相关申请交叉参考Related Application Cross Reference
本申请要求2011年10月25日提交的美国临时申请号No.61/551,163(代理人卷号No.SP11-240P)且标题为“具有改善的化学和机械耐久性的玻璃组合物”的优先权，该文的全部内容通过引用纳入本文。This application claims priority to U.S. Provisional Application No. 61/551,163 (Attorney Docket No. SP11-240P), filed October 25, 2011, and entitled "Glass Compositions Having Improved Chemical and Mechanical Durability" right, the entire content of which is incorporated herein by reference.
背景background
领域field
本发明总体涉及玻璃组合物，具体来说，涉及适用于药物包装的化学和机械耐久玻璃组合物。The present invention relates generally to glass compositions and, in particular, to chemically and mechanically durable glass compositions suitable for use in pharmaceutical packaging.
技术背景technical background
历史上，因为玻璃具有相对于其它材料的气密性、光学清晰度和优异的化学耐久性，已将玻璃用作药物包装的优选材料。具体来说，在药物包装中使用的玻璃必须具有足够的化学耐久性，从而不会影响药物包装中容纳的药物组合物的稳定性。具有合适的化学耐久性的玻璃，包括那些符合ASTM标准“1B型”的玻璃组合物，它们的化学耐久性久经考验。Historically, glass has been used as a preferred material for pharmaceutical packaging because of its airtightness, optical clarity, and superior chemical durability relative to other materials. Specifically, glass used in pharmaceutical packaging must be chemically durable enough so as not to affect the stability of the pharmaceutical composition contained within the pharmaceutical packaging. Glasses having suitable chemical durability, including those glass compositions meeting ASTM Standard "Type 1B", have proven chemical durability.
但是，把玻璃用于这些应用受到玻璃的机械性能的限制。具体来说，在制药工业中，玻璃破裂是终端用户关心的安全问题，因为破裂的包装和/或包装的内容物可能伤害终端用户。对于药物制造商，破裂是损失惨重的，因为灌装线中的破裂要求丢弃邻近的未破裂的容器，因为该容器可能包含来自破裂容器的碎片。破裂还可能要求灌装线减速或停车，降低生成效率。此外，破裂还可导致损失活性药物，导致成本增加。此外，非毁灭性的断裂(即，当玻璃有裂纹却没有破裂时)可能导致内容物失去它们的无菌性，这依次可能导致昂贵的产品召回。However, the use of glass for these applications is limited by the mechanical properties of the glass. Specifically, in the pharmaceutical industry, glass breakage is a safety concern for end users because broken packages and/or package contents may injure the end user. For pharmaceutical manufacturers, ruptures are costly because a rupture in a filling line requires the adjacent unruptured container to be discarded because it may contain fragments from the ruptured container. Cracks may also require the filling line to be slowed down or shut down, reducing production efficiency. In addition, rupture can also result in loss of active drug, leading to increased costs. Furthermore, non-catastrophic breaks (ie, when the glass is cracked but not broken) can cause the contents to lose their sterility, which in turn can lead to costly product recalls.
改善玻璃包装机械耐久性的方法之一是热学钢化该玻璃包装。热学钢化通过在成形后的快速冷却中产生表面压缩应力，来强化玻璃。对于具有平坦几何形貌(如窗户)的玻璃制品、厚度＞2毫米的玻璃制品和高热膨胀的玻璃组合物，这种技术非常可行。但是，药物玻璃包装通常具有复杂的几何形貌(小瓶、管状、安瓿瓶等)、薄的壁(～1-1.5毫米)，以及由低膨胀玻璃(30-55x10-7K-1)制备，使玻璃药物包装不适于通过热学钢化强化。One of the ways to improve the mechanical durability of glass packages is to thermally toughen the glass packages. Thermal tempering strengthens glass by creating surface compressive stresses during rapid cooling after forming. This technique works well for glazing with flat geometries such as windows, glazing >2 mm thick, and glass compositions with high thermal expansion. However, pharmaceutical glass packaging usually has complex geometries (vials, tubes, ampoules, etc.), thin walls (~1-1.5 mm), and is made of low-expansion glass (30-55x10-7 K-1 ), Making glass pharmaceutical packaging unsuitable for strengthening by thermal tempering.
化学钢化也通过引入表面压缩应力来强化玻璃。通过把制品浸没于熔盐浴中来引入应力。因为玻璃中的离子被熔盐中更大的离子取代，所以在玻璃的表面产生压缩应力。化学钢化的益处在于它可在复杂几何形貌、薄的样品上使用，且对玻璃基材的热膨胀特征相对不敏感。但是，对化学钢化具有中等敏感性(susceptibility)的玻璃组合物通常具有不良的化学耐久性，反之亦然。Chemical tempering also strengthens glass by introducing surface compressive stress. Stress is introduced by immersing the article in a molten salt bath. Compressive stress is created on the surface of the glass as the ions in the glass are replaced by larger ions in the molten salt. The benefits of chemical toughening are that it can be used on complex geometries, thin samples, and is relatively insensitive to the thermal expansion characteristics of the glass substrate. However, glass compositions with moderate susceptibility to chemical toughening generally have poor chemical durability, and vice versa.
因此，存在对玻璃组合物的需求，所述玻璃组合物是化学耐久的且易于通过离子交换化学强化以用于药物包装和类似的应用。Accordingly, a need exists for glass compositions that are chemically durable and readily chemically strengthened by ion exchange for use in pharmaceutical packaging and similar applications.
概述overview
根据一种实施方式，玻璃组合物可包括：浓度大于约70摩尔％的SiO2和Y摩尔％的碱金属氧化物。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。所述玻璃组合物可不含硼和硼的化合物。According to one embodiment, the glass composition may include SiO2 at a concentration greater than about 70 mole percent and Y mole percent alkali metal oxide. The alkali metal oxide may include Na2O in an amount greater than about8 mole percent. The glass composition may be free of boron and boron compounds.
根据另一种实施方式，玻璃组合物可包括：大于约68摩尔％SiO2；X摩尔％Al2O3；Y摩尔％碱金属氧化物；以及B2O3。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。比例(B2O3(摩尔％)/(Y摩尔％–X摩尔％)可大于0且小于0.3。According to another embodiment, a glass composition may include: greater than about 68 mole % SiO2 ; X mole % Al2 O3 ; Y mole % alkali metal oxide; and B2 O3 . The alkali metal oxide may include Na2O in an amount greater than about8 mole percent. The ratio (B2 O3 (mol%)/(Y mol%−X mol%) may be greater than 0 and less than 0.3.
还在其他实施方式中，玻璃制品可具有根据ISO719的HGB1型耐水解性。玻璃制品可包括大于约8摩尔％Na2O和小于约4摩尔％B2O3。In still other embodiments, the glass article may have a hydrolysis resistance type HGB1 according to ISO719. The glass article can include greater than about8 mole % Na2O and lessthan about4 mole % B2O3.
还在其他实施方式中，玻璃药物包装可包括：大于约70摩尔％量的SiO2；X摩尔％Al2O3；以及Y摩尔％的碱金属氧化物。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。玻璃药物包装中B2O3的浓度(摩尔％)和(Y摩尔％–X摩尔％)的比例可小于0.3。玻璃药物包装也可具有根据ISO719的HGB1型耐水解性。In still other embodiments, the glass pharmaceutical package can include:SiO2 in an amount greater than about 70 mole %; X mole %Al2O3; and Y mole % alkali metal oxide. The alkali metal oxide may include Na2O in an amount greater than about8 mole percent.The concentration (mol%)of B2O3 in the glass pharmaceutical package and the ratio of (Ymol%-Xmol%) may be less than 0.3. Glass pharmaceutical packaging can also have hydrolysis resistance type HGB1 according to ISO719.
在其他实施方式中，玻璃组合物可包括从约70摩尔％到约80摩尔％SiO2；从约3摩尔％到约13摩尔％碱土金属氧化物；X摩尔％Al2O3；以及Y摩尔％碱金属氧化物。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。比例Y:X可大于1，且玻璃组合物可不含硼和硼的化合物。In other embodiments, the glass composition may include from about 70 mole % to about 80 mole % SiO2 ; from about 3 mole % to about 13 mole % alkaline earth oxides; X mole % Al2 O3 ; and Y mole % % alkali metal oxides. The alkali metal oxide may include Na2O in an amount greater than about8 mole percent. The ratio Y:X can be greater than 1, and the glass composition can be free of boron and boron compounds.
还在另一种实施方式中，玻璃组合物可包括：从约72摩尔％到约78摩尔％SiO2；从约4摩尔％到约8摩尔％碱土金属氧化物；X摩尔％Al2O3；以及Y摩尔％碱金属氧化物。碱土金属氧化物的量可大于或等于约4摩尔％且小于或等于约8摩尔％。碱金属氧化物可包括大于或等于约9摩尔％且小于或等于约15摩尔％量的Na2O。比例Y:X可大于1。所述玻璃组合物可不含硼和硼的化合物。In yet another embodiment, the glass composition may include: from about 72 mole % to about 78 mole %SiO2 ; from about 4 mole % to about8 mole % alkaline earth oxides; X mole %Al2O3 and Y mol % alkali metal oxide. The amount of alkaline earth metal oxide can be greater than or equal to about 4 mole percent and less than or equal to about 8 mole percent. The alkali metal oxide may include Na2O in an amount greater than or equal to about9 mole percent and less than or equal to about 15 mole percent. The ratio Y:X can be greater than 1. The glass composition may be free of boron and boron compounds.
还在另一种实施方式中，玻璃组合物可包括：从约68摩尔％到约80摩尔％SiO2；从约3摩尔％到约13摩尔％碱土金属氧化物；X摩尔％Al2O3；以及Y摩尔％碱金属氧化物。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。所述玻璃组合物还可包括B2O3。比例(B2O3(摩尔％)/(Y摩尔％–X摩尔％)可大于0且小于0.3，以及比例Y:X可大于1。In yet another embodiment, the glass composition may include: from about 68 mole % to about 80 mole %SiO2 ; from about3 mole % to about 13 mole % alkaline earth oxides; X mole %Al2O3 and Y mol % alkali metal oxide. The alkali metal oxide may include Na2O in an amount greater than about8 mole percent. The glass composition may also include B2 O3 . The ratio (B2 O3 (mol %)/(Y mol %−X mol %) may be greater than 0 and less than 0.3, and the ratio Y:X may be greater than 1.
在其他实施方式中，玻璃组合物可包括：从约70摩尔％到约80摩尔％SiO2；从约3摩尔％到约13摩尔％碱土金属氧化物；X摩尔％Al2O3；以及Y摩尔％碱金属氧化物。碱金属氧化物可包括大于或等于约0.1摩尔％且小于或等于约1.0摩尔％量的CaO。X可以是大于或等于约2摩尔％且小于或等于约10摩尔％。碱金属氧化物可包括从约0.01摩尔％到约1.0摩尔％K2O。比例Y:X可大于1。所述玻璃组合物可不含硼和硼的化合物。In other embodiments, the glass composition may include: from about 70 mole % to about 80 mole % SiO2 ; from about 3 mole % to about 13 mole % alkaline earth oxides; X mole % Al2 O3 ; and Y Mole % alkali metal oxide. The alkali metal oxide may include CaO in an amount greater than or equal to about 0.1 mole percent and less than or equal to about 1.0 mole percent. X can be greater than or equal to about 2 mole percent and less than or equal to about 10 mole percent. The alkali metaloxide may include from about 0.01 mole percent to about 1.0 mole percent K2O. The ratio Y:X can be greater than 1. The glass composition may be free of boron and boron compounds.
还在其他实施方式中，玻璃组合物可包括：大于约70摩尔％且小于或等于约80摩尔％量的SiO2；从约3摩尔％到约13摩尔％碱土金属氧化物；X摩尔％Al2O3；以及Y摩尔％碱金属氧化物。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。玻璃组合物中B2O3的浓度(摩尔％)和(Y摩尔％–X摩尔％)的比例可小于0.3。比例Y:X可大于1。In still other embodiments, the glass composition may include:SiO2 in an amount greater than about 70 mole % and less than or equal to about 80 mole %; from about 3 mole % to about 13 mole % alkaline earth metal oxide; X mole % Al2 O3 ; and Y mol % alkali metal oxide. The alkali metal oxide may include Na2O in an amount greater than about8 mole percent. The concentration of B2 O3 (mol %) and the ratio of (Y mol %−X mol %) in the glass composition may be less than 0.3. The ratio Y:X can be greater than 1.
在另一种实施方式中，玻璃制品可具有根据ISO719的HGB1型耐水解性。玻璃制品的阀值扩散率在小于或等于450℃的温度下可大于约16微米2/小时。In another embodiment, the glass article may have a hydrolysis resistance type HGB1 according to ISO719. The threshold diffusivity of the glass article may be greater than about 16micron2 /hour at a temperature of less than or equal to 450°C.
还在另一实施方式中，玻璃制品可具有根据ISO719的HGB1型耐水解性。玻璃制品还可具有压缩应力层，所述压缩应力层的层深度大于25微米且表面压缩应力大于或等于350MPa。可离子交换强化所述玻璃制品，且所述离子交换强化包括在熔盐浴中把玻璃制品于小于或等于450℃的温度下处理小于或等于5小时的时间。In yet another embodiment, the glass article may have a hydrolysis resistance type HGB1 according to ISO719. The glass article may also have a compressive stress layer having a layer depth greater than 25 microns and a surface compressive stress greater than or equal to 350 MPa. The glass article may be ion exchange strengthened, and the ion exchange strengthening includes treating the glass article at a temperature of less than or equal to 450° C. for a time of less than or equal to 5 hours in a molten salt bath.
在以下的详细描述中提出了本发明的其他特征和优点，其中的部分特征和优点对本领域的技术人员而言，根据所作描述就容易看出，或者通过实施包括以下详细描述、权利要求书以及附图在内的本文所述的各种实施方式而被认识。Other features and advantages of the present invention are set forth in the following detailed description, wherein part of the features and advantages are readily apparent to those skilled in the art from the description, or through implementation, include the following detailed description, claims and The various embodiments described herein, including the accompanying drawings, are recognized.
应理解，前面的一般性描述和以下的详细描述介绍了各种实施方式，用来提供理解要求保护的主题的性质和特性的总体评述或框架。包括的附图提供了对各种实施方式的进一步的理解，附图被结合在本说明书中并构成说明书的一部分。附图以图示形式说明了本文所述的各种实施方式，并与说明书一起用来解释要求保护的主题的原理和操作。It is to be understood that both the foregoing general description and the following detailed description present various embodiments, and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated in and constitute a part of this specification. The drawings illustrate the various embodiments described herein, and together with the description serve to explain the principles and operations of the claimed subject matter.
附图简述Brief description of the drawings
图1图形化地显示了发明性和比较性玻璃组合物中碱金属氧化物和氧化铝的比例(x轴)与应变点、退火点和软化点(y轴)之间的关系；Figure 1 graphically shows the relationship between the proportion of alkali metal oxide and alumina (x-axis) and strain point, annealing point and softening point (y-axis) in inventive and comparative glass compositions;
图2图形化地显示了发明性和比较性玻璃组合物中碱金属氧化物和氧化铝的比例(x轴)与最大压缩应力和应力变化(y轴)之间的关系；Figure 2 graphically shows the relationship between the proportion of alkali metal oxide and alumina (x-axis) and the maximum compressive stress and stress change (y-axis) in inventive and comparative glass compositions;
图3图形化地显示了发明性和比较性玻璃组合物中碱金属氧化物和氧化铝的比例(x轴)与根据ISO720标准测定的耐水解性(y轴)之间的关系；Figure 3 graphically shows the relationship between the proportion of alkali metal oxide and alumina in inventive and comparative glass compositions (x-axis) and the resistance to hydrolysis (y-axis) measured according to the ISO720 standard;
图4图形化地显示了发明性和比较性玻璃组合物中的扩散率D(y轴)随比例(CaO/(CaO+MgO))(x轴)的变化；Figure 4 graphically shows the diffusivity D (y-axis) as a function of the ratio (CaO/(CaO+MgO)) (x-axis) in inventive and comparative glass compositions;
图5图形化地显示了发明性和比较性玻璃组合物中的最大压缩应力(y轴)随比例(CaO/(CaO+MgO))(x轴)的变化；Figure 5 graphically shows the maximum compressive stress (y-axis) as a function of the ratio (CaO/(CaO+MgO)) (x-axis) in inventive and comparative glass compositions;
图6图形化地显示了发明性和比较性玻璃组合物中的扩散率D(y轴)随比例(B2O3/(R2O-Al2O3))(x轴)的变化；以及Figure 6 graphically shows the diffusivity D (y-axis) as a function of the ratio (B2 O3 /(R2 O-Al2 O3 )) (x-axis) in inventive and comparative glass compositions; as well as
图7图形化地显示了发明性和比较性玻璃组合物中的根据ISO720标准测定的耐水解性(y轴)随比例(B2O3/(R2O-Al2O3))(x轴)的变化。Figure 7 graphically shows the hydrolysis resistance (y-axis) measured according to the ISO720 standard in inventive and comparative glass compositions as a function of the ratio (B2 O3 /(R2 O-Al2 O3 ))(x axis) changes.
详细描述A detailed description
现在将详细参考具有改善的化学和机械耐久性的玻璃组合物的各种实施方式。这种玻璃组合物适用于各种应用，包括，但不限于药物包装材料。还可化学强化所述玻璃组合物，由此赋予玻璃增加的机械耐久性。本文所述的玻璃组合物通常可包括二氧化硅(SiO2)、氧化铝(Al2O3)、碱土金属氧化物(如MgO和/或CaO)以及碱金属氧化物(如Na2O和/或K2O)，它们的量赋予玻璃组合物化学耐久性。此外，存在于玻璃组合物中的碱金属氧化物促进通过离子交换来化学强化所述玻璃组合物。本文将描述玻璃组合物的各种实施方式，且将参考具体的实施例来进一步阐述。Reference will now be made in detail to various embodiments of glass compositions having improved chemical and mechanical durability. Such glass compositions are suitable for a variety of applications including, but not limited to, pharmaceutical packaging materials. The glass composition can also be chemically strengthened, thereby imparting increased mechanical durability to the glass. The glass compositions described herein may generally include silicon dioxide (SiO2 ), aluminum oxide (Al2 O3 ), alkaline earth metal oxides such as MgO and/or CaO, and alkali metal oxides such as Na2 O and and/or K2 O) in amounts that impart chemical durability to the glass composition. In addition, the presence of alkali metal oxides in the glass composition facilitates chemical strengthening of the glass composition by ion exchange. Various embodiments of glass compositions will be described herein and will be further illustrated with reference to specific examples.
如本文所使用，术语“软化点”指玻璃组合物的粘度为1x107.6泊(poise)时的温度。As used herein, the term "softening point" refers to the temperature at which the glass composition has a viscosity of 1 x 107.6 poise.
如本文所使用，术语“退火点”指玻璃组合物的粘度为1x1013泊(poise)时的温度。As used herein, the term "annealing point" refers to the temperature at which the viscosity of the glass composition is1x1013 poise.
如本文所使用，术语“应变点”和“T应变”指玻璃组合物的粘度为3x1014泊(poise)时的温度。As used herein, the terms "strain point" and "Tstrain " refer to the temperature at which the glass composition has a viscosity of3x1014 poise.
如本文所使用，术语“CTE”指玻璃组合物在约室温(RT)-约300℃温度范围的热膨胀系数。As used herein, the term "CTE" refers to the coefficient of thermal expansion of a glass composition at a temperature ranging from about room temperature (RT) to about 300°C.
在本文所述的玻璃组合物的实施方式中，除非另有说明，组成成分(如SiO2、Al2O3等)的浓度具体为基于氧化物的摩尔百分数(摩尔％)。In the embodiment of the glass composition described herein, unless otherwise specified, the concentration of the constituents (such as SiO2 , Al2 O3 , etc.) is specifically the mole percentage (mol %) based on the oxide.
当用来描述玻璃组合物中特定组成成分的浓度和/或不存在该特定组成成分时，术语“不含”和“基本上不含”意指该组成成分不是故意添加到所述玻璃组合物中的。但是，玻璃组合物可包含痕量的组成成分作为污染物，或者小于0.01摩尔％的不确定量的组成成分。The terms "free" and "substantially free" when used to describe the concentration and/or absence of a particular constituent in a glass composition mean that the constituent is not intentionally added to the glass composition middle. However, glass compositions may contain trace amounts of constituents as contaminants, or indeterminate amounts of constituents less than 0.01 mole percent.
如本文所使用，术语“化学耐久性”指当暴露于特定化学条件下时，玻璃组合物抵抗降解的能力。具体来说，根据3种熟知的材料测试标准来评估本文所述的玻璃组合物的化学耐久性：2001年3月的DIN12116，其题为“玻璃的测试-对煮沸盐酸水溶液攻击的抵抗-测试和分级方法(Testing of glass-Resistance to attack by a boiling aqueous solution of hydrochloric acid-Method of test and classification)”；ISO695:1991，其题为“玻璃-对煮沸混合碱金属水溶液攻击的抵抗-测试和分级方法(Glass--Resistanceto attack by a boiling aqueous solution of mixed alkali--Method oftest and classification)”；以及ISO720:1985，其题为“玻璃-玻璃晶粒在121℃下的耐水解性-测试和分级方法(Glass--Hydrolytic resistance ofglass grains at121degrees C--Method of test and classification)”。除了上述参考的标准以外，还可根据题为“玻璃-玻璃晶粒在98℃下的耐水解性-测试和分级方法(Glass--Hydrolytic resistance of glass grains at98degrees C--Method of test and classification)”的ISO719:1985来评估玻璃的化学耐久性。ISO719标准是比ISO720标准更不严格的版本，因此，据信满足ISO720标准的特定分级的玻璃也满足ISO719标准的相应分级。本文将进一步详细描述与各标准相关的分级。As used herein, the term "chemical durability" refers to the ability of a glass composition to resist degradation when exposed to specified chemical conditions. Specifically, the chemical durability of the glass compositions described herein was evaluated according to three well-known material testing standards: DIN 12116, March 2001, entitled "Tests of Glass - Resistance to Attack by Boiling Aqueous Hydrochloric Acid - Test and classification method (Testing of glass-Resistance to attack by a boiling aqueous solution of hydrochloric acid-Method of test and classification)"; ISO695:1991, which is entitled "Glass-Resistance to attack by a boiling aqueous solution of alkali metals-Test and (Glass--Resistance to attack by a boiling aqueous solution of mixed alkaline--Method oftest and classification)"; and ISO720:1985, entitled "Glass - Resistance to hydrolysis of glass grains at 121°C - Test and Grading method (Glass--Hydrolytic resistance of glass grains at121degrees C--Method of test and classification)". In addition to the above referenced standards, it can also be tested according to the title "Glass--Hydrolytic resistance of glass grains at 98 degrees C--Method of test and classification" "ISO719:1985 to evaluate the chemical durability of glass. The ISO719 standard is a less stringent version than the ISO720 standard, and therefore, it is believed that glass meeting a particular classification of the ISO720 standard also meets the corresponding classification of the ISO719 standard. The grading associated with each standard is described in further detail herein.
本文所述的玻璃组合物是碱金属铝硅酸盐玻璃组合物，其通常可包括SiO2和一种或更多种碱金属氧化物如Na2O和/或K2O的组合。所述玻璃组合物还可包括Al2O3和至少一种碱土金属氧化物。在一些实施方式中，所述玻璃组合物可不含硼和包括硼的化合物。所述玻璃组合物是耐化学降解的，且还适于通过离子交换来化学强化。在一些实施方式中，所述玻璃组合物还可包括少量的一种或更多种其它氧化物如SnO2,ZrO2,ZnO,TiO2,As2O3等。可添加这些组分作为澄清剂(fining agent)和/或进一步增强所述玻璃组合物的化学耐久性。The glass compositions described herein are alkali aluminosilicate glass compositions, which may generally include a combination ofSiO2 and one or more alkali metal oxides such asNa2O and/orK2O . The glass composition may also include Al2 O3 and at least one alkaline earth metal oxide. In some embodiments, the glass composition may be free of boron and compounds including boron. The glass composition is resistant to chemical degradation and is also suitable for chemical strengthening by ion exchange. In some embodiments, the glass composition may also include a small amount of one or more other oxides such as SnO2 , ZrO2 , ZnO, TiO2 , As2 O3 , and the like. These components can be added as fining agents and/or to further enhance the chemical durability of the glass composition.
在本文所述的玻璃组合物的实施方式中，SiO2是该组合物的最大成分，因此是所得玻璃网络的主要成分。SiO2增强玻璃的化学耐久性，具体来说，增强玻璃组合物在酸中对分解的抵抗和玻璃组合物在水中对分解的抵抗。因此，通常期望高的SiO2浓度。但是，如果SiO2含量过高，可降低玻璃的成形性，因为更高的SiO2含量增加了熔融玻璃的难度，这依次不利地影响玻璃的成形性。在一些实施方式中，所述玻璃组合物通常包括大于或等于67摩尔％和小于或等于约80摩尔％或甚至小于或等于78摩尔％的SiO2。在一些实施方式中，所述玻璃组合物中SiO2的量可大于约68摩尔％、大于约69摩尔％或甚至大于约70摩尔％。在一些其它实施方式中，所述玻璃组合物中SiO2的量可大于72摩尔％、大于73摩尔％或甚至大于74摩尔％。例如，在一些实施方式中，所述玻璃组合物可包括从约68摩尔％至约80摩尔％或甚至至约78摩尔％的SiO2。在一些其它实施方式中，所述玻璃组合物可包括从约69摩尔％至约80摩尔％或甚至至约78摩尔％的SiO2。在一些其它实施方式中，所述玻璃组合物可包括从约70摩尔％至约80摩尔％或甚至至约78摩尔％的SiO2。还在其他实施方式中，所述玻璃组合物包括大于或等于70摩尔％且小于或等于78摩尔％的量的SiO2。在一些实施方式中，SiO2可以从约72摩尔％至约78摩尔％的量存在于所述玻璃组合物中。在一些其它实施方式中，SiO2可以从约73摩尔％至约78摩尔％的量存在于所述玻璃组合物中。在其它实施方式中，SiO2可以从约74摩尔％至约78摩尔％的量存在于所述玻璃组合物中。还在其它实施方式中，SiO2可以从约70摩尔％至约76摩尔％的量存在于所述玻璃组合物中。In the embodiments of the glass compositions described herein,SiO2 is the largest constituent of the composition and thus the major constituent of the resulting glass network.SiO2 enhances the chemical durability of the glass, specifically, the resistance of the glass composition to decomposition in acid and the resistance of the glass composition to decomposition in water. Therefore, a highSiO2 concentration is generally desired. However, if theSiO2 content is too high, the formability of the glass can be reduced because a higherSiO2 content increases the difficulty of melting the glass, which in turn adversely affects the formability of the glass. In some embodiments, the glass composition typically includes greater than or equal to 67 mole percent and less than or equal to about 80 mole percent, or even less than or equal to 78 mole percent SiO2 . In some embodiments, the amount ofSi02 in the glass composition can be greater than about 68 mole percent, greater than about 69 mole percent, or even greater than about 70 mole percent. In some other embodiments, the amount ofSi02 in the glass composition may be greater than 72 mole percent, greater than 73 mole percent, or even greater than 74 mole percent. For example, in some embodiments, the glass composition may include from about 68 mole percent to about 80 mole percent, or even to about 78 mole percent SiO2 . In some other embodiments, the glass composition may include from about 69 mol % to about 80 mol % or even to about 78 mol % SiO2 . In some other embodiments, the glass composition may include from about 70 mole percent to about 80 mole percent, or even to about 78 mole percent SiO2 . In still other embodiments, the glass composition includes SiO2 in an amount greater than or equal to 70 mole percent and less than or equal to 78 mole percent. In some embodiments,Si02 can be present in the glass composition in an amount from about 72 mole percent to about 78 mole percent. In some other embodiments,Si02 can be present in the glass composition in an amount from about 73 mole percent to about 78 mole percent. In other embodiments,SiO2 can be present in the glass composition in an amount from about 74 mole percent to about 78 mole percent. In still other embodiments,Si02 can be present in the glass composition in an amount from about 70 mole percent to about 76 mole percent.
本文所述的玻璃组合物还可包括Al2O3。Al2O3和存在于玻璃组合物中的碱金属氧化物如Na2O等结合，改善玻璃进行离子交换强化的敏感性。在本文所述的实施方式中，Al2O3可以X摩尔％的量存在于所述玻璃组合物中，同时碱金属氧化物以Y摩尔％的量存在于所述玻璃组合物中。为了促进上述对离子交换强化的敏感性，本文所述的玻璃组合物中的比例Y:X大于1。具体来说，玻璃组合物的扩散系数或者扩散率D与离子交换时碱金属离子渗透进入玻璃表面的速率相关。比例Y:X大于约0.9或甚至大于约1的玻璃的扩散率大于比例Y:X小于0.9的玻璃的扩散率。在给定离子交换时间和离子交换温度下，碱金属离子具有更大扩散率的玻璃可获得比碱金属离子具有更低扩散率的玻璃更大的层深度。此外，随着比例Y:X增加，玻璃的应变点、退火点和软化点降低，从而玻璃更加易于成形。此外，对于给定离子交换时间和离子交换温度，已发现具有比例Y:X大于约0.9且小于或等于2的玻璃包括的压缩应力，通常大于比例Y:X小于0.9或大于2的玻璃中产生的压缩应力。因此，在一些实施方式中，比例Y:X大于0.9或甚至大于1。在一些实施方式中，比例Y:X大于0.9，或甚至大于1，且小于或等于约2。还在其他实施方式中，比例Y:X可大于或等于约1.3且小于或等于约2.0，从而最大化在特定离子交换时间和离子交换温度下玻璃中包括的压缩应力的量。The glass compositions described herein may also include Al2 O3 . The combination of Al2 O3 and alkali metal oxides such as Na2 O in the glass composition improves the sensitivity of the glass for ion exchange strengthening.In embodiments described herein,Al2O3 may be present in the glass composition in an amount of X mole %, while the alkali metal oxide is present in the glass composition in an amount of Y mole %. To facilitate the aforementioned susceptibility to ion exchange strengthening, the ratio Y:X in the glass compositions described herein is greater than 1. Specifically, the diffusion coefficient or diffusivity D of a glass composition is related to the rate at which alkali metal ions permeate into the glass surface during ion exchange. Glasses with a ratio Y:X greater than about 0.9, or even greater than about 1, have a greater diffusivity than glasses with a ratio Y:X less than 0.9. For a given ion exchange time and ion exchange temperature, a glass with a greater diffusivity of alkali metal ions can achieve a greater depth of layer than a glass with a lower diffusivity of alkali metal ions. In addition, as the ratio Y:X increases, the strain point, annealing point, and softening point of the glass decrease, making the glass easier to shape. Furthermore, for a given ion exchange time and ion exchange temperature, it has been found that glasses having a ratio Y:X of greater than about 0.9 and less than or equal to 2 include compressive stresses generally greater than those produced in glasses with a ratio Y:X of less than 0.9 or greater than 2 of compressive stress. Thus, in some embodiments, the ratio Y:X is greater than 0.9 or even greater than 1. In some embodiments, the ratio Y:X is greater than 0.9, or even greater than 1, and less than or equal to about 2. In still other embodiments, the ratio Y:X may be greater than or equal to about 1.3 and less than or equal to about 2.0, thereby maximizing the amount of compressive stress included in the glass at a particular ion exchange time and ion exchange temperature.
但是，如果玻璃组合物中Al2O3的量过高，玻璃组合物对酸攻击的抵抗会降低。因此，本文所述的玻璃组合物通常包括大于或等于约2摩尔％或小于或等于约10摩尔％量的Al2O3。在一些实施方式中，该玻璃组合物中Al2O3的量是大于或等于约4摩尔％且小于或等于约8摩尔％。在一些其它实施方式中，该玻璃组合物中Al2O3的量是大于或等于约5摩尔％且小于或等于约7摩尔％。在一些其它实施方式中，该玻璃组合物中Al2O3的量是大于或等于约6摩尔％且小于或等于约8摩尔％。还在其它实施方式中，该玻璃组合物中Al2O3的量是大于或等于约5摩尔％且小于或等于约6摩尔％。However, if the amount ofAl2O3 in the glass composition is too high, the resistance of the glass composition toacid attack will be reduced. Accordingly, the glass compositions described herein typically include Al2 O3 in an amount greater than or equal to about 2 mole percent or less than or equal to about 10 mole percent. In some embodiments, the amount of Al2 O3 in the glass composition is greater than or equal to about 4 mole percent and less than or equal to about 8 mole percent. In some other embodiments, the amount of Al2 O3 in the glass composition is greater than or equal to about 5 mole percent and less than or equal to about 7 mole percent. In some other embodiments, the amount of Al2 O3 in the glass composition is greater than or equal to about 6 mole percent and less than or equal to about 8 mole percent. In still other embodiments, the amount of Al2 O3 in the glass composition is greater than or equal to about 5 mole percent and less than or equal to about 6 mole percent.
所述玻璃组合物还可包括一种或更多种碱金属氧化物如Na2O和/或K2O。碱金属氧化物促进玻璃组合物的离子交换能力，并因此促进玻璃的化学强化。碱金属氧化物可包括一种或更多种Na2O和K2O。碱金属氧化物通常以Y摩尔％的总浓度存在于玻璃组合物中。在本文所述的一些实施方式中，Y可大于约2摩尔％且小于或等于约18摩尔％。在一些其它实施方式中，Y可大于约8摩尔％、大于约9摩尔％、大于约10摩尔％或甚至大于约11摩尔％。例如，在本文所述的一些实施方式中，Y大于或等于8摩尔％且小于或等于约18摩尔％。还在其他实施方式中，Y可大于或等于9摩尔％且小于或等于约14摩尔％。The glass composition may also include one or more alkali metal oxides such as Na2O and/orK2O . Alkali metal oxides promote the ion exchange capacity of the glass composition and thus the chemical strengthening of the glass. Alkali metal oxides may include one or more ofNa2O andK2O . Alkali metal oxides are typically present in the glass composition at a total concentration of Y mole percent. In some embodiments described herein, Y can be greater than about 2 mole percent and less than or equal to about 18 mole percent. In some other embodiments, Y can be greater than about 8 mole percent, greater than about 9 mole percent, greater than about 10 mole percent, or even greater than about 11 mole percent. For example, in some embodiments described herein, Y is greater than or equal to 8 mole percent and less than or equal to about 18 mole percent. In still other embodiments, Y can be greater than or equal to 9 mole percent and less than or equal to about 14 mole percent.
主要通过在离子交换之前存在于玻璃组合物中的初始的碱金属氧化物Na2O的量，来把玻璃组合物的离子交换能力赋予该玻璃组合物。因此，在本文所述的玻璃组合物的实施方式中，存在于玻璃组合物中的碱金属氧化物至少包括Na2O。具体来说，为了在离子交换强化时在玻璃组合物获得所需的压缩强度和层深度，以所述玻璃组合物的分子量为基准计，所述玻璃组合物包括约2摩尔％-约15摩尔％量的Na2O。在一些实施方式中，以所述玻璃组合物的分子量为基准计，所述玻璃组合物包括至少约8摩尔％的Na2O。例如，Na2O的浓度可大于9摩尔％、大于10摩尔％或甚至大于11摩尔％。在一些实施方式中，Na2O的浓度可大于或等于9摩尔％或甚至大于或等于10摩尔％。例如，在一些实施方式中，所述玻璃组合物可包括大于或等于约9摩尔％且小于或等于约15摩尔％或甚至大于或等于约9摩尔％且小于或等于13摩尔％量的Na2O。The ion exchange capability of the glass composition is imparted to the glass composition primarily by the amount of initial alkali metaloxide Na2O present in the glass composition prior to ion exchange. Accordingly, in embodiments of the glass compositions described herein, the alkali metaloxide present in the glass composition includes at least Na2O. Specifically, in order to obtain the desired compressive strength and layer depth in the glass composition during ion exchange strengthening, based on the molecular weight of the glass composition, the glass composition includes about 2 mole % to about 15 mole % amount of Na2 O. In some embodiments, the glass composition includes at least about8 mole percent Na2O, based on the molecular weight of the glass composition. For example, the concentration of Na2O may be greater than9 mole percent, greater than 10 mole percent, or even greater than 11 mole percent. In some embodiments, the concentration of Na2O may be greaterthan or equal to 9 mole percent or even greater than or equal to 10 mole percent. For example, in some embodiments, the glass composition may include Na in an amount greater than or equal to about9 mole % and less than or equal to about 15 mole % or even greater than or equal to about O.
如上所述，玻璃组合物中的碱金属氧化物还可包括K2O。存在于玻璃组合物中的K2O的量，也与所述玻璃组合物的离子交换能力相关。具体来说，因为钾和钠离子的交换，随着存在于玻璃组合物中的K2O的量增加，通过离子交换获得的压缩应力降低。因此，限制存在于玻璃组合物中K2O的量是所期望的。在一些实施方式中，K2O的量大于或等于0摩尔％且小于或等于3摩尔％。在一些实施方式中，K2O的量小于或等于2摩尔％或甚至小于或等于1.0摩尔％。在玻璃组合物包括K2O的实施方式中，K2O可以下述浓度存在：大于或等于约0.01摩尔％且小于或等于约3.0摩尔％、或者甚至大于或等于约0.01摩尔％且小于或等于约2.0摩尔％。在一些实施方式中，该玻璃组合物中存在的K2O的量是大于或等于约0.01摩尔％且小于或等于约1.0摩尔％。因此，应理解K2O不必存在于玻璃组合物中。但是，当玻璃组合物包括K2O时，以所述玻璃组合物的分子量为基准计，K2O的量通常小于约3摩尔％。As noted above, the alkali metaloxide in the glass composition may also include K2O.The amount of K2O present in the glass composition is also related to the ion exchange capacity of the glass composition. Specifically, because of the exchange of potassium andsodium ions, as the amount of K2O present in the glass composition increases, the compressive stress obtained by ion exchange decreases. Therefore, it is desirable to limit the amount ofK2O present in the glass composition. In some embodiments, the amount of K2O is greaterthan or equal to 0 mole percent and less than or equal to 3 mole percent. In some embodiments, the amount of K2O is less than or equal to2 mole percent or even less than or equal to 1.0 mole percent.In embodiments where the glass composition includes K2O, the K2O may be present at a concentration of greaterthan or equal to about 0.01 mole percent and less than or equal to about 3.0 mole percent, or even greater than or equal to about 0.01 mole percent and less than or equal to Equal to about 2.0 mole %. In some embodiments, the amount of K2O present in the glass composition is greaterthan or equal to about 0.01 mole percent and less than or equal to about 1.0 mole percent. Therefore, it should be understood thatK2O need not be present in the glass composition. However, when the glass composition includes K2O, the amount of K2O is generally lessthan about3 mole percent based on the molecular weight of the glass composition.
碱土金属氧化物可存在于所述组合物中，来改善玻璃批料材料的熔融能力和增加玻璃组合物的化学耐久性。在本文所述的玻璃组合物中，存在于玻璃组合物中的碱土金属氧化物的总摩尔％通常小于存在于该玻璃组合物中的碱金属氧化物的总摩尔％，从而改善所述玻璃组合物的离子交换能力。在本文所述的实施方式中，所述玻璃组合物通常包括约3摩尔％-约13摩尔％的碱土金属氧化物。在一些实施方式中，玻璃组合物中的碱土金属氧化物的量可以是约4摩尔％-约8摩尔％，或者甚至约4摩尔％-约7摩尔％。Alkaline earth metal oxides may be present in the composition to improve the melting ability of the glass batch material and to increase the chemical durability of the glass composition. In the glass compositions described herein, the total mole % of alkaline earth metal oxides present in the glass composition is generally less than the total mole % of alkali metal oxides present in the glass composition, thereby improving the glass composition the ion exchange capacity of the substance. In embodiments described herein, the glass composition generally includes from about 3 mole percent to about 13 mole percent alkaline earth metal oxide. In some embodiments, the amount of alkaline earth metal oxide in the glass composition can be from about 4 mole percent to about 8 mole percent, or even from about 4 mole percent to about 7 mole percent.
玻璃组合物中的碱土金属氧化物可包括MgO,CaO,SrO,BaO或其组合。在一些实施方式中，碱土金属氧化物包括MgO,CaO或其组合。例如，在本文所述的实施方式中，碱土金属氧化物包括MgO。MgO以大于或等于约3摩尔％且小于或等于约8摩尔％MgO的量存在于玻璃组合物中。在一些实施方式中，以所述玻璃组合物的分子量计，MgO可以大于或等于约3摩尔％且小于或等于约7摩尔％、或者甚至大于或等于约4摩尔％且小于或等于约7摩尔％的量存在于玻璃组合物中。Alkaline earth metal oxides in the glass composition may include MgO, CaO, SrO, BaO, or combinations thereof. In some embodiments, the alkaline earth metal oxide includes MgO, CaO, or combinations thereof. For example, in embodiments described herein, the alkaline earth metal oxide includes MgO. MgO is present in the glass composition in an amount greater than or equal to about 3 mole percent and less than or equal to about 8 mole percent MgO. In some embodiments, MgO can be greater than or equal to about 3 mole percent and less than or equal to about 7 mole percent, or even greater than or equal to about 4 mole percent and less than or equal to about 7 mole percent, based on the molecular weight of the glass composition % is present in the glass composition.
在一些实施方式中，所述碱土金属氧化物还包括CaO。在这些实施方式中，以所述玻璃组合物的分子量计，CaO以约0摩尔％且小于或等于约6摩尔的量存在于玻璃组合物中。例如，存在于玻璃组合物中的CaO的量可小于或等于5摩尔％、小于或等于4摩尔％、小于或等于3摩尔％或者甚至小于或等于2摩尔％。在一些实施方式中，CaO可以大于或等于约0.1摩尔％且小于或等于约1.0摩尔％量存在于玻璃组合物中。例如，CaO可以大于或等于约0.2摩尔％且小于或等于约0.7摩尔％的量、或者甚至以大于或等于约0.3摩尔％且小于或等于约0.6摩尔％的量存在于玻璃组合物中。In some embodiments, the alkaline earth metal oxide further includes CaO. In these embodiments, CaO is present in the glass composition in an amount from about 0 mole percent to less than or equal to about 6 moles, based on the molecular weight of the glass composition. For example, the amount of CaO present in the glass composition may be less than or equal to 5 mole percent, less than or equal to 4 mole percent, less than or equal to 3 mole percent, or even less than or equal to 2 mole percent. In some embodiments, CaO can be present in the glass composition in an amount greater than or equal to about 0.1 mole percent and less than or equal to about 1.0 mole percent. For example, CaO may be present in the glass composition in an amount greater than or equal to about 0.2 mole percent and less than or equal to about 0.7 mole percent, or even in an amount greater than or equal to about 0.3 mole percent and less than or equal to about 0.6 mole percent.
在本文所述的实施方式中，玻璃组合物通常是富含MgO的(即，玻璃组合物中的MgO浓度大于玻璃组合物中其它碱土金属氧化物(包括但不限于CaO)的浓度)。形成玻璃组合物，从而该玻璃组合物是富含MgO的，改善了所得玻璃特别是在离子交换强化之后的耐水解性。此外，与富含其它碱土金属氧化物的玻璃组合物相比，富含MgO的玻璃组合物通常具有改善的离子交换性能。具体来说，从富含MgO的玻璃组合物形成的玻璃的扩散率通常大于富含其它碱土金属氧化物(如CaO)的玻璃组合物。更大的扩散率，使得能在玻璃中形成更深的层深度。与富含其它碱土金属氧化物如CaO的玻璃组合物相比，富含MgO的玻璃组合物还使得能在玻璃表面取得更高的压缩应力。此外，通常理解随着离子交换过程的进行，碱金属离子在玻璃中渗透得更深，在玻璃表面取得的最大压缩应力可能随时间而降低。但是，从富含MgO的玻璃组合物形成的玻璃比从富含CaO或富含其它碱土金属氧化物的玻璃组合物形成的玻璃(即贫MgO的玻璃)显示更低的压缩应力下降。因此，富含MgO的玻璃组合物使得能形成具有比富含其它碱土金属氧化物的玻璃更高的表面压缩应力和更大的层深度。In embodiments described herein, the glass composition is generally MgO-rich (ie, the concentration of MgO in the glass composition is greater than the concentration of other alkaline earth metal oxides, including but not limited to CaO, in the glass composition). Forming the glass composition such that the glass composition is MgO-rich improves the hydrolysis resistance of the resulting glass, particularly after ion exchange strengthening. In addition, MgO-rich glass compositions generally have improved ion exchange properties compared to glass compositions rich in other alkaline earth metal oxides. In particular, the diffusivity of glasses formed from MgO-rich glass compositions is generally greater than that of glass compositions rich in other alkaline earth metal oxides, such as CaO. Greater diffusivity enables deeper layer depths to form in the glass. MgO-rich glass compositions also enable higher compressive stresses to be achieved at the glass surface compared to glass compositions rich in other alkaline earth metal oxides, such as CaO. Furthermore, it is generally understood that the maximum compressive stress achieved at the glass surface may decrease over time as the ion exchange process proceeds and the alkali metal ions penetrate deeper into the glass. However, glasses formed from MgO-rich glass compositions exhibit lower compressive stress drops than glasses formed from CaO-rich or other alkaline earth metal oxide-rich glass compositions (ie, MgO-depleted glasses). Thus, MgO-rich glass compositions enable the formation of glasses with higher surface compressive stress and greater depth of layer than glasses rich in other alkaline earth metal oxides.
为了完全实现MgO在本文所述的玻璃组合物中的益处，已测定应最小化以摩尔％计的CaO浓度占CaO浓度和MgO浓度之和的比例(即(CaO/(CaO+MgO))。具体来说，已测定(CaO/(CaO+MgO)应小于或等于0.5。在一些实施方式中，(CaO/(CaO+MgO)小于或等于0.3或者甚至小于或等于0.2。在一些其它实施方式中，(CaO/(CaO+MgO)可甚至小于或等于0.1。To fully realize the benefits of MgO in the glass compositions described herein, it has been determined that the ratio of the CaO concentration in mole percent to the sum of the CaO concentration and the MgO concentration (ie (CaO/(CaO+MgO)) should be minimized. Specifically, it has been determined that (CaO/(CaO+MgO) should be less than or equal to 0.5. In some embodiments, (CaO/(CaO+MgO) is less than or equal to 0.3 or even less than or equal to 0.2. In some other embodiments Among them, (CaO/(CaO+MgO) may even be less than or equal to 0.1.
氧化硼(B2O3)是熔剂(flux)，可把它添加至玻璃组合物以降低在给定温度(如应变、退火和软化温度)下的粘度，由此改善玻璃的成形性。但是，已发现添加硼显著地降低了玻璃组合物中钠和钾离子的扩散率，这依次不利地影响所得玻璃的离子交换性能。具体来说，已发现与不含硼的玻璃组合物相比，添加硼显著的增加了获得给定层深度所需的时间。因此，在本文所述的一些实施方式中，最小化添加到玻璃组合物的硼的量，从而改善玻璃组合物的离子交换性能。Boron oxide (B2 O3 ) is a flux that can be added to glass compositions to lower the viscosity at a given temperature such as strain, annealing, and softening temperatures, thereby improving the formability of the glass. However, it has been found that the addition of boron significantly reduces the diffusivity of sodium and potassium ions in the glass composition, which in turn adversely affects the ion exchange properties of the resulting glass. In particular, it has been found that the addition of boron significantly increases the time required to achieve a given layer depth compared to glass compositions without boron. Accordingly, in some embodiments described herein, the amount of boron added to the glass composition is minimized, thereby improving the ion exchange properties of the glass composition.
例如，已发现可通过控制B2O3浓度与碱金属总浓度(即R2O，其中R是碱金属)和氧化铝之差的比例(即，B2O3(摩尔％)/(R2O(摩尔％)-Al2O3(摩尔％))，来减轻硼对玻璃组合物离子交换性能的影响。具体来说，已测定当B2O3/(R2O-Al2O3)的比例大于或等于约0且小于约0.3或者甚至小于约0.2时，玻璃组合物中的碱金属氧化物的扩散率不降低，并因此保持了玻璃组合物的离子交换性能。因此，在一些实施方式中，B2O3/(R2O-Al2O3)的比例大于0且小于或等于0.3。在一些实施方式中，B2O3/(R2O-Al2O3)的比例大于0且小于或等于0.2。因此，在一些实施方式中，B2O3/(R2O-Al2O3)的比例大于0且小于或等于0.15或甚至小于或等于0.1。因此，在一些其它实施方式中，B2O3/(R2O-Al2O3)的比例大于0且小于或等于0.05。把B2O3/(R2O-Al2O3)的比例维持在小于或等于0.3或甚至小于或等于0.2允许包括B2O3来降低玻璃组合物的应变点、退火点和软化点，且B2O3不会不利地影响玻璃的离子交换性能。For example, it has been found that by controlling theratioof the B2O3 concentration to the difference between the total concentration of alkali metals( ie, R2O, where R is an alkali metal) and alumina (ie, B2O3( mole %)/(R2 O (mol%)-Al2 O3 (mol%)), to reduce the impact of boron on the ion exchange performance of the glass composition. Specifically, it has been determined that when B2 O3 /(R2 O-Al2 O3 ) When the ratio is greater than or equal to about 0 and less than about 0.3 or even less than about 0.2, the diffusion rate of the alkali metal oxide in the glass composition is not reduced, and thus the ion exchange properties of the glass composition are maintained. Therefore, in In some embodiments, the ratio of B2 O3 /(R2 O—Al2 O3 ) is greater than 0 and less than or equal to 0.3. In some embodiments, the ratio of B2 O3 /(R2 O—Al2 O3 ) ratio is greater than 0 and less than or equal to 0.2. Thus, in some embodiments, the ratio of B2 O3 /(R2 O—Al2 O3 ) is greater than 0 and less than or equal to 0.15 or even less than or equal to 0.1. Therefore, in some other embodiments, the ratio of B2 O3 /(R2 O—Al2 O3 ) is greater than 0 and less than or equal to 0.05. Taking B2 O3 /(R2 O—Al2 O3 ) Maintaining a ratio of less than or equal to 0.3 or even lessthan or equal to 0.2 allows the inclusionof B2O3 to lower the strain point, annealing point, and softening pointof the glass composition withoutB2O3 adversely affecting the ion exchange properties of the glass .
在本文所述的实施方式中，玻璃组合物中的B2O3浓度通常小于或等于约4摩尔％、小于或等于约3摩尔％、小于或等于约2摩尔％或者甚至小于或等于1摩尔％。例如，在玻璃组合物中存在B2O3的实施方式中，B2O3的浓度可大于约0.01摩尔％且小于或等于4摩尔％。在一些实施方式中，B2O3的浓度可大于约0.01摩尔％且小于或等于3摩尔％。在一些实施方式中，B2O3可以大于或等于约0.01摩尔％且小于或等于2摩尔％或甚至小于或等于1.5摩尔％的量存在。或者，B2O3可以大于或等于约1摩尔％且小于或等于4摩尔％、大于或等于约1摩尔％且小于或等于3摩尔％、或甚至大于或等于约1摩尔％且小于或等于2摩尔％的量存在。在一些实施方式中，B2O3的浓度可以大于或等于约0.1摩尔％且小于或等于约1.0摩尔％量存在。In the embodiments described herein, the B2O3 concentration in the glass composition is typically less than or equal to about4 mole percent, less than or equal to about3 mole percent, less than or equal to about 2 mole percent, or even less than or equal to 1 mole percent %. For example, in embodiments where B2O3 is present in the glass composition, the concentrationof B2O3 can be greaterthan about 0.01 mole percent and lessthan or equal to4 mole percent. In some embodiments, the concentration of B2O3 can be greaterthan about 0.01 mole percent and less than or equal to3 mole percent.In some embodiments, B2O3 may be present in an amount greaterthan or equal to about 0.01 mole percent and less than or equal to 2 mole percent, or even less than or equal to 1.5 mole percent. Alternatively, B2O3 can be greaterthan or equal to about1 mole percent and less than or equal to 4 mole percent, greater than or equal to about 1 mole percent and less than or equal to 3 mole percent, or even greater than or equal to about 1 mole percent and less than or equal to An amount of 2 mole % is present.In some embodiments, the concentration of B2O3 can be present in an amount greaterthan or equal to about 0.1 mole percent and less than or equal to about 1.0 mole percent.
虽然在一些实施方式中，最小化了玻璃组合物中B2O3的浓度，来改善玻璃的形成性质又不减损玻璃的离子交换性能，但是在一些其他实施方式中，玻璃组合物不含硼和硼的化合物如B2O3。具体来说，已测定通过减少用于取得具体值的压缩应力和/或层深度所需的加工时间和/或温度，形成不含硼和硼的化合物的玻璃改善了玻璃组合物的离子交换能力。While in some embodiments theB2O3 concentration in the glass composition is minimized to improve the glass forming properties without detracting from the ion exchange propertiesof the glass, in some other embodiments the glass composition is free of boron And boron compounds such as B2 O3 . In particular, it has been determined that forming a glass free of boron and boron compounds improves the ion exchange capacity of the glass composition by reducing the processing time and/or temperature required to achieve a particular value of compressive stress and/or depth of layer .
在本文所述的玻璃组合物的一些实施方式中，玻璃组合物不含磷和含磷化合物(包括，但不限于P2O5)。具体来说，已测定制备不含磷或磷化合物的玻璃组合物，增加了该玻璃组合物的化学耐久性。In some embodiments of the glass compositions described herein, the glass composition is free of phosphorus and phosphorus-containing compounds (including, but not limited to, P2 O5 ). In particular, it has been determined that making glass compositions free of phosphorus or phosphorus compounds increases the chemical durability of the glass compositions.
除了SiO2,Al2O3、碱金属氧化物和碱土金属氧化物以外，本文所述的玻璃组合物还可任选的包括一种或更多种澄清剂，如SnO2,As2O3和/或Cl-(来自NaCl等)。当玻璃组合物中存在澄清剂时，所述澄清剂以小于或等于约1摩尔％或甚至小于或等于约0.4摩尔％的量存在。例如，在一些实施方式中，所述玻璃组合物可包括SnO2作为澄清剂。在这些实施方式中，SnO2可以大于约0摩尔％且小于或等于约1摩尔％的量、或甚至以大于或等于0.01摩尔％且小于或等于约0.30摩尔％的量存在于玻璃组合物中。In addition to SiO2 , Al2 O3 , alkali metal oxides and alkaline earth metal oxides, the glass compositions described herein may optionally include one or more fining agents such as SnO2 , As2 O3 and/or Cl- (from NaCl, etc.). When present in the glass composition, the fining agent is present in an amount less than or equal to about 1 mole percent, or even less than or equal to about 0.4 mole percent. For example, in some embodiments, the glass composition can include SnO2 as a fining agent. In these embodiments,SnO can be present in the glass composition in an amount greater than about 0 mole percent and less than or equal to about 1 mole percent, or even in an amount greater than or equal to 0.01 mole percent and less than or equal to about 0.30 mole percent .
此外，本文所述的玻璃组合物可包括一种或更多种金属氧化物，来进一步改善玻璃组合物的化学耐久性。例如，所述玻璃组合物还可包括ZnO,TiO2或ZrO2，它们各自进一步改善玻璃组合物对化学攻击的抵抗。在这些实施方式中，其它金属氧化物可以大于或等于约0摩尔％且小于或等于约2摩尔％的量存在。例如，当其它金属氧化物是ZnO时，ZnO可以大于或等于1摩尔％且小于或等于约2摩尔％的量存在。当其它金属氧化物是ZrO2或TiO2时，ZrO2或TiO2可以小于或等于约1摩尔％的量存在。Additionally, the glass compositions described herein can include one or more metal oxides to further improve the chemical durability of the glass composition. For example, the glass composition may also include ZnO, TiO2 or ZrO2 , each of which further improves the resistance of the glass composition to chemical attack. In these embodiments, the other metal oxides may be present in an amount greater than or equal to about 0 mole percent and less than or equal to about 2 mole percent. For example, when the other metal oxide is ZnO, ZnO may be present in an amount greater than or equal to 1 mole percent and less than or equal to about 2 mole percent. When the other metaloxide is ZrO2 orTiO2 , ZrO2 orTiO2 may be present in an amount less than or equal to about1 mole percent.
如上所述，玻璃组合物存在碱金属氧化物促进了通过离子交换对玻璃的化学强化。具体来说，碱金属离子如钾离子、钠离子等，在玻璃中是足够可动的，从而促进离子交换。在一些实施方式中，玻璃组合物是可离子交换的，从而形成层深度大于或等于10微米的压缩应力层。在一些实施方式中，层深度可大于或等于约25微米或甚至大于或等于约50微米。在一些实施方式中，层深度可大于或等于75微米或甚至大于或等于100微米。还在其他实施方式中，层深度可大于或等于约10微米且小于或等于约100微米。玻璃组合物在100％熔融KNO3盐浴中于350℃-500℃下处理小于约30小时或甚至小于20小时的时段后，相关的表面压缩应力可大于或等于约250MPa、大于或等于300MPa或甚至大于或等于约350MPa。As noted above, the presence of alkali metal oxides in the glass composition facilitates the chemical strengthening of the glass by ion exchange. Specifically, alkali metal ions, such as potassium ions, sodium ions, etc., are sufficiently mobile in the glass to facilitate ion exchange. In some embodiments, the glass composition is ion-exchangeable, thereby forming a compressive stress layer with a layer depth greater than or equal to 10 microns. In some embodiments, the layer depth can be greater than or equal to about 25 microns or even greater than or equal to about 50 microns. In some embodiments, the layer depth may be greater than or equal to 75 microns or even greater than or equal to 100 microns. In still other embodiments, the layer depth can be greater than or equal to about 10 microns and less than or equal to about 100 microns. The associated surface compressive stress may be greater than or equal to about 250 MPa, greater than or equal to300 MPa, or Even greater than or equal to about 350MPa.
从本文所述的玻璃组合物形成的玻璃制品除了因离子交换强化而具有改善的机械特征以外，还可具有根据ISO719的HGB2或甚至HGB1耐水解性和/或根据ISO720的HGA2或甚至HGA1耐水解性(如下文所进一步描述)。在本文所述的一些实施方式中，玻璃制品可具有压缩应力层，该压缩应力层从表面延伸至玻璃制品中大于或等于25微米或甚至大于或等于35微米的层深度。在一些实施方式中，层深度可大于或等于40微米或甚至大于或等于50微米。玻璃制品的表面压缩应力可大于或等于250MPa、大于或等于350MPa或甚至大于或等于400MPa。因为如上所述的玻璃组合物中增强的碱金属离子扩散率，本文所述的玻璃组合物有助于比常规玻璃组合物更快速地和/或在更低温度下来取得上述层深度和表面压缩应力。例如，可在小于或等于500℃或甚至小于或等于450℃的温度下，通过把玻璃制品在100％KNO3(或者KNO3和NaNO3的混合盐浴)熔融盐浴中离子交换小于或等于5小时或甚至小于或等于4.5小时的时段，来取得层深度(即大于或等于25微米)和压缩应力(即大于或等于250MPa)。在一些实施方式中，用于取得这些层深度和压缩应力的时段可小于或等于4小时或甚至小于或等于3.5小时。用于取得这些层深度和压缩应力的温度可小于或等于400℃或甚至小于或等于350℃。Glass articles formed from the glass compositions described herein may have HGB2 or even HGB1 hydrolysis resistance according to ISO719 and/or HGA2 or even HGA1 hydrolysis resistance according to ISO720, in addition to improved mechanical characteristics due to ion exchange strengthening Sex (as further described below). In some embodiments described herein, the glass article can have a compressive stress layer extending from the surface to a layer depth in the glass article of greater than or equal to 25 microns, or even greater than or equal to 35 microns. In some embodiments, the layer depth may be greater than or equal to 40 microns or even greater than or equal to 50 microns. The surface compressive stress of the glass article may be greater than or equal to 250 MPa, greater than or equal to 350 MPa, or even greater than or equal to 400 MPa. Because of the enhanced alkali metal ion diffusivity in the glass compositions described above, the glass compositions described herein facilitate achieving the aforementioned layer depths and surface compressions more rapidly and/or at lower temperatures than conventional glass compositions stress. For example, at a temperature less than or equal to 500°C or even less than or equal to 450°C, ion exchange of the glassware in a molten salt bath of 100% KNO3 (or a mixed salt bath of KNO3 and NaNO3 ) less than or equal to A period of 5 hours or even less than or equal to 4.5 hours to obtain layer depth (ie greater than or equal to 25 microns) and compressive stress (ie greater than or equal to 250 MPa). In some embodiments, the time period for obtaining these layer depths and compressive stresses may be less than or equal to 4 hours or even less than or equal to 3.5 hours. The temperature used to achieve these layer depths and compressive stresses may be less than or equal to 400°C or even less than or equal to 350°C.
当玻璃组合物的阀值扩散率在小于或等于450℃的温度下大于约16微米2/小时或甚至在小于或等于450℃的温度下大于或等于20微米2/小时时，可取得这些改善的离子交换特征。在一些实施方式中，阀值扩散率在小于或等于450℃的温度下可大于或等于约25微米2/小时或者甚至在小于或等于450℃的温度下是30微米2/小时。在一些其它实施方式中，阀值扩散率在小于或等于450℃的温度下可大于或等于约35微米2/小时或者甚至在小于或等于450℃的温度下是40微米2/小时。还在其它实施方式中，阀值扩散率在小于或等于450℃的温度下可大于或等于约45微米2/小时或者甚至在小于或等于450℃的温度下是50微米2/小时。These improvements are achieved when the threshold diffusivity of the glass composition is greater than about 16micron2 /hour at a temperature of less than or equal to 450°C or even greater than or equal to 20micron2 /hour at a temperature of less than or equal to 450°C ion exchange characteristics. In some embodiments, the threshold diffusivity may be greater than or equal to about 25micron2 /hour at a temperature of less than or equal to 450°C or even 30micron2 /hour at a temperature of less than or equal to 450°C. In some other embodiments, the threshold diffusivity may be greater than or equal to about 35micron2 /hour at a temperature of less than or equal to 450°C or even 40micron2 /hour at a temperature of less than or equal to 450°C. In still other embodiments, the threshold diffusivity may be greater than or equal to about 45micron2 /hour at a temperature of less than or equal to 450°C or even 50micron2 /hour at a temperature of less than or equal to 450°C.
本文所述的玻璃组合物的应变点通常大于或等于约525℃且小于或等于约650℃。此外，玻璃的退火点可大于或等于约560℃且小于或等于约725℃，以及退火点大于或等于约750℃且小于或等于约960℃。The glass compositions described herein generally have a strain point of greater than or equal to about 525°C and less than or equal to about 650°C. In addition, the glass may have an annealing point of greater than or equal to about 560°C and less than or equal to about 725°C, and an annealing point of greater than or equal to about 750°C and less than or equal to about 960°C.
在本文所述的实施方式中，玻璃组合物的CTE小于约70x10-7K-1或甚至小于约60x10-7K-1。相对于具有更高CTE的玻璃组合物而言，这些更低的CTE值改善了玻璃在热循环或热应力条件下的存活能力。In embodiments described herein, the glass composition has a CTE of less than about70x10-7 K-1 or even less than about60x10-7 K-1 . These lower CTE values improve the ability of the glass to survive thermal cycling or thermal stress conditions relative to glass compositions with higher CTEs.
此外，如上所述，根据DIN12116标准、ISO695标准和ISO720标准所测定，玻璃组合物是化学耐久性的和耐降解的。Furthermore, the glass composition is chemically durable and resistant to degradation as measured according to the DIN12116 standard, the ISO695 standard and the ISO720 standard, as described above.
具体来说，DIN12116标准是玻璃被置于酸性溶液中时对分解的抵抗的度量。简单来说，DIN12116标准使用称重过的具有已知表面区域的抛光玻璃样品，并随后使玻璃样品与比例量的煮沸的6M盐酸接触6小时。然后从溶液中取出样品，干燥并再次称重。暴露于酸溶液时玻璃的质量损失，是样品酸耐久性的度量，数值越小表明耐久性越大。测试结果用半质量每表面积的单位来记录，具体为毫克/分米2。DIN12116标准分裂成独立的级别。S1级别指重量损失最高至0.7毫克/分米2；S2级别指重量损失从0.7毫克/分米2到最高至1.5毫克/分米2；S3级别指重量损失从1.5毫克/分米2到最高至15毫克/分米2；以及S4级别指重量损失大于15毫克/分米2。Specifically, the DIN12116 standard is a measure of the resistance of glass to decomposition when placed in an acidic solution. Briefly, the DIN 12116 standard uses a weighed polished glass sample of known surface area and subsequently contacts the glass sample with a proportional amount of boiling 6M hydrochloric acid for 6 hours. The samples were then removed from the solution, dried and weighed again. The mass loss of the glass when exposed to an acid solution is a measure of the acid durability of the sample, with smaller numbers indicating greater durability. Test results are reported in units of half mass per surface area, specificallymg /dm2. The DIN12116 standard is split into separate levels. S1 class refers to weight loss up to 0.7 mg/dm2; S2 class refers to weight loss from 0.7mg /dm2 to up to 1.5 mg/dm2; S3 class refers to weight loss from 1.5 mg/dm2 tomax . to 15 mg/dm2 ; and S4 class refers to weight loss greater than 15 mg/dm2 .
ISO695标准是玻璃被置于碱性溶液中时对分解的抵抗的度量。简单来说，ISO695标准使用称重过的抛光玻璃样品，并随后使玻璃样品在煮沸的1M NaOH+0.5M Na2CO3溶液中放置3小时。然后从溶液中取出样品，干燥并再次称重。暴露于碱溶液时玻璃的质量损失，是样品碱耐久性的度量，数值越小表明耐久性越大。和DIN12116标准类似，ISO695标准的结果以质量每表面积的单位记录，具体为毫克/分米2。ISO695标准分裂成独立的级别。A1级别指重量损失最高达75毫克/分米2；A2级别指重量损失为从75毫克/分米2到最高达175毫克/分米2；以及A3级别指重量损失大于175毫克/分米2。The ISO695 standard is a measure of the resistance of glass to decomposition when placed in an alkaline solution. Briefly, the ISO695 standard uses weighed polished glass samples and then places the glass samples in a boiling 1M NaOH + 0.5MNa2CO3 solution for3 hours. The samples were then removed from the solution, dried and weighed again. The mass loss of the glass when exposed to an alkaline solution is a measure of the alkali durability of the sample, with smaller numbers indicating greater durability. Similar to the DIN12116 standard, the ISO695 standard results are reported in units of mass per surface area, specificallymg /dm2. The ISO695 standard is split into separate levels. Class A1 refers to weight loss up to 75 mg/dm2; Class A2 refers to weight loss from 75mg /dm2 up to 175 mg/dm2; and Class A3 refers to weight loss greater than 175mg /dm2 .
ISO720标准是玻璃在纯净的、不含CO2的水中时对降解的抵抗的度量。简单来说，ISO720标准协议使用粉碎的玻璃晶粒，在高压釜条件(121℃，2大气压)下，使所述玻璃晶粒与纯净的、不含CO2的水接触30分钟。然后，用稀HCl比色滴定溶液，以中和pH。然后，把滴定成中性溶液所需的HCl的量转化成当量的从玻璃中提取的Na2O，并以微克Na2O每玻璃重量来记录，数值越小表明耐久性越大。ISO720标准分裂成独立的类型。HGA1型指每克被测玻璃提取的当量Na2O最高达62微克；HGA2型指每克被测玻璃提取的当量Na2O大于62微克且最高达527微克；类型HGA3指每克被测玻璃提取的当量Na2O大于527微克且最高达930微克。The ISO720 standard is a measure of the resistance of glass to degradation when exposed to pure,CO2 -free water. Briefly, the ISO720 standard protocol uses crushed glass grains, which are contacted with pure,CO2 -free water for 30 minutes under autoclave conditions (121 °C, 2 atmospheres). Then, the solution was colorimetrically titrated with dilute HCl to neutralize the pH. The amount of HCl required to titrate to a neutral solution was then converted to equivalent Na2O extracted from the glass andreported in micrograms ofNa2O per weight of glass, with lower numbers indicating greater durability. The ISO720 standard splits into separate types. HGA1 type means that the equivalent Na2 O extracted per gram of the tested glass is up to 62 micrograms; HGA2 type means that the equivalent Na2 O extracted per gram of the tested glass is greater than 62 micrograms and up to 527 micrograms; type HGA3 refers to the equivalent of 527 micrograms per gram of the tested glass The extracted equivalent Na2O was greaterthan 527 micrograms and up to 930 micrograms.
ISO719标准是玻璃在纯净的、不含CO2的水中时对降解的抵抗的度量。简单来说，ISO719标准协议使用粉碎的玻璃晶粒，在98℃的温度和1大气压下，使所述玻璃晶粒与纯净的、不含CO2的水接触30分钟。然后，用稀HCl比色滴定溶液，以中和pH。然后，把滴定成中性溶液所需的HCl的量转化成当量的从玻璃中提取的Na2O，并以微克Na2O每玻璃重量来记录，数值越小表明耐久性越大。ISO719标准分裂成独立的类型。ISO719标准分裂成独立的类型。HGB1型指提取的当量Na2O最高达31微克；HGB2型指提取的当量Na2O大于31微克且最高达62微克；HGB3型指提取的当量Na2O大于62微克且最高达264微克；HGB4型指提取的当量Na2O大于264微克且最高达620微克；HGB5型指提取的当量Na2O大于620微克且最高达1085微克。本文所述的玻璃组合物具有ISO719的HGB2型耐水解性或更好，有些实施方式具有HGB1型耐水解性。The ISO719 standard is a measure of the resistance of glass to degradation when exposed to pure,CO2 -free water. Briefly, the ISO719 standard protocol uses crushed glass grains, which are contacted with pure,CO2 -free water for 30 minutes at a temperature of 98 °C and a pressure of 1 atmosphere. Then, the solution was colorimetrically titrated with dilute HCl to neutralize the pH. The amount of HCl required to titrate to a neutral solution was then converted to equivalent Na2O extracted from the glass andreported in micrograms ofNa2O per weight of glass, with lower numbers indicating greater durability. The ISO719 standard splits into separate types. The ISO719 standard splits into separate types. HGB1 type means that the extracted equivalent Na2 O is up to 31 micrograms; HGB2 type means that the extracted equivalent Na2 O is greater than 31 micrograms and up to 62 micrograms; HGB3 type means that the extracted equivalent Na2 O is greater than 62 micrograms and up to 264 micrograms; HGB4 type means that the extracted equivalent Na2 O is greater than 264 micrograms and up to 620 micrograms; HGB5 type means that the extracted equivalent Na2 O is greater than 620 micrograms and up to 1085 micrograms. The glass compositions described herein have an ISO719 type HGB2 hydrolysis resistance or better, and some embodiments have a HGB1 type hydrolysis resistance.
本文所述的玻璃组合物，在离子交换强化前后的耐酸性至少为根据DIN12116的S3级别，有些实施方式在离子交换强化之后的耐酸性至少为S2级别或甚至为S1级别。在一些其他实施方式中，玻璃组合物在离子交换强化前后的耐酸性至少为S2级别，有些实施方式在离子交换强化之后的耐酸性为S1级别。此外，本文所述的玻璃组合物，在离子交换强化前后的耐碱性至少为根据ISO695的A2级别，有些实施方式在离子交换强化之后的耐碱性至少为A1级别。此外，本文所述的玻璃组合物，在离子交换强化前后的耐水解性至少为根据ISO720的HGA2型，有些实施方式在离子交换强化之后的耐水解性为HGA1型，以及有些其它实施方式在离子交换强化前后的耐水解性为HGA1型。本文所述的玻璃组合物具有ISO719的HGB2型耐水解性或更好，有些实施方式具有HGB1型耐水解性。应理解，当参考上述根据DIN12116、ISO695、ISO720和ISO719的分级时，具有“至少”特定级别的玻璃组合物或玻璃制品，指玻璃组合物的性能与该特定级别一样好或者更好。例如，具有DIN12116“至少S2级别”耐酸性的玻璃制品，可具有DIN12116S1或S2级别。The glass compositions described herein have an acid resistance of at least S3 class according to DIN 12116 before and after ion exchange strengthening, and some embodiments have an acid resistance of at least S2 class or even S1 class after ion exchange strengthening. In some other embodiments, the glass composition has an acid resistance of at least S2 level before and after ion exchange strengthening, and some embodiments have an acid resistance of S1 level after ion exchange strengthening. In addition, the glass compositions described herein have an alkali resistance of at least A2 level according to ISO695 before and after ion exchange strengthening, and some embodiments have an alkali resistance of at least A1 level after ion exchange strengthening. In addition, the glass compositions described herein have a hydrolysis resistance of at least Type HGA2 according to ISO720 before and after ion exchange strengthening, some embodiments have a hydrolysis resistance of Type HGA1 after ion exchange strengthening, and some other embodiments have a hydrolysis resistance of at least Type HGA1 after ion exchange strengthening, and some other embodiments have a hydrolysis resistance of The hydrolysis resistance before and after exchange strengthening is HGA1 type. The glass compositions described herein have an ISO719 type HGB2 hydrolysis resistance or better, and some embodiments have a HGB1 type hydrolysis resistance. It will be understood that a glass composition or glass article having "at least" a particular class when referring to the above classifications according to DIN12116, ISO695, ISO720 and ISO719 means that the performance of the glass composition is as good or better than that particular class. For example, a glass article with DIN12116 "at least S2 grade" acid resistance may have DIN12116 S1 or S2 grade.
本文所述的玻璃组合物通过混合玻璃原料批料(如SiO2、Al2O3、碱金属氧化物、碱土金属氧化物等的粉末)来形成，从而玻璃原料批料具有所需的组成。然后，加热玻璃原料批料以形成熔融的玻璃组合物，并后续地冷却和固化以形成玻璃组合物。在固化时(即当玻璃组合物是可塑性形变的时)，可通过标准的成形技术来成形玻璃组合物，从而把玻璃组合物成形为所需的最终形式。或者，可把玻璃制品成形为定型形式(stock form)，如板、管等，并后续地再加热和成形为所需的最终形式。The glass compositions described herein are formed by mixing glass raw material batches (eg, powders ofSiO2 ,Al2O3 , alkali metal oxides, alkaline earth metal oxides, etc.) such that the glass raw material batches have the desired composition. The batch of glass raw materials is then heated to form a molten glass composition, and subsequently cooled and solidified to form a glass composition. Upon curing (ie, when the glass composition is plastically deformable), the glass composition can be shaped by standard forming techniques to form the glass composition into the desired final form. Alternatively, the glass article can be formed into a stock form, such as a plate, tube, etc., and subsequently reheated and formed into the desired final form.
可把本文所述的玻璃组合物成形为具有各种形式如板、管等的玻璃制品。但是，因为玻璃组合物的化学耐久性，本文所述的玻璃组合物特别良好地适用于成形玻璃制品，该玻璃制品用作容纳药物组合物如液体、粉末等的药物包装或药物容器。例如，本文所述的玻璃组合物可用来形成玻璃容器，所述玻璃容器具有各种形状形式包括，但不限于：真空采血管()、墨盒、注射器、安瓿瓶(ampoule)、瓶、管形瓶、试管、烧杯、小瓶等。此外，可利用通过离子交换化学强化玻璃组合物的能力，来改善这种由所述玻璃组合物成形的药物包装或玻璃制品的机械耐久性。因此，应理解，在至少一种实施方式中，在药物包装中结合了玻璃组合物，从而改善该药物包装的化学耐久性和/或机械耐久性。The glass compositions described herein can be formed into glass articles having various forms such as plates, tubes, and the like. However, because of the chemical durability of the glass compositions, the glass compositions described herein are particularly well suited for use in shaped glass articles used as pharmaceutical packaging or pharmaceutical containers containing pharmaceutical compositions such as liquids, powders, and the like. For example, the glass compositions described herein can be used to form glass containers in a variety of shapes and forms including, but not limited to: Vacuum blood collection tubes ( ), cartridges, syringes, ampoules, bottles, vials, test tubes, beakers, vials, and the like. Furthermore, the ability to chemically strengthen glass compositions by ion exchange can be exploited to improve the mechanical durability of such pharmaceutical packaging or glass articles formed from said glass compositions. Accordingly, it will be appreciated that in at least one embodiment, a glass composition is incorporated in a pharmaceutical package to improve the chemical and/or mechanical durability of the pharmaceutical package.
实施例Example
通过以下实施例进一步阐述本文所述的玻璃组合物。The glass compositions described herein are further illustrated by the following examples.
实施例1Example 1
制备了6种示例发明性玻璃组合物(组合物A-F)。各个示例玻璃组合物的具体组成见下文的表1。各个示例玻璃组合物都制备了多个样品。把各组合物的一组样品在100％KNO3的熔融盐浴中，于450℃下离子交换至少5小时，从而在样品的表面产生压缩层。压缩层的表面压缩应力为至少500MPa，且层深度为至少45微米。Six exemplary inventive glass compositions (Compositions AF) were prepared. The specific composition of each example glass composition is found in Table 1 below. Multiple samples were prepared for each example glass composition. A set of samples of each composition was ion-exchanged in a molten salt bath of 100%KNO3 at 450° C. for at least 5 hours to create a compressive layer on the surface of the samples. The compressive layer has a surface compressive stress of at least 500 MPa and a layer depth of at least 45 microns.
然后，使用上述DIN12116标准、ISO695标准和ISO720标准来测定各示例玻璃组合物的化学耐久性。具体来说，根据DIN12116标准、ISO695标准或ISO720标准中的一种来测试各示例玻璃组合物的未离子交换测试样品，从而分别测定测试样品的耐酸性、耐碱性或耐水解性。根据ISO720标准测定各示例玻璃组合物的离子交换样品的耐水解性。为了测定离子交换样品的耐水解性，把玻璃粉碎成ISO720标准所要求的粒径，在100％KNO3的熔融盐浴中，于450℃下离子交换至少5小时，从而在单个玻璃晶粒中产生压缩层，并随后根据ISO720标准测试。所有所测样品的平均结果见下文表1。Then, the chemical durability of each exemplary glass composition was determined using the above-mentioned DIN12116 standard, ISO695 standard, and ISO720 standard. Specifically, the non-ion-exchanged test samples of each exemplary glass composition were tested according to one of the DIN12116 standard, ISO695 standard or ISO720 standard, so as to determine the acid resistance, alkali resistance or hydrolysis resistance of the test samples, respectively. The hydrolysis resistance of ion-exchanged samples of each exemplary glass composition was determined according to the ISO720 standard. In order to measure the hydrolysis resistance of ion-exchange samples, the glass is crushed into the particle size required by the ISO720 standard, and ion-exchanged at 450 ° C for at least 5 hours in a molten salt bath of 100% KNO3 , so that in a single glass grain Compression layers are produced and subsequently tested according to the ISO720 standard. The average results for all samples tested are shown in Table 1 below.
如表1所示，根据本发明的DIN12116标准的测试，示例玻璃组合物A-F全部显示了玻璃质量损失小于5毫克/分米2且大于1毫克/分米2，且示例玻璃组合物E具有最低的玻璃质量损失，为1.2毫克/分米2。因此，各示例玻璃组合物的分级至少为DIN12116标准的S3级别，示例玻璃组合物E的分级是S2级别。基于这些测试结果，据信玻璃样品的耐酸性随着SiO2含量的增加而改善。As shown in Table 1, according to the test of the DIN12116 standard of the present invention, the example glass compositions AF all show glass mass loss less than 5 mg/dm2 and greater than1mg /dm2, and the example glass composition E has the lowest The glass mass loss is1.2 mg/dm2. Therefore, the classification of each exemplary glass composition is at least the S3 level of the DIN12116 standard, and the classification of the exemplary glass composition E is the S2 level. Based on these test results, it is believed that the acid resistance of the glass samples improves with increasingSiO2 content.
此外，根据ISO695标准的测试，示例玻璃组合物A-F全部显示了玻璃质量损失为小于80毫克/分米2，且示例玻璃组合物A具有最低的玻璃质量损失，为60毫克/分米2。因此，各示例玻璃组合物的分级至少为ISO695标准的A2级别，示例玻璃组合物A,B,D和F的分级是A1级别。一般地，具有更高二氧化硅含量的组合物具有更低的耐碱性，具有更高碱金属/碱土金属含量的组合物具有更高的耐碱性。Furthermore, Exemplary Glass Compositions AF all exhibit glass mass loss of less than 80 mg/dm2 , and Exemplary Glass Composition A has the lowest glass mass loss of 60 mg/dm2 when tested according to the ISO695 standard. Therefore, the classification of each exemplary glass composition is at least the grade A2 of the ISO695 standard, and the classification of the exemplary glass compositions A, B, D and F is grade A1. In general, compositions with higher silica content have lower alkali resistance and compositions with higher alkali metal/alkaline earth metal content have higher alkali resistance.
表1还显示了根据ISO720标准测试，示例玻璃组合物A-F的未离子交换测试样品全部显示至少HGA2型的耐水解性，且示例玻璃组合物C-F的耐水解性为HGA1型。据信，示例玻璃组合物C-F的耐水解性是因为相对于示例玻璃组合物A和B，玻璃组合物中的SiO2量更高且Na2O量更低。Table 1 also shows that the non-ion-exchanged test samples of Exemplary Glass Compositions AF all exhibited at least a hydrolysis resistance of type HGA2 and that Exemplary Glass Compositions CF had a hydrolysis resistance of type HGA1 when tested according to the ISO720 standard. It is believed that the hydrolysis resistance of example glass composition CF is due to the higher amount ofSi02 and lower amount ofNa20 in the glass composition relative to example glass compositions A and B.
此外，根据ISO720标准的测试，示例玻璃组合物B-F的离子交换测试样品显示更低的每克玻璃提取的Na2O量，低于相同示例玻璃组合物的未离子交换测试样品的量。In addition, ion-exchanged test samples of Exemplary Glass Composition BF exhibited lower amounts of Na2O extracted per gram of glassthan non-ion-exchanged test samples of the same Exemplary Glass Composition when tested according to the ISO720 standard.
表1：示例玻璃组合物的组成和性质Table 1: Composition and Properties of Example Glass Compositions
实施例2Example 2
制备了3种示例发明性玻璃组合物(组合物G-I)和3种比较玻璃组合物(组合物1-3)。改变各组合物中碱金属氧化物和氧化铝(即Y:X)的比例，来评估该比例对所得玻璃熔体和玻璃的各种性质的影响。各示例发明性玻璃组合物和比较玻璃组合物的具体组成见表2。测定了由各玻璃组合物形成的熔体的应变点、退火点和软化点，并见表2。此外，还测定了所得玻璃的热膨胀系数(CTE)、密度和应力光学系数(SOC)，并见表2。根据ISO720标准，测定了在100％KNO3熔盐浴中于450℃下离子交换5小时前后，从各个示例发明性玻璃组合物和各个比较性玻璃组合物的玻璃样品的耐水解性。对于离子交换的那些样品，用基础应力测试(FSM)仪器测定压缩应力，压缩应力值以所测的应力光学系数(SOC)为基础。FSM仪器把光耦合进出双折射的玻璃表面。然后，通过物质常数应力光学系数或光弹性系数(SOC或PEC)，把所测双折射与应力相联系，并得到两个参数：最大表面压缩应力(CS)和交换层深度(DOL)。还测定了玻璃中碱金属离子的扩散率和每时间的平方根的应力变化。根据下述关系，从所测层深度(DOL)和离子交换时间(t)来计算玻璃的扩散率(D)：DOL＝～1.4*(4*D*t)1/2。根据阿仑尼乌斯(Arrhenius)关系，扩散率随温度增加，因此在特定温度下报道扩散率。Three exemplary inventive glass compositions (Compositions GI) and three comparative glass compositions (Compositions 1-3) were prepared. The ratio of alkali metal oxide to alumina (ie, Y:X) in each composition was varied to evaluate the effect of this ratio on various properties of the resulting glass melts and glasses. The specific composition of each exemplary inventive glass composition and comparative glass composition is shown in Table 2. The strain point, annealing point and softening point of the melts formed from each glass composition were determined and are shown in Table 2. In addition, the coefficient of thermal expansion (CTE), density and stress optical coefficient (SOC) of the obtained glass were also measured, and are shown in Table 2. The hydrolysis resistance of glass samples from each exemplary inventive glass composition and each comparative glass composition was determined before and after ion exchange in a 100% KNO3 molten salt bath at 450° C. for 5 hours according to the ISO720 standard. For those samples that were ion-exchanged, the compressive stress was determined with a Fundamental Stress Measuring (FSM) instrument, and the compressive stress value was based on the measured Stress Optical Coefficient (SOC). The FSM instrument couples light into and out of a birefringent glass surface. Then, the measured birefringence is related to the stress through the material constant stress optical coefficient or photoelastic coefficient (SOC or PEC), and two parameters are obtained: the maximum surface compressive stress (CS) and the depth of the exchange layer (DOL). The diffusivity of alkali metal ions in the glass and the change in stress per square root of time were also determined. The diffusivity (D) of the glass was calculated from the measured depth of layer (DOL) and ion exchange time (t) according to the following relationship: DOL=˜1.4*(4*D*t)1/2 . According to the Arrhenius relationship, the diffusivity increases with temperature, so the diffusivity is reported at a specific temperature.
表2：玻璃性质随碱金属和氧化铝比例的变化Table 2: Variation of glass properties with the ratio of alkali metal and alumina
表2的数据表明碱金属和氧化铝的比例Y:X影响熔融性能、耐水解性和可通过离子交换强化获得的压缩应力。具体来说，图1图形化的显示了对于表2的玻璃组合物的应变点、退火点和软化点随比例Y:X的变化。图1表明，随着比例Y:X减小到低于0.9，玻璃的应变点、退火点和软化点快速增加。因此，为了获得易于熔融和成形的玻璃，比例Y:X应大于或等于0.9或甚至大于或等于1。The data in Table 2 show that the ratio Y:X of alkali metal and alumina affects melting properties, hydrolysis resistance and compressive stress achievable by ion exchange strengthening. In particular, Figure 1 graphically shows the strain point, annealing point, and softening point as a function of the ratio Y:X for the glass compositions of Table 2. Figure 1 shows that the strain point, annealing point and softening point of the glass increase rapidly as the ratio Y:X decreases below 0.9. Therefore, in order to obtain a glass that is easy to melt and form, the ratio Y:X should be greater than or equal to 0.9 or even greater than or equal to 1.
此外，表2中的数据表明玻璃组合物的扩散率通常随着比例Y:X而减小。因此，为了取得能快速离子交换以减少加工时间(和成本)的玻璃，比例Y:X应大于或等于0.9或甚至大于或等于1。Furthermore, the data in Table 2 show that the diffusivity of glass compositions generally decreases with the ratio Y:X. Therefore, the ratio Y:X should be greater than or equal to 0.9 or even greater than or equal to 1 in order to obtain a glass capable of rapid ion exchange to reduce processing time (and cost).
此外，图2表明对于给定的离子交换时间和离子交换温度，当比例Y:X大于或等于约0.9或甚至大于或等于约1且小于或等于约2，具体地大于或等于约1.3且小于或等于约2.0时，可获得最大压缩应力。因此，当比例Y:X大于或等于约1且小于或等于约2时，玻璃的负载忍耐强度可获得最大的改善。通常认为可通过离子交换取得的最大应力随着离子交换时段的增加而减小，如应力变化速率(即，所测压缩应力除以离子交换时间的平方根)所示。图2总体显示了应力变化速率随着比例Y:X的减小而减小。Furthermore, Figure 2 shows that for a given ion exchange time and ion exchange temperature, when the ratio Y:X is greater than or equal to about 0.9 or even greater than or equal to about 1 and less than or equal to about 2, specifically greater than or equal to about 1.3 and less than Or equal to about 2.0, the maximum compressive stress is obtained. Therefore, when the ratio Y:X is greater than or equal to about 1 and less than or equal to about 2, the greatest improvement in the load withstand strength of the glass can be obtained. It is generally believed that the maximum stress achievable by ion exchange decreases as the ion exchange period increases, as indicated by the rate of change of stress (ie, the measured compressive stress divided by the square root of the ion exchange time). Figure 2 generally shows that the rate of stress change decreases as the ratio Y:X decreases.
图3图形化地显示了耐水解性(y轴)随比例Y:X(x轴)的变化。如图3所示，玻璃的耐水解性一般随着比例Y:X的减小而改善。Figure 3 graphically shows the hydrolysis resistance (y-axis) as a function of the ratio Y:X (x-axis). As shown in Figure 3, the hydrolysis resistance of the glass generally improves as the ratio Y:X decreases.
基于上述，应理解通过把玻璃中的比例Y:X保持在大于或等于约0.9或甚至大于或等于约1且小于或等于约2，可获得具有良好熔融性能、优异离子交换性能和优异耐水解性的玻璃。Based on the foregoing, it should be understood that by maintaining the ratio Y:X in the glass at greater than or equal to about 0.9, or even greater than or equal to about 1 and less than or equal to about 2, a glass having good melting properties, excellent ion exchange properties, and excellent resistance to hydrolysis can be obtained sexual glass.
实施例3Example 3
制备了3种示例发明性玻璃组合物(组合物J-L)和3种比较玻璃组合物(组合物4-6)。改变玻璃组合物中MgO和CaO的浓度，来制备富含MgO的组合物(即，组合物J-L和4)和富含CaO的组合物(即，组合物5-6)。还改变了MgO和CaO的相对量，从而玻璃组合物具有不同的(CaO/(CaO+MgO)比例值。各示例发明性玻璃组合物和比较玻璃组合物的具体组成见下文表3。用相对于实施例2的描述来测定各个组合物的性质。Three exemplary inventive glass compositions (Compositions J-L) and three comparative glass compositions (Compositions 4-6) were prepared. The concentrations of MgO and CaO in the glass compositions were varied to prepare MgO-rich compositions (ie, Compositions J-L and 4) and CaO-rich compositions (ie, Compositions 5-6). The relative amounts of MgO and CaO were also varied so that the glass compositions had different values for the (CaO/(CaO+MgO) ratio. The specific composition of each exemplary inventive glass composition and comparative glass composition is shown in Table 3 below. The properties of each composition were determined as described in Example 2.
表3：玻璃性质随CaO含量的变化Table 3: Variation of glass properties with CaO content
图4图形化地显示了表3所列组合物的扩散率D随(CaO/(CaO+MgO)比例的变化。具体来说，图4表明随着(CaO/(CaO+MgO)比例增加，所得玻璃中碱金属离子的扩散率降低，由此降低该玻璃的离子交换性能。这种趋势得到表3和图5中数据的支持。图5图形化地显示了最大压缩应力和应力变化速率(y轴)随比例(CaO/(CaO+MgO)的变化。图5表明随着比例(CaO/(CaO+MgO)增加，对于给定离子交换温度和离子交换时间而言可获得的最大压缩应力降低。图5还表明随着比例(CaO/(CaO+MgO)增加，应力变化速率增加(即，变得更负面和更不利)。Figure 4 graphically shows the variation of the diffusivity D of the compositions listed in Table 3 with the (CaO/(CaO+MgO) ratio. Specifically, Figure 4 shows that as the (CaO/(CaO+MgO) ratio increases, The diffusion rate of alkali metal ions in the resulting glass is reduced, thereby reducing the ion exchange performance of the glass. This trend is supported by the data in Table 3 and Figure 5. Figure 5 graphically shows the maximum compressive stress and the rate of change of stress ( y-axis) as a function of the ratio (CaO/(CaO+MgO). Figure 5 shows that as the ratio (CaO/(CaO+MgO) increases, the maximum compressive stress achievable for a given ion exchange temperature and ion exchange time decrease. Figure 5 also shows that the rate of stress change increases (ie, becomes more negative and less favorable) as the ratio (CaO/(CaO+MgO) increases.
因此，基于表3和图4和5的数据，应理解可通过最小化比例(CaO/(CaO+MgO)来制备具有更高扩散率的玻璃。已测定，当(CaO/(CaO+MgO)比例小于约0.5时，可制备具有合适扩散率的玻璃。当(CaO/(CaO+MgO)比例小于约0.5时，玻璃的扩散率减少了为了取得给定压缩应力和层深度所需的离子交换加工时间。或者，因比例(CaO/(CaO+MgO)而具有更高扩散率的玻璃，对于给定离子交换温度和离子交换时间而言，可取得更高的压缩应力和层深度。Therefore, based on the data in Table 3 and Figures 4 and 5, it is understood that glasses with higher diffusivities can be prepared by minimizing the ratio (CaO/(CaO+MgO). It has been determined that when (CaO/(CaO+MgO) When the ratio is less than about 0.5, glasses with suitable diffusivity can be produced. When the (CaO/(CaO+MgO) ratio is less than about 0.5, the diffusivity of the glass reduces the ion exchange required to achieve a given compressive stress and layer depth Processing time. Alternatively, a glass with a higher diffusivity due to the ratio (CaO/(CaO+MgO) can achieve higher compressive stress and layer depth for a given ion exchange temperature and ion exchange time.
此外，表3中的数据还表明通过增加MgO的浓度来降低(CaO/(CaO+MgO)比例，通常改善玻璃对通过ISO720标准所测的水解降解的耐受性。Furthermore, the data in Table 3 also show that decreasing the (CaO/(CaO+MgO) ratio by increasing the concentration of MgO generally improves the resistance of the glass to hydrolytic degradation as measured by the ISO720 standard.
实施例4Example 4
制备了3种示例发明性玻璃组合物(组合物M-O)和3种比较玻璃组合物(组合物7-9)。玻璃组合物中的B2O3浓度从0摩尔％到约4.6摩尔％变化，从而所得玻璃具有不同的B2O3/(R2O-Al2O3)比例值。各示例发明性玻璃组合物和比较玻璃组合物的具体组成见下文表4。用相对于实施例2和3的描述来测定各个玻璃组合物的性质。Three exemplary inventive glass compositions (Composition MO) and three comparative glass compositions (Compositions 7-9) were prepared.The B2O3 concentration in the glass composition was varied from 0 mole % to about 4.6 mole %, so that the resulting glasses had different values for the B2O3/(R2O-Al2O3) ratio. The specific composition of each exemplary inventive glass composition and comparative glass composition is shown in Table 4 below. The properties of the respective glass compositions were determined as described with respect to Examples 2 and 3.
表4：玻璃性质随B2O3含量的变化Table4 : Variationof glass properties with B2O3 content
图6图形化地显示了表4中的玻璃组合物的扩散率D(y轴)随表4中玻璃组合物的比例B2O3/(R2O-Al2O3)(x轴)的变化。如图6所示，玻璃中碱金属离子的扩散率通常随着比例B2O3/(R2O-Al2O3)的增加而降低。Figure 6 graphically shows the diffusivity D (y-axis) of the glass compositions in Table 4 as a function of the ratio B2 O3 /(R2 O-Al2 O3 ) (x-axis) of the glass compositions in Table 4 The change. As shown in Figure6 , the diffusivity of alkali metal ions in glasses generally decreases with increasing ratio B2O3/( R2O-Al2O3) .
图7图形化地显示了表4所示玻璃组合物中的根据ISO720标准测定的耐水解性(y轴)随比例(B2O3/(R2O-Al2O3))(x轴)的变化。如图6所示，玻璃组合物的耐水解性通常随着比例B2O3/(R2O-Al2O3)的增加而改善。Figure 7 graphically shows the hydrolysis resistance (y-axis) measured according to the ISO720 standard versus the ratio (B2 O3 /(R2 O-Al2 O3 )) (x-axis) in the glass compositions shown in Table 4 )The change. As shown in FIG. 6 , the hydrolysis resistance of the glass composition generally improves with increasing ratio B2 O3 /(R2 O—Al2 O3 ).
基于图6和7，应理解最小化比例B2O3/(R2O-Al2O3)改善玻璃中碱金属离子的扩散率，由此改善玻璃的离子交换特征。此外，增加比例B2O3/(R2O-Al2O3)还通常改善玻璃对水解降解的抵抗。此外，已发现玻璃在酸溶液中对降解的抵抗(如根据DIN12116标准所测)，通常随着B2O3浓度的降低而改善。因此，把比例B2O3/(R2O-Al2O3)保持在小于或等于约0.3，为玻璃提供改善的水解和酸抵抗以及提供改善离子交换特征。Based on Figures 6 and 7, it is understood that minimizing the ratio B2 O3 /(R2 O—Al2 O3 ) improves the diffusion rate of alkali metal ions in the glass, thereby improving the ion exchange characteristics of the glass. Furthermore, increasing the ratio B2 O3 /(R2 O—Al2 O3 ) also generally improves the resistance of the glass to hydrolytic degradation. Furthermore, it has been found that the resistance of glasses to degradation in acid solutions (as measured according to the DIN12116 standard) generally improves with decreasing B2O3 concentration. Thus, maintaining the ratio B2 O3 /(R2 O—Al2 O3 ) at less than or equal to about 0.3 provides the glass with improved hydrolysis and acid resistance as well as improved ion exchange characteristics.
应理解，本文所述的玻璃组合物还离子交换后，具有化学耐久性和机械耐久性。这些性质使所述玻璃组合物非常适用于各种应用，包括，但不限于药物包装材料。It should be understood that the glass compositions described herein are also chemically and mechanically durable after ion exchange. These properties make the glass compositions well suited for a variety of applications including, but not limited to, pharmaceutical packaging materials.
基于上述，限制应理解公开了玻璃组合物和由玻璃组合物形成的玻璃制品的各种方面。根据低于方面，玻璃组合物可包括：浓度大于约70摩尔％的SiO2和Y摩尔％的碱金属氧化物。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。所述玻璃组合物可不含硼和硼的化合物。Based on the foregoing, the limitations should be understood to disclose various aspects of glass compositions and glass articles formed from the glass compositions. According to a lower aspect, the glass composition may include SiO2 at a concentration greater than about 70 mole percent and Y mole percent alkali metal oxide. The alkali metal oxide may include Na2O in an amount greater than about8 mole percent. The glass composition may be free of boron and boron compounds.
在第二方面中，第一方面所述的玻璃组合物包括大于或等于约72摩尔％量的SiO2。In a second aspect, the glass composition of the first aspect includesSi02 in an amount greater than or equal to about 72 mole percent.
在第三方面中，第一或第二方面所述的玻璃组合物不含磷和磷的化合物。In a third aspect, the glass composition according to the first or second aspect does not contain phosphorus and phosphorus compounds.
在第四方面中，从第一到第三方面任一项所述的玻璃组合物还包括X摩尔％Al2O3，其中比例Y:X大于1。In a fourth aspect, the glass composition of any one of the first to third aspects further comprises X mole % Al2 O3 , wherein the ratio Y:X is greater than 1.
在第五方面中，第四方面的玻璃组合物的比例Y:X小于或等于2。In the fifth aspect, the ratio Y:X of the glass composition of the fourth aspect is 2 or less.
在第六方面中，第四或第五方面的玻璃组合物的Al2O3的量大于或等于约2摩尔％且小于或等于约10摩尔％。In a sixth aspect, the glass composition of the fourth or fifth aspect has an amount of Al2 O3 greater than or equal to about 2 mole percent and less than or equal to about 10 mole percent.
在第七方面中，第一到第五方面任一项所述的玻璃组合物还包括从约3摩尔％到约13摩尔％的碱土金属氧化物。In a seventh aspect, the glass composition of any one of the first to fifth aspects further includes from about 3 mol % to about 13 mol % of an alkaline earth metal oxide.
在第八方面中，第七方面的碱土金属氧化物包括MgO和CaO，CaO以大于或等于约0.1摩尔％且小于或等于约1.0摩尔％的量存在，且比例(CaO(摩尔％)/(CaO(摩尔％)+MgO(摩尔％)))小于或等于0.5。In an eighth aspect, the alkaline earth metal oxide of the seventh aspect includes MgO and CaO, CaO is present in an amount greater than or equal to about 0.1 mol % and less than or equal to about 1.0 mol %, and the ratio (CaO (mol %)/( CaO(mol%)+MgO(mol%))) is less than or equal to 0.5.
在第九方面中，玻璃组合物可包括大于约68摩尔％SiO2；X摩尔％Al2O3和Y摩尔％碱金属氧化物；以及B2O3。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。比例(B2O3(摩尔％)/(Y摩尔％–X摩尔％)可大于0且小于0.3。In a ninth aspect, the glass composition can include greater than about 68 mol % SiO2 ; X mol % Al2 O3 and Y mol % alkali metal oxide; and B2 O3 . The alkali metal oxide may include Na2O in an amount greater than about8 mole percent. The ratio (B2 O3 (mol%)/(Y mol%−X mol%) may be greater than 0 and less than 0.3.
在第十方面中，第九方面所述的玻璃组合物包括大于或等于约72摩尔％量的SiO2。In a tenth aspect, the glass composition of the ninth aspect includesSiO2 in an amount greater than or equal to about 72 mole percent.
在第十一方面中，第九方面或第十方面的玻璃组合物包括大于或等于约0.01摩尔％且小于或等于约4摩尔％量的B2O3。In an eleventh aspect, the glass composition of the ninth or tenth aspect includes B2O3 in an amount greaterthan or equal to about 0.01 mole percent and less than or equal to about4 mole percent.
在第十二方面中，第九到第十一方面任一项的玻璃组合物，其中玻璃组合物的比例Y:X大于1。In the twelfth aspect, the glass composition of any one of the ninth to eleventh aspects, wherein the ratio Y:X of the glass composition is greater than 1.
在第十三方面中，第十四方面的比例Y:X小于或等于2。In the thirteenth aspect, the ratio Y:X of the fourteenth aspect is 2 or less.
第十四方面包括第九或第十三方面任一项的玻璃组合物，其中X大于或等于约2摩尔％且小于或等于约10摩尔％。A fourteenth aspect includes the glass composition of any one of the ninth or thirteenth aspects, wherein X is greater than or equal to about 2 mole percent and less than or equal to about 10 mole percent.
第十五方面包括第九或第十四方面任一项的玻璃组合物，其中玻璃组合物不含磷和磷的化合物。A fifteenth aspect includes the glass composition of any one of the ninth or fourteenth aspects, wherein the glass composition does not contain phosphorus and phosphorus compounds.
第十六方面包括第九或第十五方面任一项的玻璃组合物，其中玻璃组合物还包括MgO和CaO，CaO以大于或等于约0.1摩尔％且小于或等于约1.0摩尔％的量存在，且比例(CaO(摩尔％)/(CaO(摩尔％)+MgO(摩尔％)))小于或等于0.5。A sixteenth aspect includes the glass composition of any one of the ninth or fifteenth aspects, wherein the glass composition further comprises MgO and CaO, CaO being present in an amount greater than or equal to about 0.1 mole percent and less than or equal to about 1.0 mole percent , and the ratio (CaO (mol %)/(CaO (mol %)+MgO (mol %))) is less than or equal to 0.5.
在第十七方面中，玻璃制品可具有根据ISO719的HGB1型耐水解性。玻璃制品可包括大于约8摩尔％Na2O和小于约4摩尔％B2O3。In a seventeenth aspect, the glass article may have a hydrolysis resistance type HGB1 according to ISO719. The glass article can include greater than about8 mole % Na2O and lessthan about4 mole % B2O3.
在第十八方面中，第十七方面的玻璃制品还可包括X摩尔％Al2O3和Y摩尔％碱金属氧化物，其中比例(B2O3(摩尔％)/(Y摩尔％–X摩尔％)大于0且小于0.3。In an eighteenth aspect, the glass article of the seventeenth aspect may further comprise X mol % Al2 O3 and Y mol % alkali metal oxide, wherein the ratio (B2 O3 (mol %)/(Y mol % - X mole %) is greater than 0 and less than 0.3.
在第十九方面中，第十七到第十八方面任一项的玻璃制品还包括压缩应力层，该压缩应力层的压缩应力大于或等于约250MPa。In a nineteenth aspect, the glass article of any one of the seventeenth to eighteenth aspects further comprises a compressively stressed layer having a compressive stress of greater than or equal to about 250 MPa.
第二十方面包括第十七到第十九方面任一项的玻璃制品，其中玻璃制品至少具有根据DIN12116的S3级别耐酸性。A twentieth aspect includes the glass article of any one of the seventeenth to nineteenth aspects, wherein the glass article has at least a class S3 acid resistance according to DIN12116.
第二十一方面包括第十七到第二十方面任一项的玻璃制品，其中玻璃制品至少具有根据ISO695的A2级别耐碱性。A twenty-first aspect includes the glass article of any one of aspects 17 to 20, wherein the glass article has at least class A2 alkali resistance according to ISO695.
第二十二方面包括第十七到第二十一方面任一项的玻璃制品，其中玻璃制品具有根据ISO720的HGA1型耐水解性。A twenty-second aspect includes the glass article of any one of the seventeenth to twenty-first aspects, wherein the glass article has HGA1 type hydrolysis resistance according to ISO720.
在第二十三方面中，玻璃药物包装可包括：大于约70摩尔％量的SiO2；X摩尔％Al2O3；以及Y摩尔％的碱金属氧化物。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。玻璃药物包装中B2O3的浓度(摩尔％)和(Y摩尔％–X摩尔％)的比例可小于0.3。玻璃药物包装也可具有根据ISO719的HGB1型耐水解性。In a twenty-third aspect, a glass pharmaceutical package can comprise:SiO2 in an amount greater than about 70 mole %; X mole %Al2O3; and Y mole % alkali metal oxide. The alkali metal oxide may include Na2O in an amount greater than about8 mole percent.The concentration (mol%)of B2O3 in the glass pharmaceutical package and the ratio of (Ymol%-Xmol%) may be less than 0.3. Glass pharmaceutical packaging can also have hydrolysis resistance type HGB1 according to ISO719.
第二十四方面包括第二十三方面的玻璃药物包装，其中SiO2的量大于或等于72摩尔％且小于或等于约78摩尔％。A twenty-fourth aspect includes the glass pharmaceutical package of the twenty-third aspect, wherein the amount ofSiO2 is greater than or equal to 72 mole % and less than or equal to about 78 mole %.
第二十五方面包括第二十三方面到二十四方面的玻璃药物包装，其中X大于或等于约4摩尔％且小于或等于约8摩尔％。A twenty-fifth aspect includes the glass pharmaceutical packaging of aspects twenty-third to twenty-fourth, wherein X is greater than or equal to about 4 mole % and less than or equal to about 8 mole %.
第二十六方面包括第二十三到第二十五方面的玻璃药物包装，其中比例Y:X大于1。A twenty-sixth aspect includes the glass pharmaceutical packaging of aspects twenty-third to twenty-fifth, wherein the ratio Y:X is greater than one.
第二十七方面包括第二十三到第二十六方面的玻璃药物包装，其中比例Y:X小于2。A twenty-seventh aspect includes the glass pharmaceutical packaging of aspects 23-26, wherein the ratio Y:X is less than 2.
第二十八方面包括第二十三到第二十七方面的玻璃药物包装，所述玻璃药物包装还包括从约4摩尔％到约8摩尔％的碱土金属氧化物。A twenty-eighth aspect includes the glass pharmaceutical packaging of aspects twenty-third to twenty-seventh, further comprising from about 4 mole % to about 8 mole % of an alkaline earth metal oxide.
第二十九方面包括第二十三到第二十八方面的玻璃药物包装，其中所述玻璃药物包装还包括MgO和CaO，CaO以大于或等于约0.2摩尔％且小于或等于约0.7摩尔％的量存在，且比例(CaO(摩尔％)/(CaO(摩尔％)+MgO(摩尔％)))小于或等于0.5。A twenty-ninth aspect includes the glass pharmaceutical packaging of aspects twenty-third to twenty-eighth, wherein the glass pharmaceutical packaging further comprises MgO and CaO, CaO at greater than or equal to about 0.2 mole % and less than or equal to about 0.7 mole % The amount exists, and the ratio (CaO (mol %)/(CaO (mol %)+MgO (mol %))) is less than or equal to 0.5.
第三十方面包括第二十三到第二十九方面任一项的玻璃药物包装，其中所述玻璃药物包装具有根据ISO720的HGA1型耐水解性。A thirtieth aspect includes the glass pharmaceutical package of any one of the twenty-third to twenty-ninth aspects, wherein the glass pharmaceutical package has a hydrolysis resistance type HGA1 according to ISO720.
在第三十一方面中，玻璃组合物可包括：从约70摩尔％到约80摩尔％SiO2；从约3摩尔％到约13摩尔％碱土金属氧化物；X摩尔％Al2O3；以及Y摩尔％碱金属氧化物。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。比例Y:X可大于1，且玻璃组合物可不含硼和硼的化合物。In a thirty-first aspect, the glass composition can comprise: from about 70 mole % to about 80 mole %SiO2 ; from about 3 mole % to about 13 mole % alkaline earth oxides; X mole %Al2O3; and Y mol % alkali metal oxide. The alkali metal oxide may include Na2O in an amount greater than about8 mole percent. The ratio Y:X can be greater than 1, and the glass composition can be free of boron and boron compounds.
在第三十二方面中，玻璃组合物可包括：从约72摩尔％到约78摩尔％SiO2；从约4摩尔％到约8摩尔％碱土金属氧化物；X摩尔％Al2O3；以及Y摩尔％碱金属氧化物。碱土金属氧化物的量可大于或等于约4摩尔％且小于或等于约8摩尔％。碱金属氧化物可包括大于或等于约9摩尔％且小于或等于约15摩尔％量的Na2O。比例Y:X可大于1。所述玻璃组合物可不含硼和硼的化合物。In a thirty-second aspect, the glass composition can comprise: from about 72 mole % to about 78 mole %Si02 ; from about4 mole % to about8 mole % alkaline earth metal oxides; X mole % Al203; and Y mol % alkali metal oxide. The amount of alkaline earth metal oxide can be greater than or equal to about 4 mole percent and less than or equal to about 8 mole percent. The alkali metal oxide may include Na2O in an amount greater than or equal to about9 mole percent and less than or equal to about 15 mole percent. The ratio Y:X can be greater than 1. The glass composition may be free of boron and boron compounds.
在第三十三方面中，玻璃组合物可包括：从约68摩尔％到约80摩尔％SiO2；从约3摩尔％到约13摩尔％碱土金属氧化物；X摩尔％Al2O3；以及Y摩尔％碱金属氧化物。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。所述玻璃组合物还可包括B2O3。比例(B2O3(摩尔％)/(Y摩尔％–X摩尔％)可大于0且小于0.3，以及比例Y:X可大于1。In a thirty third aspect, the glass composition can comprise: from about 68 mole % to about 80 mole %Si02 ; from about3 mole % to about 13 mole % alkaline earth oxides; X mole %Al203 ; and Y mol % alkali metal oxide. The alkali metal oxide may include Na2O in an amount greater than about8 mole percent. The glass composition may also include B2 O3 . The ratio (B2 O3 (mol %)/(Y mol %−X mol %) may be greater than 0 and less than 0.3, and the ratio Y:X may be greater than 1.
在第三十四方面中，玻璃组合物可包括：从约70摩尔％到约80摩尔％SiO2；从约3摩尔％到约13摩尔％碱土金属氧化物；X摩尔％Al2O3；以及Y摩尔％碱金属氧化物。碱金属氧化物可包括大于或等于约0.1摩尔％且小于或等于约1.0摩尔％量的CaO。X可大于或等于约2摩尔％且小于或等于约10摩尔％。碱金属氧化物可包括从约0.01摩尔％到约1.0摩尔％K2O。比例Y:X可大于1。所述玻璃组合物可不含硼和硼的化合物。In a thirty-fourth aspect, the glass composition can comprise: from about 70 mole % to about 80 mole %Si02 ; from about 3 mole % to about 13 mole % alkaline earth oxides; X mole %Al2O3; and Y mol % alkali metal oxide. The alkali metal oxide may include CaO in an amount greater than or equal to about 0.1 mole percent and less than or equal to about 1.0 mole percent. X can be greater than or equal to about 2 mole percent and less than or equal to about 10 mole percent. The alkali metaloxide may include from about 0.01 mole percent to about 1.0 mole percent K2O. The ratio Y:X can be greater than 1. The glass composition may be free of boron and boron compounds.
在第三十五方面中，玻璃组合物可包括：大于约70摩尔％且小于或等于约80摩尔％量的SiO2；从约3摩尔％到约13摩尔％碱土金属氧化物；X摩尔％Al2O3；以及Y摩尔％碱金属氧化物。所述碱金属氧化物可包括大于约8摩尔％量的Na2O。玻璃组合物中B2O3的浓度(摩尔％)和(Y摩尔％–X摩尔％)的比例可小于0.3。比例Y:X可大于1。In a thirty-fifth aspect, the glass composition can include:SiO2 in an amount greater than about 70 mole % and less than or equal to about 80 mole %; from about 3 mole % to about 13 mole % alkaline earth metal oxide; X mole % Al2 O3 ; and Y mol % alkali metal oxide. The alkali metal oxide may include Na2O in an amount greater than about8 mole percent. The concentration of B2 O3 (mol %) and the ratio of (Y mol %−X mol %) in the glass composition may be less than 0.3. The ratio Y:X can be greater than 1.
在第三十六方面中，第三十一到三十五方面任一项的玻璃组合物，其中所述SiO2以小于或等于78摩尔％的量存在。In the thirty-sixth aspect, the glass composition of any one of the thirty-first to thirty-fifth aspects, wherein theSiO2 is present in an amount less than or equal to 78 mole %.
第三十七方面包括第三十一到三十六方面任一项的玻璃组合物，其中碱土金属氧化物的量大于或等于约4摩尔％且小于或等于约8摩尔％。A thirty-seventh aspect includes the glass composition of any one of aspects thirty-first through thirty-six, wherein the amount of alkaline earth metal oxide is greater than or equal to about 4 mole percent and less than or equal to about 8 mole percent.
第三十八方面包括第三十一到三十七方面任一项的玻璃组合物，其中所述碱土金属氧化物包括MgO和CaO，且比例(CaO(摩尔％)/(CaO(摩尔％)+MgO(摩尔％)))小于或等于0.5。A thirty-eighth aspect includes the glass composition of any one of the thirty-first to thirty-seventh aspects, wherein the alkaline earth metal oxide includes MgO and CaO, and the ratio (CaO (mol %)/(CaO (mol %) +MgO(mol%))) is less than or equal to 0.5.
第三十九方面包括第三十一到三十八方面任一项的玻璃组合物，其中所述碱土金属氧化物包括从约0.1摩尔％到小于或等于约1.0摩尔％CaO。A thirty-ninth aspect includes the glass composition of any one of aspects thirty-first through thirty-eighth, wherein the alkaline earth metal oxide comprises from about 0.1 mole percent to less than or equal to about 1.0 mole percent CaO.
第四十方面包括第三十一到三十九方面任一项的玻璃组合物，其中碱土金属氧化物包括从约3摩尔％到约7摩尔％MgO。A fortieth aspect includes the glass composition of any one of aspects thirty-first through thirty-ninth, wherein the alkaline earth metal oxide comprises from about 3 mole percent to about 7 mole percent MgO.
第四十一方面包括第三十一、第三十二或第三十四方面任一项的玻璃组合物，其中X大于或等于约2摩尔％且小于或等于约10摩尔％。A forty-first aspect includes the glass composition of any one of aspects thirty-first, thirty-second, or thirty-fourth, wherein X is greater than or equal to about 2 mole percent and less than or equal to about 10 mole percent.
第四十二方面包括第三十一到第四十一方面任一项的玻璃组合物，其中碱金属氧化物包括大于或等于约9摩尔％Na2O且小于或等于约15摩尔％Na2O。A forty-second aspect includes the glass composition of any one of aspects 31 to 41, wherein the alkali metal oxide comprises greater than or equal to about9 mole % Na2O and less than or equal to about 15 mole %Na2 O.
第四十三方面包括第三十一到第四十二方面任一项的玻璃组合物，其中比例Y:X小于或等于2。A forty-third aspect includes the glass composition of any one of aspects 31-42, wherein the ratio Y:X is 2 or less.
第四十四方面包括第三十一到第四十三方面任一项的玻璃组合物，其中比例Y:X大于或等于1.3且小于或等于2.0。A forty-fourth aspect includes the glass composition of any one of aspects 31 to 43, wherein the ratio Y:X is greater than or equal to 1.3 and less than or equal to 2.0.
第四十五方面包括第三十一到第四十四方面任一项的玻璃组合物，其中所述碱金属氧化物还包括小于或等于约3摩尔％量的K2O。A forty-fifth aspect includes the glass composition of any one of aspects 31-44, wherein the alkali metal oxide further includes K20 in an amount less than or equal to about3 mole percent.
第四十六方面包括第三十一到第四十五方面任一项的玻璃组合物，其中玻璃组合物不含磷和磷的化合物。A forty-sixth aspect includes the glass composition of any one of the thirty-first to forty-fifth aspects, wherein the glass composition does not contain phosphorus and phosphorus compounds.
第四十七方面包括第三十一到第四十六方面任一项的玻璃组合物，其中碱金属氧化物包括大于或等于约0.01摩尔％且小于或等于约1.0摩尔％量的K2O。A forty-seventh aspect includes the glass composition of any one of aspects thirty-first through forty-sixth, wherein the alkali metaloxide includes K20 in an amount greater than or equal to about 0.01 mole percent and less than or equal to about 1.0 mole percent .
第四十八方面包括第三十二或第三十四方面任一项的玻璃组合物，其中SiO2的量大于或等于约70摩尔％。A forty-eighth aspect includes the glass composition of any one of aspects thirty-second or thirty-fourth, wherein the amount ofSi02 is greater than or equal to about 70 mole percent.
第四十九方面包括第三十二或第三十四方面任一项的玻璃组合物，其中比例(B2O3(摩尔％)/(Y摩尔％–X摩尔％)小于0.2。A forty-ninth aspect includes the glass composition of any one of aspects thirty-second or thirty-fourth, wherein the ratio (B2 O3 (mol %)/(Y mol %-X mol %) is less than 0.2.
第五十方面包括第三十二或第三十四方面任一项的玻璃组合物，其中B2O3的量小于或等于约4.0摩尔％。A fiftieth aspect includes the glass composition of any one of aspects thirty-second or thirty- fourth, wherein the amount of B2O3 is less than or equal to about 4.0 mole percent.
第五十一方面包括第五十方面任一项的玻璃组合物，其中B2O3的量大于或等于约0.01摩尔％。A fifty-first aspect includes the glass composition of any one of the fiftieth aspects, wherein the amountof B2O3 is greaterthan or equal to about 0.01 mole percent.
第五十二方面包括第三十四方面任一项的玻璃组合物，其中所述玻璃组合物不含硼和硼的化合物。A fifty-second aspect includes the glass composition of any one of the thirty-fourth aspect, wherein the glass composition does not contain boron and boron compounds.
第五十三方面包括第三十一到第三十四方面任一项的玻璃组合物，其中SiO2的浓度大于或等于约72摩尔％。A fifty-third aspect includes the glass composition of any one of aspects thirty-first through thirty-fourth, wherein the concentration of SiO2 is greater than or equal to about 72 mole percent.
第五十四方面包括第三十一到第五十三方面任一项的玻璃组合物，其中SiO2的浓度大于或等于约73摩尔％。A fifty-fourth aspect includes the glass composition of any one of aspects thirty-first through fifty-third, wherein the concentration ofSiO2 is greater than or equal to about 73 mole percent.
在第五十五方面中，由第三十一到第五十四方面任一项的玻璃组合物形成玻璃制品。In a fifty-fifth aspect, a glass article is formed from the glass composition of any one of the thirty-first to fifty-fourth aspects.
第五十六方面包括第五十五方面的玻璃制品，其中玻璃制品具有根据ISO719的HGB1型耐水解性。A fifty-sixth aspect includes the glass article of the fifty-fifth aspect, wherein the glass article has hydrolysis resistance type HGB1 according to ISO719.
第五十七方面包括第五十五到第五十六方面任一项的玻璃制品，其中玻璃制品在离子交换后，具有根据ISO720的HGA1型耐水解性。A fifty-seventh aspect includes the glass article of any one of aspects fifty-fifth to fifty-sixth, wherein the glass article has HGA1 type hydrolysis resistance according to ISO720 after ion exchange.
第五十八方面包括第五十五到第五十七方面任一项的玻璃制品，其中玻璃制品在离子交换前后，具有根据ISO720的HGA1型耐水解性。A fifty-eighth aspect includes the glass article of any one of aspects fifty-fifth to fifty-seventh, wherein the glass article has HGA1 type hydrolysis resistance according to ISO720 before and after ion exchange.
第五十九方面包括第五十五到第五十八方面任一项的玻璃制品，其中玻璃制品至少具有根据DIN12116的S3级别耐酸性。A fifty-ninth aspect includes the glass article of any one of aspects fifty-fifth to fifty-eighth, wherein the glass article has at least class S3 acid resistance according to DIN12116.
第六十方面包括第五十五到第五十九方面任一项的玻璃制品，其中玻璃制品至少具有根据ISO695的A2级别耐碱性。A sixtieth aspect includes the glass article of any one of aspects fifty-fifth to fifty-ninth, wherein the glass article has at least a class A2 alkali resistance according to ISO695.
第六十一方面包括第五十五到第六十方面任一项的玻璃制品，其中玻璃制品是药物包装。A sixty-first aspect includes the glass article of any one of aspects fifty-fifth to sixtieth, wherein the glass article is a pharmaceutical package.
第六十二方面包括第五十五到第六十一方面任一项的玻璃制品，其中玻璃制品是离子交换强化的。A sixty-second aspect includes the glass article of any one of aspects fifty-fifth to sixty-first, wherein the glass article is ion exchange strengthened.
第六十三方面包括第五十五到第六十二方面任一项的玻璃制品，其中玻璃制品还包括压缩应力层，该压缩应力层的层深度大于或等于10微米，且压缩应力大于或等于约250MPa。A sixty-third aspect includes the glass article of any one of aspects fifty-fifth to sixty-second, wherein the glass article further includes a compressive stress layer, the compressive stress layer has a layer depth greater than or equal to 10 microns, and the compressive stress is greater than or equal to Equal to about 250MPa.
在第六十四方面中，玻璃制品可具有根据ISO719的HGB1型耐水解性。玻璃制品的阀值扩散率在小于或等于450℃的温度下可大于16微米2/小时。In a sixty-fourth aspect, the glass article may have a hydrolysis resistance type HGB1 according to ISO719. The threshold diffusivity of the glass article may be greater than 16micron2 /hour at a temperature of less than or equal to 450°C.
第六十五方面包括第六十四方面的玻璃制品，其中阀值扩散率在小于或等于450℃的温度下可大于20微米2/小时。A sixty-fifth aspect includes the glass article of aspect sixty-fourth, wherein the threshold diffusivity may be greater than 20micron2 /hour at a temperature of less than or equal to 450°C.
第六十六方面包括第六十三到第六十四方面任一项的玻璃制品，其中玻璃制品在离子交换后，具有根据ISO720的HGA1型耐水解性。A sixty-sixth aspect includes the glass article of any one of aspects 63rd to 64th, wherein the glass article has a hydrolysis resistance type HGA1 according to ISO720 after ion exchange.
第六十七方面包括第六十四到第六十六方面任一项的玻璃制品，所述玻璃制品还包括层深度大于25微米的压缩应力。A sixty-seventh aspect includes the glass article of any one of aspects 64-66, further comprising a compressive stress with a depth of layer greater than 25 microns.
第六十八方面包括第六十七方面的玻璃制品，其中层深度大于35微米。A sixty-eighth aspect includes the glass article of the sixty-seventh aspect, wherein the layer depth is greater than 35 microns.
第六十九方面包括第六十三到第六十八方面任一项的玻璃制品，其中玻璃制品是离子交换强化的，所述离子交换强化包括在熔盐浴中把玻璃制品于小于或等于450℃的温度下处理小于或等于5小时的时间。A sixty-ninth aspect includes the glass article of any one of aspects 63 to 68, wherein the glass article is ion exchange strengthened, the ion exchange strengthening comprising treating the glass article in a molten salt bath to a temperature less than or equal to Treatment at a temperature of 450°C for a period of less than or equal to 5 hours.
第七十方面包括第六十三到第六十九方面任一项的玻璃制品，所述玻璃制品还包括大于或等于350MPa的表面压缩应力。A seventieth aspect includes the glass article of any one of aspects 63 to 69, further comprising a surface compressive stress greater than or equal to 350 MPa.
第七十一方面包括第六十三到第七十方面任一项的玻璃制品，其中表面压缩应力大于或等于400MPa。A seventy-first aspect includes the glass article of any one of aspects 63 to 70, wherein the surface compressive stress is greater than or equal to 400 MPa.
第七十二方面包括第六十三到第七十一方面任一项的玻璃制品，其中玻璃制品是离子交换强化的，所述离子交换强化包括在熔盐浴中把玻璃制品于小于或等于450℃的温度下处理小于或等于5小时的时间。A seventy-second aspect includes the glass article of any one of aspects 63 to 71, wherein the glass article is ion exchange strengthened, the ion exchange strengthening comprising treating the glass article in a molten salt bath to a temperature less than or equal to Treatment at a temperature of 450°C for a period of less than or equal to 5 hours.
第七十二方面包括第六十三到第七十二方面任一项的玻璃制品，其中玻璃制品是药物包装。A seventy-second aspect includes the glass article of any one of aspects 63 to 72, wherein the glass article is a pharmaceutical packaging.
在第七十三方面中，玻璃制品可具有根据ISO719的HGB1型耐水解性。玻璃制品还可具有压缩应力层，所述压缩应力层的层深度大于25微米且表面压缩应力大于或等于350MPa。可离子交换强化所述玻璃制品，且所述离子交换强化包括在熔盐浴中把玻璃制品于小于或等于450℃的温度下处理小于或等于5小时的时间。In a seventy-third aspect, the glass article may have a hydrolysis resistance type HGB1 according to ISO719. The glass article may also have a compressive stress layer having a layer depth greater than 25 microns and a surface compressive stress greater than or equal to 350 MPa. The glass article may be ion exchange strengthened, and the ion exchange strengthening includes treating the glass article at a temperature of less than or equal to 450° C. for a time of less than or equal to 5 hours in a molten salt bath.
第七十四方面包括第七十三方面的玻璃制品，其中玻璃制品在离子交换后，具有根据ISO720的HGA1型耐水解性。A seventy-fourth aspect includes the glass article of the seventy-third aspect, wherein the glass article has a hydrolysis resistance type HGA1 according to ISO720 after ion exchange.
第七十五方面包括第七十三到第七十四方面任一项的玻璃制品，其中玻璃制品的阀值扩散率在小于或等于450℃的温度下大于16微米2/小时。A seventy-fifth aspect includes the glass article of any one of aspects 73 to 74, wherein the glass article has a threshold diffusivity greater than 16microns2 /hour at a temperature of 450°C or less.
第七十六方面包括第七十三到第七十五方面的玻璃制品，其中阀值扩散率在小于或等于450℃的温度下可大于20微米2/小时。A seventy-sixth aspect includes the glass articles of aspects seventy-third to seventy-fifth, wherein the threshold diffusivity may be greater than 20micron2 /hour at a temperature of less than or equal to 450°C.
第七十七方面包括第七十三到第七十六方面任一项的玻璃制品，其中玻璃制品是药物包装。A seventy-seventh aspect includes the glass article of any one of aspects 73 to 76, wherein the glass article is a pharmaceutical packaging.
本领域的技术人员显而易见的是，可以在不偏离要求专利权的主题的精神和范围的情况下，对本文所述的实施方式进行各种修改和变动。因此，本说明书旨在涵盖本文所述的各种实施方式的修改和变化形式，只要这些修改和变化形式落在所附权利要求及其等同内容的范围之内。It will be apparent to those skilled in the art that various modifications and variations can be made in the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, this description is intended to cover the modifications and variations of the various embodiments described herein provided they come within the scope of the appended claims and their equivalents.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611002783.2ACN106746599B (en) | 2011-10-25 | 2012-10-25 | Glass compositions with improved chemical and mechanical durability |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161551163P | 2011-10-25 | 2011-10-25 | |
| US61/551,163 | 2011-10-25 | ||
| PCT/US2012/061867WO2013063238A1 (en) | 2011-10-25 | 2012-10-25 | Glass compositions with improved chemical and mechanical durability |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611002783.2ADivisionCN106746599B (en) | 2011-10-25 | 2012-10-25 | Glass compositions with improved chemical and mechanical durability |
| Publication Number | Publication Date |
|---|---|
| CN103987671A CN103987671A (en) | 2014-08-13 |
| CN103987671Btrue CN103987671B (en) | 2016-11-30 |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102892722A (en)* | 2010-05-19 | 2013-01-23 | 旭硝子株式会社 | Glass for chemical strengthening and glass plate for display device |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102892722A (en)* | 2010-05-19 | 2013-01-23 | 旭硝子株式会社 | Glass for chemical strengthening and glass plate for display device |
| Publication | Publication Date | Title |
|---|---|---|
| JP7432570B2 (en) | Glass compositions with improved chemical and mechanical durability | |
| CN103987671B (en) | Glass composition with improved chemical and mechanical durability |
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| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |