 O 3 content in the glass is at least 17%, preferably, at least 18%; but Al 2 O 3 is a very refractory oxide, which can quickly increase the high-temperature viscosity of the glass, which makes it more difficult to clarify and homogenize the glass, and the concentration of bubble defects in the glass increases greatly, so the Al 2 O 3 content in the glass At most 22%, preferably at most 21%.
- Na 2 O is one of the essential components of the glass.
- the high concentration of Na 2 O in the glass makes the glass contain enough Na + to exchange with the K + ion in the molten salt of potassium nitrate, resulting in high compression on the glass surface stress.
- Na 2 O can provide a large number of free oxygen sources, which can damage the glass silicon oxide network structure, greatly reduce the viscosity of the glass, and help the glass melt and clarify. Therefore, the content of Na 2 O in the present invention is not less than 10 %, Preferably, not less than 11%, more preferably, not less than 12%. However, if the concentration of Na 2 O is too high, the mechanical properties and chemical stability of the glass will be deteriorated.
- Na 2 O is more prone to dissolve with hydrogen ions in water and dissolve into it.
- the chemical properties of the glass surface are accelerated, so the content of Na 2 O in the glass is at most 16%, preferably at most 16%.
- Li 2 O The glass component contains at most 1% Li 2 O, which is an unnecessary component. A certain Li 2 O concentration in the glass helps to reduce the melting viscosity of the glass, thereby improving the melting effect, but high Li 2 O tends to hinder the exchange of Na + and K + . Preferably, the glass does not contain Li 2 O.
- K 2 O is a non-essential component in glass.
- K 2 O can improve the melting and clarification effect of glass; when maintaining a high K 2 O concentration in glass helps to obtain a high compressive stress layer, but this compressive stress layer It is not necessarily the result of ion exchange between potassium ions and sodium ions in molten salt; at the same time, the high K 2 O concentration reduces the surface compressive stress caused by glass ion exchange more significantly; in addition, the chemical stability of high K 2 O concentration in glass deteriorates, making The acid resistance of glass becomes poor. Therefore, the K 2 O content in the glass of the present invention is at most 1%, preferably 0, which is mainly introduced through raw material impurities.
- B 2 O 3 The B 2 O 3 component in the glass is a network-forming oxide, which can significantly reduce the viscosity of high-temperature glass; high concentration B 2 O 3 has oxide volatilization during high-temperature melting, which is not conducive to the stability of the glass composition. And B 2 O 3 can reduce the glass strain point temperature, and it tends to be on the glass surface, the glass surface resistance performance is degraded. Ion exchange experiments show that high B 2 O 3 concentration is not conducive to the glass to obtain high compressive stress and high stress layer depth, so the B 2 O 3 content is less than 2%, preferably 0.
- P 2 O 5 in glass is a glass-forming body component, which is connected to each other by a [PO 4 ] tetrahedron to form a network, but the network structure formed by P 2 O 5 is a layer, and the layers are mutually driven by Van der Waals forces The connection makes the glass network structure loose, and the network gap becomes larger, which is conducive to the mutual diffusion of Na ions in the glass and K ions in the molten salt.
- the ion exchange plays a role in promoting the glass strengthening process, which can quickly obtain a higher compressive stress layer makes an important impact.
- P 2 O 5 in glass has low viscosity, poor chemical stability and large coefficient of thermal expansion. Therefore, low concentration of P 2 O 5 can provide glass with good chemical stability. High concentration of P 2 O 5 makes the glass surface resistant to acid Deterioration. Therefore, the P 2 O 5 content is at most 5%, preferably 1 to 4%.
- ZnO in glass belongs to a divalent metal oxide, which is a component of the outer body of the glass network, which has a destructive effect on the structure of the glass network, reduces the melting temperature of the glass, is a good flux, and is good for clarification.
- Zn 2+ exists in six-coordinated [ZnO 6 ] and four-coordinated [ZnO 4 ] states, in which the six-coordinated [ZnO 6 ] structure is denser, while the four-coordinated [ZnO 6 ] structure
- the structure of ZnO 4 ] is relatively loose, and the number of four coordinations increases with the increase of alkali metal oxides.
- ZnO content has a positive effect on improving glass ion exchange efficiency, exchange depth and glass surface strength, but too high concentration of ZnO tends to form zinc spinel (ZnAl 2 O 4 ) or zinc silicate (Zn 2 SiO 4 ), thereby increasing the devitrification temperature of the glass. Therefore, the content of ZnO is controlled at 1-8%. The priority is 2 to 6%.
- MgO in glass belongs to a divalent metal oxide, which is a component of the outer body of the glass network, which destroys the structure of the glass network, reduces the melting temperature of the glass, and is beneficial to clarification.
- the high MgO concentration has a limited effect on improving the strength of the glass; and in terms of the acid resistance of the glass, the effect of MgO is worse than that of ZnO. Therefore, the MgO content is at most 1%.
- SrO in glass is a divalent metal oxide, which is the outer component of the glass network, which can damage the structure of the glass network, reduce the melting temperature of the glass, and facilitate clarification.
- high SrO concentration increases the glass density, and the raw material cost is expensive.
- the SrO content is therefore at most 0.5%.
- the glass of the present invention contains a chemical clarifier.
- SnO 2 is the main high-temperature clarifier, and it is environmentally friendly and non-toxic, but SnO 2 at high concentration is prone to generate excessive oxygen, causing excessive bubbles to remain in the glass, and its content is at most 0.5%.
- CeO 2 is an oxidizing clarifying agent and can also be a decolorizing agent to increase the glass transmittance. However, if the concentration is too high, it will easily cause the glass to color and reduce the transmittance. Therefore, its content is at most 0.5%.
- the zinc phosphorus aluminum silicate glass of the present invention has high surface compressive stress, which is obtained by increasing the strain point temperature of the glass and reducing the stress relaxation phenomenon during the ion exchange process.
- All oxides in the glass that damage the results of the glass network such as Na 2 O, K 2 O, and Li 2 O, have the most obvious effect on reducing the strain point temperature of the glass; and the components in the glass that are conducive to the formation of the network structure
- Al 2 O 3 , SiO 2 and P 2 O 5 have the most obvious effect on increasing the strain temperature, so the glass in the present invention has a high concentration of SiO 2 , Al 2 O 3 and P 2 O 5 content, SiO 2 + Al 2 O 3 + P 2 O 5 ⁇ 76wt% and limit (MgO + ZnO + SrO + Al 2 O 3 ) / (Li 2 O + Na 2 O
- the glass in the present invention has a good weak acid resistance.
- the present invention improves the weak acid resistance of the glass through three aspects. On the one hand, it increases the content of SiO 2 in the glass. This composition is particularly effective in improving the weak acid resistance of the glass. SiO in the glass is required.
- the concentration is not less than 56wt%; on the one hand, the composition of Li 2 O, Na 2 O, K 2 O, and Al 2 O 3 in the glass that reduces the weak acid resistance of the glass surface is limited, and the limiting conditions are (Li 2 O + Na 2 O + K 2 O + Al 2 O 3 ) / SiO 2 ⁇ 0.60; on the other hand, a high ZnO concentration is introduced to reduce the MgO concentration to improve the ability of the glass to withstand weak acids.
- the present invention obtains glass with high surface compressive stress and compressive stress layer strengthening glass by increasing the strain point temperature of the glass and improving the ion exchange efficiency of the glass through a reasonable composition ratio; on the other hand, the present invention Invented to increase the content of SiO 2 in glass and limit the composition of Li 2 O, Na 2 O, K 2 O, and Al 2 O 3 in glass to reduce the weak acid resistance of the glass surface and introduce ZnO concentration in high aluminum glass components , Reduce the MgO concentration, thereby improving the ability of the glass to withstand weak acids.
- Sample preparation for Embodiment 1-12 and Comparative Example 1-2 Weigh according to the purity and moisture content of raw materials such as quartz sand, alumina, sodium carbonate, etc., and mix them uniformly to obtain uniform ingredients; then remove the ingredients from plastic bottles Transfer to a 800ml platinum crucible, place the platinum crucible in a high temperature furnace of silicon molybdenum rods, gradually increase the temperature to 1650 ° C, hold the temperature for 4-8 hours, accelerate the discharge of glass bubbles and eliminate the homogenization of the glass by stirring.
- raw materials such as quartz sand, alumina, sodium carbonate, etc.
- the molten liquid is poured into a heat-resistant stainless steel mold for molding, and then the glass block is taken out and moved into a box annealing furnace for heat treatment at 630 ° C for about 2 hours, and then reduced to 570 ° C at a rate of less than 1 ° C / min , And then naturally cooled to room temperature.
- the glass block is cut and grinded to meet the relevant test samples. In order to obtain more stable measurement results, chemical grade compound raw materials should be selected.
- RO is the sum of the mass fractions of MgO, ZnO and SrO
- R2O is the sum of the mass fractions of Li 2 O, Na 2 O and K 2 O.
- T softening the softening point temperature at 10 7.6 poises of glass, measured according to the standard method of ASTM C-338 "Standard Test Method for Softening Point of Glass";
- T anneal the annealing point temperature at 10 13 poises of glass viscosity, measured according to the standard method of ASTM C-336 "Standard Test Method for Annealing Point and Strain Point of Glass by Fiber Elongation";
- T stain the stress point temperature of the glass with a viscosity of 10 14.5 poise, measured according to the standard method of ASTM C-336 "Standard Test Method for Annealing Point and Strain Point of Glass by Fiber Elongation";
- DOL Depth of Layer of Surface Compression Stress Layer, which is tested by Japan Origami Industrial Co., Ltd. FSM-6000LE surface stress meter.
- Weight loss rate per unit area cut the glass into regular-shaped glass pieces, mount the samples for rough grinding, and finally use 2000 mesh sandpaper to finely grind the upper and lower surfaces of the glass samples. After drying, the sample is immersed in the oxalic acid solution with PH ⁇ 2, the temperature is set to 60 °C, and the time is 6 hours; a ten thousandth precision balance is used to measure the change in glass quality before and after immersion, and the weak acidity of the glass is calculated by measuring the glass surface The weight loss ratio in the solution.
- d density (g / ml), according to "GB / T 7962.20-2010 colorless optical glass test method-density test method "standard, the ambient temperature is 22 ⁇ 0.5 °C;
- CTE Coefficient of Linear Thermal Expansion, abbreviated as ASTM E228 "Standard Test Method for Linear Thermal Expansion of Solid Materials With a Push-Rod Dilatometer "standard method for measurement, the temperature range is 30 °C ⁇ 300 °C. ⁇ ⁇
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Abstract
一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃，以质量份数计，所述玻璃包含的组分为：SiO 2 56-65%，Al 2O 3 17-22%，Na 2O 10-16%，K 2O 0-1%，Li 2O 0-1%，P 2O 5 0-5%，B 2O 3 0-2%，MgO 0-5%，ZnO 1-8%，TiO 2 0-1%，SrO 0-0.5%，CeO 2 0-5%，各组分之和为100%；玻璃的应变点温度≥580℃，压缩应力值≥900MPa，压缩应力层≥35μm。
Description
本发明涉及玻璃材料技术领域，具体涉及一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃。
随着触摸屏和显示器市场的发展和需求，带动了触摸屏和显示器盖板玻璃迅速发展和需求。伴随人们对智能手机等移动终端装置外观以及性能的追求，盖板玻璃从传统的2D外形，逐步向2.5D、3D外形过渡。这也对作为保护屏幕用的盖板玻璃性能提出了更为苛刻的要求。但是，普通的硅酸盐玻璃强度还是不能满足日常使用需求，如手机的多次跌落以及与尖锐物体的碰撞等，都会造成屏幕的破损。要求盖板玻璃需要具有高的抗断裂、抗弯曲以及抗摔落性能，对于厚度小于1mm的盖板玻璃，一般需要通过化学钢化处理使玻璃具有表面压应力（Compressive Stress,简称CS）和一定深度的离子交换层（Depth of Layer,简称DOL），同时具有较高的CS和DOL玻璃可以有效的抑制玻璃表面缺陷扩展，从而提高玻璃表面硬度、抗刮伤性以及抗摔落性能。
当玻璃进行离子交换时，玻璃的离子交换效果取决于离子交换的温度和时间，温度越高，离子交换的速度越快，压应力层越深，但表面压缩应力值越小，主要是离子交换过程中，玻璃存在应力松弛现象。一般可通过降低离子交换的温度减轻玻璃的应力松弛，从而维持较高的表面压缩应力值，但同时离子交换的效率降低，导致压缩应力层过低，因此，很难同时达到高表面压缩应力值和高压缩应力层。
此外，随着2.5D、3D等曲面造型的触控显示屏渐成为主流产品，玻璃被要求加工成具有2.5D 、3D曲面造型的产品。当玻璃从2D被加工成2.5D和3D时，需要对玻璃表面进行造型加工，例如采用CNC制程加工2.5D玻璃以及采用热弯成型制程加工3D玻璃，玻璃表面不可避免的在加工制程中受到损伤，且玻璃表面残留许多脏污，例如氧化铈等抛光粉。为除去玻璃表面的脏污，一般采用弱酸性清洗剂对玻璃进行清洗，例如采用PH≈2的草酸溶液，因此，要求玻璃表面具有一定耐弱酸性能，避免玻璃表面不被弱酸破坏而产生可见划伤，从而降低玻璃的透过率影响良率。尤其当玻璃中引入一定量的P
2O
5组分后，玻璃的化学稳定性降低，从而使玻璃的耐弱酸性能降低；目前未见过能解决上述问题的报道。
本发明的目的在于提供一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃，该玻璃同时具有高表面压缩应力、高压缩应力层和耐弱酸性。
为实现上述目的，本发明采用如下技术方案：
一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃，以质量分数计，所述玻璃包含的组分为SiO
2 56～65 %，Al
2O
3
17～22%，Na
2O
10～16 %，K
2O
0～1%， Li
2O
0～1%， P
2O
5
0～5%， B
2O
3
0～2%，MgO 0～0.5%，ZnO 1~8%，TiO
2 0～1%，SrO 0～0.5%，SnO
2 0～0.5%，CeO
2 0～0.5%，各组分之和为100%。
所述玻璃的组分中，SiO
2+Al
2O
3+P
2O
3≥78%，(MgO+ZnO+SrO+Al
2O
3)
/( Li
2O+Na
2O+K
2O+B
2O
3)
≥1.3，玻璃的应变点温度≥580℃，压缩应力值≥900MPa，压缩应力层≥35μm。
优选地，所述玻璃的组分中，SiO
2+Al
2O
3+P
2O
3≥80%，(Al
2O
3+P
2O
5)/ZnO＞3，(MgO+ZnO+SrO+Al
2O
3)/(
Li
2O+Na
2O+K
2O+B
2O
3) ≥1.5，玻璃的应变点温度≥600℃，压缩应力层≥40μm。
所述玻璃的组分中，（Li
2O+Na
2O+K
2O + Al
2O
3）/SiO
2＜0.60，玻璃具有耐弱酸性，且在60℃草酸溶液中浸泡6hrs后单位面积重量损失率≤0.15mg/cm
3。
以下对各成分的含量进行数值限定的理由加以说明：
SiO
2：SiO
2为主要玻璃成形体，属必需成分之一，主要构成了玻璃网状主结构，其赋予玻璃较佳的化学稳定性、机械性能和成型性能。玻璃中SiO
2成分属于酸性物质侵蚀的主要组分，且其能提高玻璃的应变点温度，因此SiO
2含量至少为56 %，优选地，至少为59 %，更优选地，至少为60 %；但高SiO
2含量会使玻璃熔化温度提高，从而导致玻璃出现大量小气泡的缺陷，同时也会降低玻璃离子交换后的表面压缩应力和压缩应力层，因此SiO
2含量至多为65%，优选地，至多为64 %，更优选地，至多为63 %。
Al
2O
3：Al
2O
3为玻璃的必需成分之一，属于网络中间体组成。在高碱浓度玻璃成分中，碱性离子对Al
3+离子进行电荷平衡，使多数氧化铝倾向于成为玻璃铝氧四面体，构成了玻璃网状主结构，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在玻璃中体积比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，为玻璃在离子交换过程提供交换通道，提高玻璃压缩应力层深，同时高Al
2O
3浓度玻璃具有高应变点温度，从而使得玻璃离子交换后玻璃维持较高的压缩成应力，玻璃中Al
2O
3含量至少为17 %，优选地，至少为18 %；但Al
2O
3属于极难熔氧化物，其能快速提高玻璃高温粘度，致使玻璃澄清均化难度加大，玻璃中的气泡缺陷浓度大量增加，因此在玻璃中Al
2O
3含量至多为22 %，优选地，至多为21 %。
Na
2O：Na
2O为玻璃的必需成分之一，玻璃中高浓度的Na
2O，使得玻璃中含有足够多的Na+，与硝酸钾熔盐中K+离子进行交换，从而在玻璃表面产生高压缩应力。此外，Na
2O可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，因此，本发明中Na
2O含量不低于10 %，优选地，不低于11%，更优选地，不低于12%。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，因此玻璃中Na
2O含量至多为16 %，优选地，至多为16 %。
Li
2O：玻璃组分至多包含1 %Li
2O，其属于非必要成分。玻璃中一定Li
2O浓度有助于降低玻璃的熔化粘度，从而改善熔化效果，但高Li
2O倾向于阻碍Na
+和K
+交换，优选地，玻璃中不含Li
2O。
K
2O：玻璃中K
2O属于非必要成分，K
2O可以改善玻璃熔化与澄清效果；当玻璃中维持较高K
2O浓度有助于获得高压缩应力层，但这种压缩应力层未必是熔盐中钾离子与钠离子发生离子交换而形成；同时高K
2O浓度对玻璃离子交换产生的表面压应力降低更为明显；此外，玻璃中高K
2O浓度化学稳定性劣化，使玻璃抗酸性变差。因此，本发明的玻璃中K
2O含量至多为1%，优选为0，其主要通过原料杂质引入。
B
2O
3：玻璃中B
2O
3成分属于网络形成体氧化物，可明显降低高温玻璃粘度；高浓度B
2O
3在高温熔制过程中存在氧化物挥发现象，不利于玻璃成分稳定，且B
2O
3能降低玻璃应变点温度，且其倾向于在玻璃表面上，玻璃表面抗耐性能劣化。离子交换的实验表明，高 B
2O
3浓度不利于玻璃获得高压缩应力和高应力层深度，因此B
2O
3含量小于2 %，优选为0。
P
2O
5：玻璃中P
2O
5属于玻璃形成体成分，其以[PO
4]四面体相互连成网络，但P
2O
5形成的网络结构属于层状，且层间由范德华力相互连接，使玻璃网络结构呈疏松状态，网络空隙变大，有利于玻璃中Na离子和熔盐中K离子进行相互扩散，玻璃强化工艺过程中离子交换起促进作用，对快速获得较高压缩应力层起重要作用。但玻璃中P
2O
5具有粘度小，化学稳定性差和热膨胀系数大作用，因此低浓度P
2O
5能提供玻璃具有较好化学稳定性，高浓度的P
2O
5使玻璃表面的抗酸性劣化。因此P
2O
5含量至多为5%，优选1～4 %。
ZnO：玻璃中ZnO属于二价金属氧化物，其为玻璃网络外体成分，对玻璃网络结构起破坏作用，降低玻璃熔化温度，是良好的助熔剂，有利于澄清。在高碱金属氧化物硅酸盐玻璃中，Zn
2+存在六配位[ZnO
6]和四配位[ZnO
4]状态，其中六配位[ZnO
6]结构较为致密，而四配位[ZnO
4]结构较为疏松，四配位数量随碱金属氧化物增加而增加。当四配位[ZnO
4]含量较多时，玻璃网络更为疏松，有利于玻璃中离子（Na
+）迁移，从而提高玻璃离子交换层深度，相比同族的CaO、MgO和SrO对离子交换的阻碍作用，ZnO含量对提高玻璃离子交换效率、交换深度和提高玻璃表面强度具有积极作用，但过高浓度的ZnO倾向于形成锌尖晶石（ZnAl
2O
4）或硅酸锌（Zn
2SiO
4），从而提高玻璃的失透温度。因此ZnO含量控制在1～8 %。优先为2～6 %。
MgO：玻璃中MgO属于二价金属氧化物，其为玻璃网络外体成分，对玻璃网络结构起破坏作用，降低玻璃熔化温度，有利于澄清。但高MgO浓度对玻璃强度提高作用有限；并且在玻璃的抗酸性能方面，MgO效果比ZnO效果差，因此，MgO含量至多为1%。
SrO：玻璃中SrO属于二价金属氧化物，其为玻璃网络外体成分，对玻璃网络结构起破坏作用，降低玻璃熔化温度，有利于澄清。但高SrO浓度提高玻璃密度，且原料成本昂贵。因此SrO含量至多为0.5 %。
除上述的氧化物之外，本发明的玻璃中含有化学澄清剂。其中SnO
2为主要高温澄清剂，且环保无毒，但高浓度的SnO
2易于产生过量氧，造成过多气泡残留在玻璃中，其含量至多为0.5 %。其中CeO
2为氧化澄清剂，也可为脱色剂，提高玻璃透过率，但浓度过高，易导致玻璃着色，从而降低透过率，因此，其含量至多为0.5 %。
本发明的锌磷铝硅酸盐玻璃玻璃具有高表面压缩应力，是通过提高玻璃的应变点温度，降低离子交换过程中的应力松弛现象获得的。玻璃中凡是对玻璃网络结果起破坏作用的氧化物，例如Na
2O、K
2O和Li
2O，其对降低玻璃应变点温度的作用最明显；而玻璃中有利于形成网络结构的组分，例如Al
2O
3、SiO
2和P
2O
5对提高应变温度起作用最明显，因此本发明中玻璃具有高浓度的SiO
2、Al
2O
3和P
2O
5含量，SiO
2+Al
2O
3+P
2O
5≥76wt%并限制(MgO+ZnO+SrO+Al
2O
3)/(
Li
2O+Na
2O
+K
2O+B
2O
3)≥1.3。优选地，SiO
2+Al
2O
3+P
2O
5≥80wt%；优选地，(MgO+ZnO+SrO
+Al
2O
3)/(
Li
2O+Na
2O+K
2O+B
2O
3)≥1.5；从而改善玻璃的离子交换效率，缩短玻璃强化时间，改善玻璃的表面压缩应力值和压缩应力层。
本发明中的玻璃具有良好的耐弱酸的能力，本发明通过三方面改善玻璃的耐弱酸性能，一方面提高玻璃中SiO
2组成含量，该组成对改善玻璃耐弱酸效果尤为明显，要求玻璃中SiO
2浓度不低于56wt%；一方面对玻璃中Li
2O、Na
2O、K
2O和Al
2O
3导致玻璃表面的耐弱酸能力降低成分进行限制，限制条件为（Li
2O+Na
2O+K
2O
+ Al
2O
3）/SiO
2＜0.60；另一方面，引入高ZnO浓度，降低MgO浓度来改善玻璃耐弱酸的能力。
本发明的显著优点在于：本发明一方面通过合理的成分配比提高玻璃的应变点温度和改善玻璃的离子交换效率，获得具有高表面压缩应力值和压缩应力层强化玻璃；另一方面，本发明提高玻璃中SiO
2组成含量，并对玻璃中Li
2O、Na
2O、K
2O和Al
2O
3导致玻璃表面的耐弱酸能力降低成分进行限制和在高铝玻璃成分中引入ZnO浓度，降低MgO浓度，从而改善改善玻璃耐弱酸的能力。
以下结合具体实施例对本发明做进一步说明，但本发明不仅仅限于这些实施例。
实施例1-12和对比例1-2：
1、测试样品制备
实施案1-12及对比例1-2的样品制备：依据石英砂、氧化铝、碳酸钠等原料纯度与水分含量进行称量，进行均匀混合获得均匀的配料；然后将配合料从塑料瓶中转移至约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4～8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进行630℃约2小时的热处理，随后以小于1℃/分的速率降至570℃，之后自然冷却至室温。将玻璃块进行切割研磨制备成符合相关测试样品。为取得更加稳定的测量结果，应选择化学级的配合原料。
实施案1-12及对比例1-2的样品包含的成分如表一所示：
表一 实施例1-12及对比例1-2
表中RO为MgO、ZnO和SrO质量分数之和，R2O为Li
2O、Na
2O和K
2O质量份数之和。
表一实施例1-12及对比例1-2（续）
2、物理性质符号及测量方法定义
实施例1-12及对比例1-2玻璃的物理性质如表二所示，其定义及解释如下所示：
（1）T
softening：玻璃粘度为10
7.6泊时的软化点温度，根据ASTM
C-338《Standard Test Method for Softening Point
of Glass》标准方法测量；
（2）T
anneal:
玻璃粘度为10
13泊时的退火点温度，根据ASTM C-336《Standard
Test Method for Annealing Point and Strain Point of Glass by Fiber Elongation》标准方法测量；
（3）T
stain:
玻璃粘度为10
14.5泊时的应力点温度，根据ASTM C-336《Standard
Test Method for Annealing Point and Strain Point of Glass by Fiber Elongation》标准方法测量；
（4）CS：表面压缩应力Compressive Stress简称，即采用日本折原工业有限公司FSM-6000LE表面应力计进行测试。
（5）DOL：表面压缩应力层 Depth of Layer简称，采用日本折原工业有限公司FSM-6000LE表面应力计进行测试。
（6）单位面积重量损失率：将玻璃切割成规则形状的玻璃片，镶样进行粗磨，最后采用2000目砂纸对玻璃样品上下表面进行精磨。干燥后将样品浸没在PH≈2的草酸溶液中，温度设定为60℃，时间为6小时；采用万分之一精密天平测量浸泡前后玻璃质量变化，通过测量玻璃表面积计算获得玻璃在弱酸性溶液中的重量损失比。
（7）d:密度（克/毫升），根据《GB/T
7962.20-2010 无色光学玻璃测试方方法-密度测试方法》标准进行测量，环境温度为22±0.5℃；
（8）CTE：平均线热膨胀系数 Coefficient of Linear Thermal Expansion简称，采用ASTM E228 《Standard
Test Method for Linear Thermal Expansion of Solid Materials With a Push-Rod
Dilatometer》 标准方法进行测量，温度范围为30℃～300℃ 。
表二 实施例1-12及对比例1-2
表二 实施例1-12及对比例1-2（续）
从表1和表2可知，（1）虽然对比例1玻璃的应变点高于580℃，离子交换后玻璃表面获得高压缩应力值，但玻璃中ZnO＞9%，且(Al
2O
3+P
2O
5)/ZnO＜3%，故压缩应力层较差，低于35μm，由此可知离子交换效率明显比实施例1-12玻璃低；且由于对比例1玻璃中SiO
2含量低于56%，（Li
2O+Na
2O+K
2O
+ Al
2O
3）/SiO
2＜0.60，对比例1玻璃在PH=2和60℃的草酸溶液中，浸泡6小时后，单位面积重量损失率为2.23 mg/cm
3，玻璃耐弱酸性能差，在玻璃后端草酸浸泡清洗中，玻璃表面将被弱酸侵蚀从而造成强度下降或表面出现雾化。（2）对比例2玻璃的应变点温度较低，离子交换后玻璃表面获得压缩应力值低，同时其压缩应力层较差，低于35μm；即使SiO
2含量高于56wt%,但（Li
2O+Na
2O+K
2O
+ Al
2O
3）/SiO
2＜0.60，对比例1玻璃在PH=2和60℃的草酸溶液中，浸泡6小时后，单位面积重量损失率为0.18mg/cm
3，在玻璃后端草酸浸泡清洗中，玻璃表面将被弱酸侵蚀从而造成强度下降或表面出现雾化。
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。
Claims (6)
- 一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃，其特征在于：以质量分数计，所述玻璃包含的组分为：SiO 2 56～65 %，Al 2O 3 17～22%，Na 2O 10～16 %，K 2O 0～1%，Li 2O 0～1%，P 2O 5 0～5%，B 2O 3 0～2%，MgO 0～0.5%，ZnO 1~8%，TiO 2 0～1%，SrO 0～0.5%，SnO 2 0～0.5%，CeO 2 0～0.5%，各组分之和为100%；所述玻璃的组分以质量分数计：SiO 2+Al 2O 3+P 2O 3≥78%，(MgO+ZnO+SrO+Al 2O 3)/( Li 2O+Na 2O+K 2O+B 2O 3) ≥1.3，(Al 2O 3+P 2O 5)/ZnO＞3；所述玻璃的应变点温度≥580℃；所述玻璃是能进行快速离子交换的。
- 根据权利要求1所述的一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃，其特征在于：所述玻璃的组分以质量分数计：SiO 2+Al 2O 3+P 2O 3≥80%。
- 根据权利要求1所述的一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃，其特征在于：所述玻璃的压缩应力层≥35μm。
- 根据权利要求1所述的一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃，其特征在于：所述玻璃的压缩应力值≥900MPa。
- 根据权利要求1所述的一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃，其特征在于：所述玻璃在60℃草酸溶液中浸泡6hrs后单位面积重量损失率≤0.15mg/cm 3。
- 根据权利要求1所述的一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃，其特征在于：所述玻璃的组分以质量分数计：（Li 2O+Na 2O+K 2O + Al 2O 3）/SiO 2＜0.60。
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2018
- 2018-10-17 CN CN201811211310.2A patent/CN109020192A/zh active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008108332A1 (ja) * | 2007-03-02 | 2008-09-12 | Nippon Electric Glass Co., Ltd. | 強化板ガラスとその製造方法 |
| JP2015224155A (ja) * | 2014-05-27 | 2015-12-14 | コニカミノルタ株式会社 | 化学強化可能なガラス |
| CN107056047A (zh) * | 2017-06-08 | 2017-08-18 | 东旭科技集团有限公司 | 一种玻璃组合物及其制备方法和应用 |
| CN107651837A (zh) * | 2017-09-27 | 2018-02-02 | 东旭集团有限公司 | 一种用于保护显示器件的玻璃组合物及其制备方法 |
| CN109020192A (zh) * | 2018-10-17 | 2018-12-18 | 科立视材料科技有限公司 | 一种具有高应变点、可快速离子交换和耐弱酸性的锌磷铝硅酸盐玻璃 |
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