技术领域technical field
本发明属于玻璃材料领域，具体涉及一种可快速进行离子交换的含锂铝硅酸盐玻璃。The invention belongs to the field of glass materials, in particular to a lithium-containing aluminosilicate glass capable of rapid ion exchange.
背景技术Background technique
铝硅酸盐玻璃材料经离子交换强化后，被广泛应用于电子显示产品的防护覆盖产品，因此对可强化铝硅酸盐玻璃的力学性能提出了更高的要求，使得铝硅酸盐玻璃必须具有更高的表面压缩应力（Compressive Stress，简称CS）和更深的表面压缩应力层深（Depth ofLayer，简称DOL）。Aluminosilicate glass materials are widely used in protective covering products of electronic display products after being strengthened by ion exchange. It has higher surface compressive stress (Compressive Stress, referred to as CS) and deeper surface compressive stress layer depth (Depth of Layer, referred to as DOL).
铝硅酸盐玻璃的强化一般是利用玻璃表面离子半径较小的离子（例如Na+和Li+）与熔盐中离子(例如K+和Na+)相互置换，其中由于Li+具有更小的离子半径，交换速度和交换深度较Na+交换更好。现有技术中披露了很多可强化的铝硅酸盐玻璃。The strengthening of aluminosilicate glass generally uses ions with smaller ionic radii on the glass surface (such as Na+ and Li+ ) to replace each other with ions in molten salts (such as K+ and Na+ ), because Li+ has a smaller Ionic radius, exchange speed and exchange depth are better than Na+ exchange. A number of strengthenable aluminosilicate glasses are disclosed in the prior art.
专利CN102971267A提供一种可离子交换玻璃，其不含锂，并含有0.1-10摩尔%的P2O5以及至少5摩尔%的Al2O3。P2O5的存在使得玻璃能够比不含P2O5的同等玻璃进行更快并且达到更大深度的离子交换。但是相比于含锂的玻璃，该玻璃材料很难短时间内获得较高的压缩层深度。Patent CN102971267A provides an ion-exchangeable glass, which does not contain lithium, and contains 0.1-10 mol% of P2 O5 and at least 5 mol% of Al2 O3 .The presence ofP2O5enables the glass to ion exchange faster and to a greater depth than an equivalent glass withoutP2O5 . However, compared with lithium-containing glass, it is difficult for this glass material to obtain a higher compression layer depth in a short time.
专利CN105683106A提供了一种含硼和磷的可离子交换玻璃，提供了含有SiO2、Al2O3、Na2O、MgO、B2O3和P2O5的可离子交换玻璃。这些经过离子交换的玻璃在45或50微米(μm)深度的压缩应力大于900兆帕斯卡(MPa)，部分玻璃展现出至少1吉帕斯卡(GPa)的压缩应力。这些玻璃的离子交换速率远快于其他碱性铝硅酸盐玻璃的情况，并且经过离子交换的玻璃耐受冲击破坏的损坏。但该玻璃含有足量的B2O3且不含有Li2O，因此玻璃压缩应力层提高有限。Patent CN105683106A provides an ion-exchangeable glass containing boron and phosphorus, and provides an ion-exchangeable glass containing SiO2 , Al2 O3 , Na2 O, MgO, B2 O3 and P2 O5 . These ion-exchanged glasses exhibit compressive stresses greater than 900 megapascals (MPa) at depths of 45 or 50 micrometers (μm), with some glasses exhibiting compressive stresses of at least 1 gigapascal (GPa). The ion exchange rate of these glasses is much faster than is the case with other alkali aluminosilicate glasses, and the ion exchanged glasses are resistant to damage from impact damage. However, the glass contains a sufficient amount of B2 O3 and does not contain Li2 O, so the improvement of the glass compressive stress layer is limited.
专利CN103648996A提供了一种具有高压缩应力层的铝硅酸盐玻璃制品。所述玻璃制品包括至少约50摩尔%SiO2和至少约11摩尔%Na2O，且具有处于至少约900MPa压缩应力下的层，以及从该玻璃制品的表面延伸进入该玻璃的层深度为至少约30微米。但该玻璃含有较高浓度的Na2O，且不含P2O5，玻璃难以在短时间内获得较高的压应力和离子交换层深度。Patent CN103648996A provides an aluminosilicate glass product with a high compressive stress layer. The glass article comprises at least about 50 mole %SiO2 and at least about11 mole % Na2O, and has a layer under a compressive stress of at least about 900 MPa, and a layer extending from the surface of the glass article into the glass to a depth of at least about 30 microns. However, the glass contains a relatively high concentration of Na2 O and does not contain P2 O5 , so it is difficult for the glass to obtain high compressive stress and ion exchange layer depth in a short time.
专利CN107531563A提供了一种强化玻璃，该强化玻璃是板厚为0.6mm以下且在表面具有经化学强化而成的压缩应力层的强化玻璃。但玻璃中Li2O浓度小于2wt%，因此压缩应力层深度提高有限。Patent CN107531563A provides a tempered glass, the tempered glass is tempered glass with a plate thickness of 0.6mm or less and a compressive stress layer formed by chemical strengthening on the surface. However, the concentration of Li2 O in the glass is less than 2wt%, so the increase in the depth of the compressive stress layer is limited.
专利US20170197869Al提供了一种强化玻璃，但玻璃中含有足够高的B2O3成分，将导致表面压应力降低，且对玻璃中离子交换起抑制作用，难以快速获得高离子交换层深度。Patent US20170197869Al provides a strengthened glass, but the glass contains a sufficiently high B2 O3 composition, which will reduce the surface compressive stress and inhibit the ion exchange in the glass, making it difficult to quickly obtain a high ion exchange layer depth.
本发明基于以上不足，提供了一种具有高压缩应力和高压缩应力层的铝硅酸盐玻璃。Based on the above deficiencies, the present invention provides an aluminosilicate glass with high compressive stress and a high compressive stress layer.
发明内容Contents of the invention
本发明的目的在于针对现有技术的不足，提供一种可快速进行离子交换的含锂铝硅酸盐玻璃。通过将锂和磷成分同时引入至玻璃组成中，并合理控制玻璃中钠含量，可以快速实现高离子交换层的深度，从而提高玻璃耐刮擦的能力。The object of the present invention is to provide a lithium-containing aluminosilicate glass capable of rapid ion exchange in view of the deficiencies in the prior art. By simultaneously introducing lithium and phosphorus components into the glass composition, and reasonably controlling the sodium content in the glass, a high ion exchange layer depth can be quickly achieved, thereby improving the scratch resistance of the glass.
为实现本发明的目的，采用如下技术方案：For realizing the purpose of the present invention, adopt following technical scheme:
一种可快速进行离子交换的含锂铝硅酸盐玻璃，组成以摩尔百分比计，包含58~68%SiO2，12~18% Al2O3，4~8% Li2O，7~11% Na2O，0.1~8% MgO，0~3% ZnO，0~2% SrO，1~4% P2O5和0~0.5% SnO2；其中，R2O/Al2O3≤1.2，2.5≤RO≤11，R2O是含锂铝硅酸玻璃中一价阳离子氧化物总和，RO是含锂铝硅酸玻璃二价阳离子氧化物总和。A lithium-containing aluminosilicate glass capable of rapid ion exchange, the composition is calculated by molar percentage, including 58~68% SiO2 , 12~18% Al2 O3 , 4~8% Li2 O, 7~11 % Na2 O, 0.1~8% MgO, 0~3% ZnO, 0~2% SrO, 1~4% P2 O5 and 0~0.5% SnO2 ; among them, R2 O/Al2 O3 ≤ 1.2, 2.5≤RO≤11, R2 O is the sum of monovalent cation oxides in lithium-containing aluminosilicate glass, RO is the sum of divalent cation oxides in lithium-containing aluminosilicate glass.
优选的，所述的可快速进行离子交换的含锂铝硅酸盐玻璃，组成以摩尔百分比计，包含60~66% SiO2，12~18% Al2O3，4~6% Li2O，7~11% Na2O，1~6% MgO，0~3% ZnO，0~2% SrO，1~4% P2O5，0~0.5% SnO2，其中R2O/Al2O3≤1.0，4≤RO≤7，R2O是含锂铝硅酸玻璃中一价阳离子氧化物总和，RO是含锂铝硅酸玻璃二价阳离子氧化物总和。Preferably, the lithium-containing aluminosilicate glass capable of rapid ion exchange is composed of 60-66% SiO2 , 12-18% Al2 O3 , 4-6% Li2 O , 7~11% Na2 O, 1~6% MgO, 0~3% ZnO, 0~2% SrO, 1~4% P2 O5 , 0~0.5% SnO2 , where R2 O/Al2 O3 ≤1.0, 4≤RO≤7, R2 O is the sum of monovalent cation oxides in lithium-containing aluminosilicate glass, RO is the sum of divalent cation oxides in lithium-containing aluminosilicate glass.
优选的，所述的可快速进行离子交换的含锂铝硅酸盐玻璃中，MgO浓度不低于3摩尔%。Preferably, in the lithium-containing aluminosilicate glass capable of rapid ion exchange, the concentration of MgO is not lower than 3 mol%.
优选的，所述的可快速进行离子交换的含锂铝硅酸盐玻璃中，B2O3浓度不高于0.1摩尔%。Preferably, in the lithium-containing aluminosilicate glass capable of rapid ion exchange, the concentration of B2 O3 is not higher than 0.1 mol%.
优选的，所述的可快速进行离子交换的含锂铝硅酸盐玻璃中，K2O浓度不高于0.1摩尔%。Preferably, the concentration of K2 O in the lithium-containing aluminosilicate glass capable of rapid ion exchange is not higher than 0.1 mol%.
所述的可快速进行离子交换的含锂铝硅酸盐玻璃，应变点温度大于550℃；维氏硬度大于600MPa。The lithium-containing aluminosilicate glass capable of rapid ion exchange has a strain point temperature greater than 550° C. and a Vickers hardness greater than 600 MPa.
所述的可快速进行离子交换的含锂铝硅酸盐玻璃，压缩应力层深至少50μm。In the lithium-containing aluminosilicate glass capable of rapid ion exchange, the depth of the compressive stress layer is at least 50 μm.
所述的可快速进行离子交换的含锂铝硅酸盐玻璃，压缩应力区域压缩应力至少500MPa。The lithium-containing aluminosilicate glass capable of rapid ion exchange has a compressive stress of at least 500 MPa in the compressive stress region.
本发明所提供的含锂铝硅酸盐玻璃，其不含有快速降低玻璃离子交换表面区域的压应力的硼和钾成分（含量均不高于0.1摩尔%），而通过引入适量的二价阳离子氧化物和控制低水平的一价阳离子碱金属氧化物，获得具有高维氏硬度值的玻璃；同时提高含锂铝硅酸玻璃的低温特性，可以减少玻璃离子交换过程中应力松弛量，从而获得高表面压应力；此外，适量的二价阳离子氧化物可提高玻璃抵抗外力损坏能力和高抗裂性能。The lithium-containing aluminosilicate glass provided by the present invention does not contain boron and potassium components (the contents are not higher than 0.1 mol%) that rapidly reduce the compressive stress in the ion exchange surface area of the glass, and by introducing an appropriate amount of divalent cations Oxide and control the low level of monovalent cationic alkali metal oxide to obtain glass with high Vickers hardness value; at the same time, improving the low temperature characteristics of lithium-containing aluminosilicate glass can reduce the amount of stress relaxation in the glass ion exchange process, thereby obtaining High surface compressive stress; in addition, an appropriate amount of divalent cation oxide can improve the glass's resistance to external damage and high crack resistance.
本发明所述玻璃中SiO2主要为玻璃成形体，必需成分之一，构成了玻璃网状主结构。玻璃中含浓度58～68摩尔%的SiO2，足够多的SiO2赋予玻璃较佳化学稳定性、机械性能和成型性能。但SiO2会过高地提高熔融温度，尤其玻璃中存在高浓度的氧化铝的条件下，SiO2浓度应控制在低于约68摩尔%，优选低于约66摩尔%，更优选低于约64摩尔%；玻璃中过低的SiO2浓度会导致玻璃的耐老化性能和表面机械性能趋于劣化，增加超薄玻璃在冷加工和清洗过程中产生划伤几率。因此，SiO2浓度应控制在高于约58摩尔%，优选高于约60摩尔%，更优选高于约62摩尔%。TheSiO2 in the glass of the present invention is mainly a glass forming body, one of the essential components, and constitutes the main structure of the glass network. The glass contains SiO2 with a concentration of 58-68 mol%, enough SiO2 endows the glass with better chemical stability, mechanical properties and formability. But SiO2 will increase the melting temperature too high, especially under the condition of high concentration of alumina in the glass, SiO2 concentration should be controlled at less than about 68 mol%, preferably less than about 66 mol%, more preferably less than about 64 Mole %; Too low SiO2 concentration in the glass will lead to deterioration of the aging resistance and surface mechanical properties of the glass, and increase the chance of scratching the ultra-thin glass during cold processing and cleaning. Therefore, theSiO2 concentration should be controlled above about 58 mole percent, preferably above about 60 mole percent, more preferably above about 62 mole percent.
本发明所述玻璃中Al2O3为必需成分之一，属于网络中间体组成，在高碱浓度玻璃成分中，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。Al2O3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，更为玻璃在离子交换过程提供交换通道，极大提高玻璃压缩成应力和压缩成应力层深，但Al2O3属于极难熔氧化物，其能快速提高玻璃粘度，致使玻璃澄清均化难度加大，玻璃中气泡和铂铑异物缺陷数量将急剧增加；虽然氧化锂成分能快速降低玻璃熔点，但更高浓度使得玻璃液相线温度快速提高，难以成型。因此在玻璃中浓度约12摩尔%～18摩尔%的Al2O3，优选约12摩尔%～17摩尔%。Al2O3 is one of the essential components in the glass of the present invention, which belongs to the composition of network intermediates.In the high alkali concentration glass components, most of the alumina tends to become glass alumina tetrahedrons, forming a glass network main structure. Thereby improving glass stability and mechanical properties. The volume of the alumina tetrahedron formed by Al2 O3 in the glass is larger than that of the silica tetrahedron, and the volume of the glass expands, thereby reducing the density of the glass and providing exchange channels for the glass during the ion exchange process, which greatly Increase the glass compression stress and compression stress layer depth, but Al2 O3 is an extremely refractory oxide, which can quickly increase the viscosity of the glass, making it more difficult to clarify and homogenize the glass, and the number of bubbles and platinum-rhodium foreign matter defects in the glass will decrease. Rapid increase; although the lithium oxide component can quickly reduce the melting point of the glass, the higher concentration makes the liquidus temperature of the glass rise rapidly, making it difficult to form. Thus the concentration of Al2 O3 in the glass is about 12 mol % to 18 mol %, preferably about 12 mol % to 17 mol %.
本发明玻璃中Li2O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，Li2O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Al2O3浓度提供可能性，本发明中Li2O浓度不低于约4摩尔%，如低于4摩尔%浓度，玻璃中Li+和Na+交换量不足，难以获得高压缩应力层深度；但高浓度Li2O浓度玻璃，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，同时如果玻璃具有过低的低温特性，例如应变点温度低于约550℃，在玻璃离子交换过程中，应力松弛现象越明显，难以获得高表面压应力，因此，本发明中Li2O浓度低于约8摩尔%，优选约4摩尔%～6摩尔%。Li2 O in the glass of the present invention belongs to one of the ion exchange components. The present invention has proved through a large number of experiments that the lithium-containing glass can be exchanged with Li+ and Na+ in the glass at a suitable temperature to obtain high compression quickly. stress layer depth. In addition, Li2 O can rapidly reduce the viscosity of the glass, especially at high temperature, which is beneficial to the melting and clarification of the glass, and provides the possibility for a high concentration of Al2 O3 in the glass. The concentration of Li2 O in the present invention is not low At about 4 mol%, if the concentration is lower than 4 mol%, the Li+ and Na+ exchange amount in the glass is insufficient, and it is difficult to obtain a high compressive stress layer depth; but the liquidus temperature of the high-concentration Li2 O concentration glass increases with the glass Viscosity is reduced, so that the glass becomes easy to devitrify. At the same time, if the glass has too low low-temperature characteristics, such as the strain point temperature is lower than about 550 ° C, the stress relaxation phenomenon is more obvious during the glass ion exchange process, and it is difficult to obtain a high surface area. Compressive stress, therefore, the concentration of Li2 O in the present invention is less than about 8 mol%, preferably about 4-6 mol%.
玻璃中Na2O为必需成分之一，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。同时较高浓度的Na2O为玻璃化学强化提供可能。因此，本发明中Na2O浓度不低于约7摩尔%。但Na2O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，Na2O更容易倾向与水中的氢离子交换出而溶入水中，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Na2O浓度可以通过含钠熔盐中通过Li+和Na+交换，可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Na2O浓度优选低于约11摩尔%。Na2 O is one of the essential components in glass, which provides a large source of free oxygen, which 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, the higher concentration of Na2 O provides the possibility of chemical strengthening of the glass. Therefore, the Na2O concentration in the present invention is not less than about7 mole %. However, if the concentration of Na2 O is too high, the mechanical properties and chemical stability of the glass will deteriorate. Especially in silicate glass with high alumina concentration and phosphorus content, Na2 O tends to exchange with hydrogen ions in water and dissolve. Into the water, accelerate the change of the chemical properties of the glass surface; in the lithium-containing glass composition, the Na2 O concentration on the glass surface can be exchanged by Li+ and Na+ in the sodium-containing molten salt, so that the glass surface can maintain a high concentration of Na concentration, To ensure the Na ion concentration required for K+ and Na+ exchange in the glass surface in the potassium-containing molten salt, the Na2 O concentration in the glass is preferably lower than about 11 mol%.
本发明人大量实验证实玻璃中维持较高K2O浓度有助于获得高压缩应力层的深度，但这种压缩应力层未必为熔盐中钾离子与钠离子发生离子交换而形成，但本发明中高压缩应力层主要通过Li+和Na+交换形成，本发明的玻璃中K2O浓度低于0.1摩尔%，其主要通过原料杂质浓度引入。A large number of experiments by the inventors have confirmed that maintaining a relatively high K2 O concentration in the glass is helpful to obtain the depth of the high compressive stress layer, but this compressive stress layer may not be formed by ion exchange between potassium ions and sodium ions in molten salt, but this In the invention, the high compressive stress layer is mainly formed through the exchange of Li+ and Na+ , and the concentration of K2 O in the glass of the invention is lower than 0.1 mol%, which is mainly introduced through the concentration of raw material impurities.
本发明中一价阳离子氧化物R2O浓度与Al2O3浓度比值控制小于等于1.2，过高R2O/Al2O3浓度比值降低玻璃应变点温度和表面维氏硬度，难以达到应变点温度大于等于550℃和强化前的维氏硬度大于等于600MPa。In the present invention, the ratio of monovalent cation oxide R2 O concentration to Al2 O3 concentration is controlled to be less than or equal to 1.2. Too high R2 O/Al2 O3 concentration ratio reduces glass strain point temperature and surface Vickers hardness, making it difficult to achieve strain The point temperature is greater than or equal to 550°C and the Vickers hardness before strengthening is greater than or equal to 600MPa.
B2O3成分属于网络形成体氧化物，可明显降低玻璃的应变点温度，且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。大量实验表明，对于玻璃离子交换性能而言，B2O3不利于玻璃高压缩应力和高应力层深度，因此本发明中将B2O3浓度小于0.1摩尔%，优选B2O3浓度为0摩尔%。The B2 O3 component belongs to the network former oxide, which can significantly reduce the strain point temperature of the glass, and the volatilization of oxides occurs during the high-temperature melting process, which is not conducive to the stability of the glass components. A large number of experiments have shown that for the ion exchange performance of glass, B2 O3 is not conducive to the high compressive stress and high stress layer depth of glass, so in the present invention, the B2 O3 concentration is less than 0.1 mol%, and the B2 O3 concentration is preferably 0 mol%.
本发明中P2O5属于玻璃形成体成分，其以[PO4]四面体相互连成网络，但P2O5形成的网络结构属于层状，且层间由范德华力相互连接，因此，玻璃中P2O5具有粘度小，化学稳定性差和热膨胀系数大作用。但本发明实验表明，P2O5浓度对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。因此本发明中将P2O5浓度限制在1摩尔%～4摩尔%，优选P2O5浓度在1.5摩尔%～3.5摩尔%之间。In the present invention, P2 O5 belongs to the glass former component, and it forms a network with [PO4 ] tetrahedra, but the network structure formed by P2 O5 is layered, and the layers are connected to each other by van der Waals force. Therefore, P2 O5 in glass has low viscosity, poor chemical stability and large thermal expansion coefficient. However, the experiment of the present invention shows that the concentration of P2 O5 promotes the ion exchange in the glass strengthening process, and plays an important role in quickly obtaining a higher compressive stress layer. Therefore, in the present invention, the P2 O5 concentration is limited to 1 mol % to 4 mol %, preferably the P2 O5 concentration is between 1.5 mol % to 3.5 mol %.
本发明的玻璃中含有二价阳离子氧化物，其为玻璃网络外体成分，破坏玻璃结构的完整性，降低玻璃熔化温度，是良好的助熔剂，利于澄清，但同时提高了玻璃的线热膨胀系数值，降低玻璃的应变点温度值，同时提高玻璃弹性模量和机械性能。二价阳离子氧化物在提高玻璃表面压缩应力方面具有优势，本发明中实验表明，玻璃中ZnO和SrO对提高玻璃表面压缩应力与MgO处于同一水平，尤为重要的是，ZnO对玻璃强化性能中强化应力层深具有改善效果。本发明玻璃中MgO浓度约为0.1摩尔～8摩尔%，优选MgO浓度为3摩尔%～8摩尔%。本发明中玻璃中ZnO浓度约为0摩尔%～3摩尔%，但玻璃中过高ZnO浓度会导致玻璃析晶倾向明显增加，因此优选ZnO浓度约为0.5摩尔%～2摩尔%。本发明中玻璃中SrO浓度约为0摩尔%～3摩尔%，优选SrO浓度约为0摩尔～2摩尔%。The glass of the present invention contains divalent cationic oxide, which is the outer body component of the glass network, destroys the integrity of the glass structure, reduces the melting temperature of the glass, is a good flux, and is beneficial to clarification, but at the same time increases the linear thermal expansion coefficient of the glass value, reducing the strain point temperature value of the glass, while improving the elastic modulus and mechanical properties of the glass. Divalent cation oxides have advantages in improving the compressive stress of the glass surface. Experiments in the present invention show that ZnO and SrO in the glass are at the same level as MgO for improving the compressive stress of the glass surface. What is more important is that ZnO strengthens the glass strengthening performance. The depth of the stress layer has an improvement effect. The MgO concentration in the glass of the present invention is about 0.1 mol% to 8 mol%, preferably the MgO concentration is 3 mol% to 8 mol%. In the present invention, the ZnO concentration in the glass is about 0 mol% to 3 mol%, but too high ZnO concentration in the glass will lead to a significant increase in the crystallization tendency of the glass, so the preferred ZnO concentration is about 0.5 mol% to 2 mol%. In the present invention, the SrO concentration in the glass is about 0 mol% to 3 mol%, preferably the SrO concentration is about 0 mol% to 2 mol%.
本发明中二价阳离子氧化物RO含量控制在2.5摩尔%～11摩尔%之间，如浓度高于11摩尔%，则玻璃中高二价阳离子氧化物浓度将阻碍离子交换的效率明显增加且玻璃液相线温度增加，不利于生产制程；如浓度低于2.4摩尔%，则玻璃粘度过高，优选4摩尔%～7摩尔%。In the present invention, the RO content of divalent cation oxides is controlled between 2.5 mol% and 11 mol%. If the concentration is higher than 11 mol%, the high concentration of divalent cation oxides in the glass will hinder the efficiency of ion exchange from significantly increasing and the glass liquid The increase of the phase line temperature is not conducive to the production process; if the concentration is lower than 2.4 mol%, the glass viscosity is too high, preferably 4 mol% to 7 mol%.
除上述的氧化物之外，本发明的玻璃中含化学澄清剂，其中SnO2浓度控制在约0～0.5摩尔%。In addition to the above-mentioned oxides, the glass of the present invention contains a chemical clarifying agent, wherein theSnO2 concentration is controlled at about 0-0.5 mol%.
本发明中玻璃制品通过玻璃中小离子与熔盐中大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，所述压缩应力层来源含锂离子与钠离子交换形成，以及钠离子与钾离子交换形成。所述玻璃的离子交换过程描述如下：将退火后玻璃块制备成厚度约0.7mm玻璃薄片，采用超声波进行清洗备用；将玻璃薄片进行250℃～300℃预热处理后，将玻璃制品浸泡在380℃～430℃熔盐中，所述熔盐含有高于20%比例硝酸钠的硝酸钾熔盐，浸泡时间约20～120分钟，再将玻璃薄片取出浸泡在380～410℃熔盐中，所述熔盐中含有低于20%硝酸钠的硝酸钾熔盐中，浸泡时间为10～90分钟；将玻璃进行取出表面熔盐处理待测试。In the present invention, the glass product is ion-exchanged by small ions in the glass and large ions in the molten salt so as to generate compressive stress and a compressive stress layer on the glass surface. ion exchange formation. The ion exchange process of the glass is described as follows: the annealed glass block is prepared into a glass sheet with a thickness of about 0.7 mm, which is cleaned by ultrasonic wave for standby; after the glass sheet is preheated at 250 ° C to 300 ° C, the glass product is soaked in ℃～430℃ molten salt, the molten salt contains potassium nitrate molten salt with a proportion higher than 20% of sodium nitrate, soaking time is about 20～120 minutes, and then the glass flakes are taken out and soaked in 380～410℃ molten salt. In the potassium nitrate molten salt containing less than 20% sodium nitrate in the molten salt, the immersion time is 10 to 90 minutes; the glass is taken out of the surface and treated with molten salt for testing.
玻璃薄片表面形成压缩应力和压缩应力层参照图1所示，在表面形成含有CS1和CS2压缩应力值，以及DOL1和DOL2压缩应力层，以及在玻璃薄片中心区域形成张应力CT。The compressive stress and compressive stress layer formed on the surface of the glass sheet are shown in Figure 1, and the compressive stress value of CS1 and CS2, and the compressive stress layer of DOL1 and DOL2 are formed on the surface, and the tensile stress CT is formed in the central area of the glass sheet.
本发明与现有技术比较具有以下优点：Compared with the prior art, the present invention has the following advantages:
1）本发明玻璃中通过引入锂（Li2O浓度不低于约4摩尔%）和磷（P2O5浓度限制在1摩尔%～4摩尔%），可以快速实现高离子交换层的深度，从而提高玻璃耐刮擦的能力，使玻璃具有高压缩应力和压缩应力层；1) By introducing lithium (the concentration of Li2 O is not less than about 4 mol%) and phosphorus (the concentration of P2 O5 is limited to 1 mol% to 4 mol%) in the glass of the present invention, a high ion exchange layer depth can be quickly achieved , so as to improve the scratch resistance of the glass, so that the glass has a high compressive stress and a compressive stress layer;
2）本发明玻璃通过优化一价阳离子氧化物（R2O/ Al2O3浓度比值小于等于1.2）和二价阳离氧化物氧化物（RO含量控制在2.5摩尔%～11摩尔%），使玻璃具有高维氏硬度值。2) The glass of the present invention optimizes monovalent cation oxides (R2 O/ Al2 O3 concentration ratio is less than or equal to 1.2) and divalent cation oxides (RO content is controlled at 2.5 mol% to 11 mol%), Make glass with high Vickers hardness value.
附图说明Description of drawings
图1为玻璃离子交换后表面压缩应力分布图；厚度为t的玻璃经离子交换后，在玻璃表面形成钠钾交换层，即表面压应力层CS1、离子交换层DOL1和锂钠交换层，即表面压应力层CS2、离子交换层DOL2，并在玻璃内部形成具有中心张应力（Central Tensile Stress,简称CT）。Figure 1 is the surface compressive stress distribution diagram of the glass after ion exchange; the glass with a thickness of t forms a sodium-potassium exchange layer on the glass surface after ion exchange, that is, the surface compressive stress layer CS1, the ion exchange layer DOL1 and the lithium-sodium exchange layer, namely Surface compressive stress layer CS2, ion exchange layer DOL2, and form a central tensile stress (Central Tensile Stress, CT for short) inside the glass.
具体实施方式Detailed ways
为进一步公开而不是限制本发明，以下结合实例对本发明作进一步的详细说明。In order to further disclose rather than limit the present invention, the present invention will be further described in detail below in conjunction with examples.
1）测试样品制备1) Test sample preparation
本发明实施例中，表2为表1中2号配方依据各原料纯度与水分含量制备成配合料；按表1所示原料组成进行称重混合后，以获得均匀的配料；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进行600℃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。In the embodiment of the present invention, Table 2 is that No. 2 formula in Table 1 is prepared into a batch according to the purity and moisture content of each raw material; after weighing and mixing the raw materials shown in Table 1, to obtain a uniform batching; then the batch Transfer from the plastic bottle to about 800ml platinum crucible, put the platinum crucible into the silicon-molybdenum rod high-temperature furnace, gradually raise the temperature to 1650°C, hold the temperature for 3-8 hours, accelerate the discharge of glass bubbles and homogenize and eliminate the glass by stirring . After melting, pour the molten liquid into a heat-resistant stainless steel mold for molding, then take out the glass block and move it into a box-type annealing furnace for heat treatment at 600°C for about 2 hours, and then lower it to 550°C at a rate of less than 1°C/min , and then naturally cooled to room temperature. In order to obtain more stable measurement results, chemical-grade raw materials should be selected.
2）中文→物理性质符号及测量方法定义2) Chinese→Physical property symbols and definitions of measurement methods
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.密度：根据ASTM C693阿基米德法测试，环境温度为22±0.5℃；A. Density: Tested according to ASTM C693 Archimedes method, the ambient temperature is 22±0.5°C;
B.液相线温度：即采用玻璃在温差炉中失透的最高温度表示，通常失透过程时长为24小时；B. Liquidus temperature: it is represented by the highest temperature of glass devitrification in a temperature difference furnace, and the devitrification process usually takes 24 hours;
C.软化点温度：玻璃粘度为软化点温度107.6泊时的温度，根据ASTM C-338纤维伸长检测方法测量；C. Softening point temperature: the temperature at which the glass viscosity is the softening point temperature of 107.6 poises, measured according to the ASTM C-338 fiber elongation detection method;
D.退火点温度：玻璃粘度为1013泊时的温度，根据ASTM C-336纤维伸长检测方法测量；D. Annealing point temperature: the temperature when the glass viscosity is 1013 poise, measured according to the ASTM C-336 fiber elongation detection method;
E.应变点温度：玻璃粘度为1014.5泊时的温度，根据ASTM C-336纤维伸长检测方法测量；E. Strain point temperature: the temperature at which the glass viscosity is 1014.5 poise, measured according to the ASTM C-336 fiber elongation detection method;
F.CS1、DOL1为玻璃离子交换后采用FSM-6000LE表面应力仪利用光波导技术测试玻璃的CS1、DOL1；F.CS1 and DOL1 are the CS1 and DOL1 of the glass after ion exchange by using FSM-6000LE surface stress meter and optical waveguide technology;
G.CS2、DOL2为玻璃离子交换后采用SLP-1000表面应力仪利用散射光弹性技术测试CS2、DOL2值；G.CS2 and DOL2 are the values of CS2 and DOL2 measured by SLP-1000 surface stress meter using scattering photoelasticity technology after glass ion exchange;
H.维氏硬度：采用TMVP-1S 维氏硬度计测试未强化和强化后玻璃表面维氏硬度值，测试条件为：施加作用力200g，施加时间为15s。H. Vickers hardness: Use TMVP-1S Vickers hardness tester to test the Vickers hardness value of the unstrengthened and strengthened glass surface. The test conditions are: apply force 200g, and apply time for 15s.
表1实施例1-10的玻璃组成The glass composition of table 1 embodiment 1-10
表2 表1中编号为2的玻璃配合料化学组成Table 2 Chemical composition of glass batches numbered 2 in Table 1
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 above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810766723.0ACN108585481A (en) | 2018-07-13 | 2018-07-13 | A lithium-containing aluminosilicate glass capable of rapid ion exchange |
| PCT/CN2019/095289WO2020011167A1 (en) | 2018-07-13 | 2019-07-09 | Lithium-containing aluminosilicate glass capable of undergoing rapid ion exchange |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810766723.0ACN108585481A (en) | 2018-07-13 | 2018-07-13 | A lithium-containing aluminosilicate glass capable of rapid ion exchange |
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| CN108585481Atrue CN108585481A (en) | 2018-09-28 |
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| CN201810766723.0APendingCN108585481A (en) | 2018-07-13 | 2018-07-13 | A lithium-containing aluminosilicate glass capable of rapid ion exchange |
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| RJ01 | Rejection of invention patent application after publication | Application publication date:20180928 | |
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