相关申请交叉参考Related Application Cross Reference
本申请要求2013年7月9日提交的美国申请第13/937707号的优先权，其要求2011年9月28日提交的题为“Light-WeightHybridGlassLaminates(轻量化混合玻璃层叠体)”的申请系列第13/247,182号的非临时申请的优先权，并且与其共同待审作为其部分继续申请，该申请又根据35U.S.C.§119要求2011年6月24日提交的美国临时申请系列第61/500,766号的优先权，本文以分别以它们作为基础并将其全文通过引用结合于此。This application claims priority to U.S. Application Serial No. 13/937707, filed July 9, 2013, which claims serial application titled "Light-Weight Hybrid Glass Laminates," filed September 28, 2011 Priority of non-provisional application Ser. No. 13/247,182, and co-pending therewith as a continuation-in-part, which in turn claims U.S. Provisional Application Serial No. 61/500,766 filed June 24, 2011 under 35 U.S.C. §119 Nos., which are hereby individually based and are hereby incorporated by reference in their entirety.
背景技术Background technique
本发明一般地涉及玻璃层叠体，更具体地，涉及混合玻璃层叠体，其包括化学强化的外部玻璃窗格和非化学强化的内部玻璃窗格。此类混合层叠体的特征在于轻量化、良好的消音性能以及高抗冲性。具体来说，所揭示的混合层叠体满足用于非挡风玻璃应用的商业适用的冲击测试标准。The present invention relates generally to glass laminates and, more particularly, to hybrid glass laminates comprising a chemically strengthened outer glass pane and a non-chemically strengthened inner glass pane. Such hybrid laminates are characterized by low weight, good sound dampening properties and high impact resistance. Specifically, the disclosed hybrid laminates meet commercially applicable impact test standards for non-windshield applications.
玻璃层叠体可用作建筑和运输应用(包括汽车、铁路车辆和飞机)中的窗户和玻璃窗。本文所用的玻璃窗是壁或者其他结构的透明或半透明部分。用于建筑和汽车应用的常见类型的玻璃窗包括透明和有色玻璃，包括层叠玻璃。包括用塑化聚(乙烯醇丁缩醛)(PVB)片分开的相对玻璃片的层叠玻璃窗，可用作例如窗户、挡风玻璃或者天窗。在某些应用中，希望玻璃层叠体具有高机械强度和声衰减性质，从而提供安全阻隔的同时降低来自外部来源的声传输。Glass laminates are useful as windows and glazing in construction and transportation applications, including automobiles, rail vehicles, and aircraft. As used herein, a glazing is a transparent or translucent portion of a wall or other structure. Common types of glazing used in architectural and automotive applications include clear and tinted glass, including laminated glass. Laminated glazing comprising opposing glass sheets separated by plasticized poly(vinyl butyral) (PVB) sheets can be used, for example, as windows, windshields or sunroofs. In certain applications, it is desirable for glass laminates to have high mechanical strength and sound attenuating properties to provide a safety barrier while reducing sound transmission from external sources.
在许多车辆应用中，燃料经济性与车辆重量相关。因此，希望降低此类应用中玻璃窗的重量，而不损害强度和声衰减性质。关于这一点，对于玻璃层叠体来说，下述情况是优选的：相对于外部冲击事件例如蓄意强行进入或与石头或冰雹接触时具有机械牢固性，又能适当地耗散由内部冲击事件例如与乘坐者的接触(如在碰撞中)造成的能量(和裂纹)。此外，政府法规对于道路车辆正要求更高的燃料里程和更低的二氧化碳排放。因此，不断努力降低这些车辆的重量的同时维持现有政府和工业安全标准。已经开发了非玻璃窗口材料，例如聚碳酸酯，其降低了车辆重量，但是无法提供合适的环境抗性、抗碎片性和其他考虑。但是，本发明的实施方式提供了明显的重量降低、安全合规性、有效的耐用性并降低了车辆撞击事件中的破裂可能性。鉴于前文所述，需要薄的、轻量化玻璃窗，其具有与较厚、较重的玻璃窗相比拟的耐久性和消音性能。In many vehicle applications, fuel economy is related to vehicle weight. Therefore, it is desirable to reduce the weight of glazing in such applications without compromising strength and sound attenuation properties. In this regard, it is preferred for a glass laminate to be mechanically robust against external impact events such as deliberate forced entry or contact with stones or hailstones, yet adequately dissipate damage caused by internal impact events such as Energy (and cracks) from contact with the occupant (as in a crash). In addition, government regulations are requiring higher fuel mileage and lower carbon dioxide emissions for road vehicles. Accordingly, there are ongoing efforts to reduce the weight of these vehicles while maintaining existing government and industry safety standards. Non-glazed window materials, such as polycarbonate, have been developed that reduce vehicle weight, but fail to provide suitable environmental resistance, fragment resistance, and other considerations. However, embodiments of the present invention provide significant weight reduction, safety compliance, effective durability, and reduced likelihood of rupture in the event of a vehicle impact. In view of the foregoing, there is a need for thin, lightweight glazing that has comparable durability and sound deadening performance to thicker, heavier glazing.
发明内容Contents of the invention
根据本发明的一个方面，玻璃层叠体包括外部玻璃片，内部玻璃片以及在外部玻璃片和内部玻璃片之间形成的聚合物中间层。为了优化玻璃层叠体的冲击性能，外部玻璃片包括化学强化玻璃并且厚度可以小于或等于1mm，同时，内部玻璃片包括非化学强化玻璃并且厚度可以小于或等于2.5mm。在一些实施方式中，聚合物中间层(例如聚乙烯醇丁缩醛或PVB)的厚度可以小于或等于1.6mm。所揭示的混合玻璃层叠体构造可优选地响应冲击来分散应力。例如，所揭示的混合玻璃层叠体可以响应外部冲击事件，提供优异的抗冲性和抗破裂性，又能响应内部冲击事件适当的耗散能量和裂纹。According to one aspect of the invention, a glass laminate includes an outer glass sheet, an inner glass sheet, and a polymer interlayer formed between the outer glass sheet and the inner glass sheet. To optimize the impact performance of the glass laminate, the outer glass sheet comprises chemically strengthened glass and may be less than or equal to 1 mm in thickness, while the inner glass sheet comprises non-chemically strengthened glass and may be less than or equal to 2.5 mm in thickness. In some embodiments, the thickness of the polymeric interlayer (eg, polyvinyl butyral or PVB) may be less than or equal to 1.6 mm. The disclosed hybrid glass laminate construction can preferably distribute stress in response to impact. For example, the disclosed hybrid glass laminates can provide excellent impact and fracture resistance in response to external impact events, while adequately dissipating energy and cracking in response to internal impact events.
本发明的一个非限制性实施方式提供了如下玻璃层叠结构，其具有非化学强化的外部玻璃片、化学强化的内部玻璃片以及位于外部玻璃片和内部玻璃片之间的至少一层聚合物中间层，其中，内部玻璃片的厚度约为0.5-1.5mm，并且其中，外部玻璃片的厚度约为1.5-3.0mm。One non-limiting embodiment of the present invention provides a glass laminate structure having a non-chemically strengthened outer glass sheet, a chemically strengthened inner glass sheet, and at least one polymer intermediate layer between the outer glass sheet and the inner glass sheet layer, wherein the thickness of the inner glass sheet is about 0.5-1.5 mm, and wherein the thickness of the outer glass sheet is about 1.5-3.0 mm.
本发明的另一个非限制性实施方式提供了如下玻璃层叠结构，其具有非化学强化的外部玻璃片、化学强化的内部玻璃片以及位于外部玻璃片和内部玻璃片之间的至少一层聚合物中间层，其中，内玻璃层的表面压缩应力约为250-900MPa。Another non-limiting embodiment of the present invention provides a glass laminate having a non-chemically strengthened outer glass sheet, a chemically strengthened inner glass sheet, and at least one layer of polymer between the outer glass sheet and the inner glass sheet The middle layer, wherein, the surface compressive stress of the inner glass layer is about 250-900MPa.
在以下的详细描述中给出了要求保护的主题内容的其他特征和优点，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所要求保护的主题而被认识。Other features and advantages of the claimed subject matter are given in the following detailed description, some of which are readily apparent to those skilled in the art from the description, or include the following detailed description, The claimed subject matter described herein, including the claims and drawings, is recognized.
应理解的是，前面的一般性描述和以下的详细描述都介绍了本发明的实施方式，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本发明的进一步的理解，附图被结合在本说明书中并构成说明书的一部分。附图举例说明了本发明的各种实施方式，并与描述一起用来解释所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 embodiments of the invention, 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 invention, and are incorporated in and constitute a part of this specification. The drawings illustrate various embodiments of the invention, and together with the description serve to explain the principles and operations of the claimed subject matter.
附图说明Description of drawings
出于示意性目的，在附图中示出优选形式，但是，应理解，本文所揭示和所讨论的实施方式不限于所示的精确配置和手段。For illustrative purposes, the preferred forms are shown in the drawings, but it should be understood that the embodiments disclosed and discussed herein are not limited to the precise arrangements and instrumentalities shown.
图1是根据本发明的一些实施方式的示例性平面混合玻璃层叠体的示意图。Figure 1 is a schematic diagram of an exemplary planar hybrid glass laminate according to some embodiments of the present invention.
图2是根据本发明的其他实施方式的示例性弯曲混合玻璃层叠体的示意图。2 is a schematic illustration of an exemplary curved hybrid glass laminate according to other embodiments of the present invention.
图3是根据本发明的其他实施方式的示例性弯曲混合玻璃层叠体的示意图。3 is a schematic illustration of an exemplary curved hybrid glass laminate according to other embodiments of the present invention.
图4是根据本发明的额外实施方式的示例性弯曲混合玻璃层叠体的示意图。4 is a schematic illustration of an exemplary curved hybrid glass laminate according to additional embodiments of the present invention.
具体实施方式detailed description
在以下描述中，相同的附图标记表示附图所示的若干视图中类似或相应的部分。还应理解，除非另外指出，术语如“顶部”，“底部”，“向外”，“向内”等是方便词语，不构成对术语的限制。此外，每当将一个组描述为包含一组要素中的至少一个要素和它们的组合时，应将其理解为所述组可以单个要素或相互组合的形式包含任何数量的这些所列要素，或者主要由它们组成，或者由它们组成。In the following description, the same reference numerals denote similar or corresponding parts in the several views shown in the drawings. It should also be understood that terms such as "top", "bottom", "outwardly", "inwardly", etc. are words of convenience and do not constitute limitations of the terms unless otherwise indicated. Furthermore, whenever a group is described as comprising at least one of a set of elements and combinations thereof, it will be understood that the set may contain any number of those listed elements, either singly or in combination with each other, or Consists mainly of them, or consists of them.
类似地，每当将一个组描述为由一组要素中的至少一个要素或它们的组合组成时，应将其理解为所述组可以单个要素或相互组合的形式由任何数量的这些所列要素组成。除非另外说明，否则，列举的数值范围同时包括所述范围的上限和下限。除非另外说明，否则，本文所用的不定冠词“一个”和“一种”及其相应的定冠词“该”表示“至少一(个/种)”，或者“一(个/种)或多(个/种)”。Similarly, whenever a group is described as consisting of at least one of a group of elements or a combination of them, it is to be understood that the group may consist of any number of those listed elements, either singly or in combination. composition. Unless otherwise stated, the recited numerical ranges include both the upper and lower limits of the stated range. Unless otherwise stated, the indefinite articles "a" and "an" and their corresponding definite articles "the" as used herein mean "at least one" or "a" or Multiple (one/species)".
提供以下对本发明的描述，作为按其目前已知实施方式来揭示本发明内容。本领域技术人员将会认识到，可以对本文所述的实施方式做出许多改变，同时仍能获得本发明的有益结果。还显而易见的是，本发明所需的有益结果中的一部分可以通过选择本发明的一些特征而不利用其他的特征来获得。因此，本领域技术人员会认识到，对本发明的许多更改和修改都是可能的，在某些情况下甚至可能是理想的，并且是本发明的一部分。因此，提供以下描述作为对本发明原理的说明，不构成对本发明的限制。The following description of the invention is provided as a disclosure of the invention in its presently known embodiments. Those skilled in the art will recognize that many changes can be made to the embodiments described herein while still obtaining the beneficial results of the present invention. It will also be apparent that some of the desired beneficial results of the invention can be obtained by selecting some of the features of the invention without utilizing others. Accordingly, those skilled in the art will recognize that many changes and modifications to the present invention are possible and can even be desirable in certain circumstances and are a part of the present invention. Accordingly, the following description is provided as an illustration of the principles of the invention and not as a limitation of the invention.
本领域技术人员应理解的是，本文所述的示例性实施方式可以具有各种改进而不背离本发明的精神和范围。因此，描述并不旨在也不应理解为限制于给出的例子，而是应该具有所附权利要求及其等价形式所提供的完全保护宽度。此外，还可使用本发明的一些特征，而相应地不使用其它特征。因此，提供示例或示意实施方式的以下说明，来显示本发明的原理，而不构成其限制，且可包括对本发明的修改和置换。Those skilled in the art will appreciate that various modifications may be made to the exemplary embodiments described herein without departing from the spirit and scope of the invention. Accordingly, the description is not intended and should not be read as limited to the examples given, but should be given the full breadth of protection afforded by the appended claims and their equivalents. Furthermore, some features of the invention may be used without correspondingly using other features. Accordingly, the following description of example or illustrative embodiments is provided to illustrate the principles of the invention, not to limit it, and may include modifications and permutations of the invention.
本文所揭示的玻璃层叠体构造成包括外部化学强化玻璃片和内部非化学强化玻璃片。如本文所限定，当使用玻璃层叠体时，外部玻璃片将接近或接触环境，而内部玻璃片将接近或接触包括所述玻璃层叠体的结构或车辆(例如汽车)的内部(例如，客舱)。The glass laminates disclosed herein are constructed to include an outer sheet of chemically strengthened glass and an inner sheet of non-chemically strengthened glass. As defined herein, when using a glass laminate, the exterior glass sheet will be in proximity to or in contact with the environment, while the interior glass sheet will be in proximity to or in contact with the structure comprising the glass laminate or the interior (e.g., passenger compartment) of a vehicle (e.g., an automobile) .
如图1所示是示例性玻璃层叠体。玻璃层叠体100包括外部玻璃片110、内部玻璃片120和聚合物中间层130。聚合物中间层可以分别与相应的外部玻璃片和内部玻璃片直接物理接触(例如，与它们层叠)。外部玻璃片110具有外表面112和内表面114。类似的，内部玻璃片120具有外表面122和内表面124。如示例性实施方式所示，外部玻璃片110的内表面114和内部玻璃片120的内表面124分别与聚合物中间层130接触。An exemplary glass laminate is shown in FIG. 1 . Glass laminate 100 includes an outer glass sheet 110 , an inner glass sheet 120 and a polymer interlayer 130 . The polymer interlayer may be in direct physical contact with (eg, laminated to) the respective outer and inner glass sheets, respectively. The outer glass sheet 110 has an outer surface 112 and an inner surface 114 . Similarly, inner glass sheet 120 has an outer surface 122 and an inner surface 124 . As shown in the exemplary embodiment, inner surface 114 of outer glass sheet 110 and inner surface 124 of inner glass sheet 120 are each in contact with polymeric interlayer 130 .
在使用过程中，希望玻璃层叠体能能够抵抗响应外部冲击事件的破裂。但是，响应内部冲击事件，例如玻璃层叠体被车辆的乘坐者撞击时，希望所述玻璃层叠体将乘坐者保持在车辆中，且耗散冲击后的能量以使得损伤最小化。模拟发生于车辆内部的冲击事件的ECER43人头模型测试，是要求层叠玻璃窗响应具体的内部冲击而断裂的常规测试。During use, it is desirable that the glass laminate be resistant to fracture in response to an external impact event. However, in response to an internal impact event, such as when a glass laminate is struck by an occupant of a vehicle, it is desirable that the glass laminate hold the occupant in the vehicle and dissipate post-impact energy to minimize damage. The ECER43 head phantom test, which simulates an impact event occurring inside a vehicle, is a routine test requiring laminated glazing to break in response to a specific interior impact.
不希望受到理论的限制，当玻璃片/聚合物中间层/玻璃片层叠体的一块窗格受到冲击时，受冲击玻璃片的相对表面以及相对玻璃片的外表面处于拉伸状态中。玻璃片/聚合物中间层/玻璃片层叠体在双轴负载下计算的应力分布表明：负载率低时，受到冲击的玻璃片的相对表面的拉伸应力的大小可相当于(或甚至稍微大于)相对玻璃片的外表面所经受的拉伸应力的大小。但是，当负载率高时(这通常也是汽车中经受的冲击的特点)，相对玻璃片的外表面的拉伸应力的大小，可能远大于受到冲击的玻璃片的相对表面的拉伸应力。如本文所揭示，通过将混合玻璃层叠体构造成具有化学强化的外部玻璃片和非化学强化的内部玻璃片，可同时优化对于外部冲击事件和内部冲击事件的抗冲性。Without wishing to be bound by theory, when a pane of the glass sheet/polymer interlayer/glass sheet laminate is impacted, the opposing surface of the impacted glass sheet and the outer surface of the opposing glass sheet are in tension. Stress distributions calculated for glass sheet/polymer interlayer/glass sheet laminates under biaxial loading show that at low loading rates, the magnitude of the tensile stress on the opposite surface of the glass sheet subjected to impact can be comparable (or even slightly greater than ) relative to the magnitude of the tensile stress experienced by the outer surface of the glass sheet. However, when the load rate is high (as is often the case with impacts experienced in automobiles), the magnitude of the tensile stress on the outer surface of the opposing glass sheet may be much greater than the tensile stress on the opposing surface of the impacted glass sheet. As disclosed herein, by constructing a hybrid glass laminate with chemically strengthened outer glass sheets and non-chemically strengthened inner glass sheets, impact resistance to both external impact events and internal impact events can be optimized simultaneously.
合适的内部玻璃片是非化学强化玻璃片，例如钠钙玻璃。任选地，内部玻璃片可进行热强化。在将钠钙玻璃用作非化学强化的玻璃片的实施方式中，可以使用常规的装饰材料和方法(例如玻璃料釉和丝网印刷)，这可简化玻璃层叠体制造工艺。可将有色钠钙玻璃片结合到混合玻璃层叠体，从而实现电磁谱上所需的透过率和/或衰减。A suitable inner glass sheet is a non-chemically strengthened glass sheet, such as soda lime glass. Optionally, the inner glass sheets can be heat strengthened. In embodiments where soda-lime glass is used as the non-chemically strengthened glass sheet, conventional decoration materials and methods such as frit glaze and screen printing can be used, which can simplify the glass laminate manufacturing process. Tinted soda-lime glass sheets can be incorporated into hybrid glass laminates to achieve desired transmission and/or attenuation across the electromagnetic spectrum.
可以通过离子交换过程对合适的外部玻璃片进行化学强化。在该过程中，通常将玻璃片在熔盐浴中浸没一段预定的时间，玻璃片表面处或者表面附近的离子与来自盐浴的较大金属离子发生交换。在一个实施方式中，熔盐浴的温度约为430℃，预定的时间约为8小时。较大离子结合到玻璃中，通过在近表面区域产生压缩应力来强化玻璃片。在玻璃的中心区域内诱发了相应的拉伸应力，以平衡压缩应力。Suitable outer glass sheets may be chemically strengthened by an ion exchange process. In this process, the glass sheet is typically immersed in a molten salt bath for a predetermined period of time, and ions at or near the surface of the glass sheet are exchanged with larger metal ions from the salt bath. In one embodiment, the temperature of the molten salt bath is about 430° C., and the predetermined time is about 8 hours. Larger ions are incorporated into the glass, strengthening the glass sheet by creating compressive stress in the near-surface region. A corresponding tensile stress is induced in the central region of the glass to balance the compressive stress.
适用于形成混合玻璃层叠体的示例性可离子交换玻璃是碱性铝硅酸盐玻璃或者碱性铝硼硅酸盐玻璃，但是也考虑其他玻璃组合物。如本文所用，“可离子交换”表示玻璃能够通过尺寸更大或更小的同价态阳离子交换位于玻璃表面处或附近的阳离子。一种示例性玻璃组合物包含SiO2、B2O3和Na2O，其中，(SiO2+B2O3)≥66摩尔％，并且Na2O≥9摩尔％。在一个实施方式中，玻璃片包含至少6重量％的氧化铝。在另一个实施方式中，玻璃片包含一种或多种碱土氧化物，使得碱土氧化物的含量至少为5重量％。在一些实施方式中，合适的玻璃组合物还包含K2O、MgO和CaO中的至少一种。在一个特定实施方式中，玻璃可包含61-75摩尔％的SiO2；7-15摩尔％的Al2O3；0-12摩尔％的B2O3；9-21摩尔％的Na2O；0-4摩尔％的K2O；0-7摩尔％的MgO；以及0-3摩尔％的CaO。Exemplary ion-exchangeable glasses suitable for use in forming hybrid glass laminates are alkali aluminosilicate glasses or alkali aluminoborosilicate glasses, although other glass compositions are also contemplated. As used herein, "ion-exchangeable" means that the glass is capable of exchanging cations located at or near the surface of the glass with equivalent cations of larger or smaller size. An exemplary glass composition comprises SiO2 , B2 O3 , and Na2 O, wherein (SiO2 +B2 O3 )≧66 mol % and Na2 O ≧9 mol %. In one embodiment, the glass sheet comprises at least 6% by weight alumina. In another embodiment, the glass flake comprises one or more alkaline earth oxides such that the content of alkaline earth oxides is at least 5% by weight.In some embodiments, suitable glass compositions also include at least one of K2O, MgO, and CaO. In a particular embodiment, the glass may comprise 61-75 mole % SiO2 ; 7-15 mole % Al2 O3 ; 0-12 mole % B2 O3 ; 9-21 mole % Na2 O 0-4 mole % K2O; 0-7 mole % MgO; and 0-3 mole % CaO.
适合形成混合玻璃层叠体的另一种示例性玻璃组合物包含：60-70摩尔％的SiO2；6-14摩尔％的Al2O3；0-15摩尔％的B2O3；0-15摩尔％的Li2O；0-20摩尔％的Na2O；0-10摩尔％的K2O；0-8摩尔％的MgO；0-10摩尔％的CaO；0-5摩尔％的ZrO2；0-1摩尔％的SnO2；0-1摩尔％的CeO2；小于50ppm的As2O3；以及小于50ppm的Sb2O3；其中12摩尔％≤(Li2O+Na2O+K2O)≤20摩尔％，并且0摩尔％≤(MgO+CaO)≤10摩尔％。Another exemplary glass composition suitable for forming a hybrid glass laminate comprises: 60-70 mole % SiO2 ; 6-14 mole % Al2 O3 ; 0-15 mole % B2 O3 ; 0- 15 mol% of Li2 O; 0-20 mol% of Na2 O; 0-10 mol% of K2 O; 0-8 mol% of MgO; 0-10 mol% of CaO; 0-5 mol% of ZrO2 ; 0-1 mol% SnO2 ; 0-1 mol% CeO2 ; less than 50ppm As2 O3 ; and less than 50ppm Sb2 O3 ; wherein 12 mol%≤(Li2 O+Na2 O+K2 O)≤20 mol%, and 0 mol%≤(MgO+CaO)≤10 mol%.
另一种示例性玻璃组合物包含：63.5-66.5摩尔％的SiO2；8-12摩尔％的Al2O3；0-3摩尔％的B2O3；0-5摩尔％的Li2O；8-18摩尔％的Na2O；0-5摩尔％的K2O；1-7摩尔％的MgO；0-2.5摩尔％的CaO；0-3摩尔％的ZrO2；0.05-0.25摩尔％的SnO2；0.05-0.5摩尔％的CeO2；小于50ppm的As2O3；以及小于50ppm的Sb2O3；其中，14摩尔％≤(Li2O+Na2O+K2O)≤18摩尔％，并且2摩尔％≤(MgO+CaO)≤7摩尔％。Another exemplary glass composition comprises: 63.5-66.5 mol % SiO2 ; 8-12 mol % Al2 O3 ; 0-3 mol % B2 O3 ; 0-5 mol % Li2 O 8-18 mol% Na2 O; 0-5 mol% K2 O; 1-7 mol% MgO; 0-2.5 mol% CaO; 0-3 mol% ZrO2 ; % of SnO2 ; 0.05-0.5 mole % of CeO2 ; less than 50 ppm of As2 O3 ; and less than 50 ppm of Sb2 O3 ; wherein, 14 mole %≤(Li2 O+Na2 O+K2 O) ≤18 mol%, and 2 mol%≤(MgO+CaO)≤7 mol%.
在一个具体实施方式中，碱性铝硅酸盐玻璃包含氧化铝、至少一种碱金属以及在一些实施方式中大于50摩尔％的SiO2，在其他实施方式中至少为58摩尔％的SiO2，以及在其他实施方式中至少为60摩尔％的SiO2，其中该比例其中，组分的比例以摩尔％计，以及改性剂是碱金属氧化物。在一些特定实施方式中，该玻璃包含以下组分、基本由以下组分组成或者由以下组分组成：58-72摩尔％的SiO2、9-17摩尔％的Al2O3、2-12摩尔％的B2O3、8-16摩尔％的Na2O以及0-4摩尔％的K2O，其中，该比例In a specific embodiment, the alkali aluminosilicate glass comprises alumina, at least one alkali metal, and in some embodiments greater than 50 mole %SiO2 and in other embodiments at least 58 mole %SiO2 , and in other embodiments at least 60 mole % SiO2 , wherein the ratio Wherein, the ratio of the components is in mole %, and the modifier is an alkali metal oxide. In some specific embodiments, the glass comprises, consists essentially of, or consists of 58-72 mole % SiO2 , 9-17 mole % Al2 O3 , 2-12 Mole % of B2 O3 , 8-16 mole % of Na2 O and 0-4 mole % of K2 O, wherein the ratio
在另一个实施方式中，碱性铝硅酸盐玻璃包含以下组分、基本由以下组分组成、或者由以下组分组成：61-75摩尔％的SiO2；7-15摩尔％的Al2O3；0-12摩尔％的B2O3；9-21摩尔％的Na2O；0-4摩尔％的K2O；0-7摩尔％的MgO；以及0-3摩尔％的CaO。In another embodiment, the alkali aluminosilicate glass comprises, consists essentially of, or consists of 61-75 mol % SiO2 ; 7-15 mol % Al2 0-12 mole % B2O3;9-21 mole % Na2O; 0-4 mole % K2O; 0-7 mole % MgO; and0-3 mole % CaO .
在另一个实施方式中，碱性铝硅酸盐玻璃基材包含以下组分、基本由以下组分组成、或者由以下组分组成：60-70摩尔％的SiO2；6-14摩尔％的Al2O3；0-15摩尔％的B2O3；0-15摩尔％的Li2O；0-20摩尔％的Na2O；0-10摩尔％的K2O；0-8摩尔％的MgO；0-10摩尔％的CaO；0-5摩尔％的ZrO2；0-1摩尔％的SnO2；0-1摩尔％的CeO2；小于50ppm的As2O3；以及小于50ppm的Sb2O3；其中12摩尔％≤Li2O+Na2O+K2O≤20摩尔％，并且0摩尔％≤MgO+CaO≤10摩尔％。In another embodiment, the alkali aluminosilicate glass substrate comprises, consists essentially of, or consists of 60-70 mol % SiO2 ; 6-14 mol % Al2 O3 ; 0-15 mole % B2 O3 ; 0-15 mole % Li2 O; 0-20 mole % Na2 O; 0-10 mole % K2 O; % MgO; 0-10 mol% CaO; 0-5 mol% ZrO2; 0-1 mol%SnO2; 0-1 mol% CeO2; lessthan 50ppmAs2O3 ; Sb2 O3 ; wherein 12 mol% ≤ Li2 O + Na2 O + K2 O ≤ 20 mol %, and 0 mol % ≤ MgO + CaO ≤ 10 mol %.
在另一个实施方式中，碱性铝硅酸盐玻璃包含以下组分、基本由以下组分组成、或者由以下组分组成：64-68摩尔％的SiO2；12-16摩尔％的Na2O；8-12摩尔％的Al2O3；0-3摩尔％的B2O3；2-5摩尔％的K2O；4-6摩尔％的MgO；以及0-5摩尔％的CaO，其中，66摩尔％≤SiO2+B2O3+CaO≤69摩尔％；Na2O+K2O+B2O3+MgO+CaO+SrO>10摩尔％；5摩尔％≤MgO+CaO+SrO≤8摩尔％；(Na2O+B2O3)-Al2O3≤2摩尔％；2摩尔％≤Na2O-Al2O3≤6摩尔％；以及4摩尔％≤(Na2O+K2O)-Al2O3≤10摩尔％。In another embodiment, the alkali aluminosilicate glass comprises, consists essentially of, or consists of 64-68 mol % SiO2 ; 12-16 mol % Na2 O; 8-12 mole % Al2 O3 ; 0-3 mole % B2 O3 ; 2-5 mole % K2 O; 4-6 mole % MgO; and 0-5 mole % CaO , wherein, 66 mol%≤SiO2 +B2 O3 +CaO≤69 mol%; Na2 O+K2 O+B2 O3 +MgO+CaO+SrO>10 mol%; 5 mol%≤MgO+ CaO+SrO≤8mol %; (Na2O+ B2O3)-Al2O3≤2mol %; 2mol%≤Na2O-Al2O3≤6mol %; and 4mol%≤ (Na2 O+K2 O)—Al2 O3 ≦10 mol%.
在一些实施方式中，化学强化玻璃和非化学强化玻璃配料有0-2摩尔％的选自下组的至少一种澄清剂，包括：Na2SO4、NaCl、NaF、NaBr、K2SO4、KCl、KF、KBr以及SnO2。In some embodiments, chemically strengthened glass and non-chemically strengthened glass batches have 0-2 mole % of at least one fining agent selected from the group consisting of:Na2SO4 ,NaCl ,NaF , NaBr,K2SO4 , KCl, KF, KBr and SnO2 .
在一个示例性实施方式中，化学强化玻璃中的钠离子可以被来自熔盐浴的钾离子替换，但是具有较大原子半径的其他碱金属离子(例如铷或铯)也可以替换玻璃中较小的碱金属离子。根据具体实施方式，玻璃中较小的碱金属离子可以被Ag+离子替换。类似地，其它碱金属盐，例如但不限于硫酸盐以及卤化物等，可以用于离子交换过程。In one exemplary embodiment, the sodium ions in the chemically strengthened glass can be replaced by potassium ions from the molten salt bath, but other alkali metal ions with larger atomic radii (such as rubidium or cesium) can also replace the smaller ones in the glass. of alkali metal ions. Depending on the specific embodiment, the smaller alkali metal ions in the glass can be replaced by Ag+ ions. Similarly, other alkali metal salts, such as but not limited to sulfates and halides, etc., can be used in the ion exchange process.
在低于玻璃网络会发生松弛的温度下用较大离子替换较小离子，在玻璃表面上产生离子分布，这导致应力曲线。进入的离子的较大体积在表面上产生压缩应力(CS)，在玻璃中心产生张力(中心张力，或者CT)。压缩应力与中心张力的关系如下式所示：Replacing smaller ions with larger ions at temperatures below which relaxation of the glass network occurs creates a distribution of ions across the glass surface, which results in a stress profile. The larger volume of incoming ions creates compressive stress (CS) at the surface and tension in the center of the glass (central tension, or CT). The relationship between compressive stress and central tension is as follows:
式中，t是玻璃片的总厚度，以及DOL是交换深度，也称为层深度。where t is the total thickness of the glass sheet, and DOL is the exchange depth, also known as layer depth.
根据各个实施方式，混合玻璃层叠体包括离子交换的玻璃，其具有多种所需性质，包括轻量化、高抗冲性和改善的声衰减。According to various embodiments, the hybrid glass laminate includes ion-exchanged glass that has various desirable properties, including lightweight, high impact resistance, and improved sound attenuation.
在一个实施方式中，化学强化的玻璃片的表面压缩应力可以至少为300MPa，例如至少400、450、500、550、600、650、700、750或者800MPa，层深度至少约为20μm(例如，至少约为20、25、30、35、40、45或者50μm)和/或大于40MPa(例如，大于40、45或者50MPa)但是小于100MPa(例如，小于100、95、90、85、80、75、70、65、60或者55MPa)的中心张力。In one embodiment, the chemically strengthened glass sheet may have a surface compressive stress of at least 300 MPa, such as at least 400, 450, 500, 550, 600, 650, 700, 750, or 800 MPa, with a layer depth of at least about 20 μm (e.g., at least about 20, 25, 30, 35, 40, 45 or 50 μm) and/or greater than 40 MPa (for example, greater than 40, 45 or 50 MPa) but less than 100 MPa (for example, less than 100, 95, 90, 85, 80, 75, 70, 65, 60 or 55MPa) central tension.
化学强化的玻璃片的弹性模量可以约为60-85GPa(例如，60、65、70、75、80或85GPa)。玻璃片和聚合物中间层的弹性模量可同时影响所得到的玻璃层叠体的机械性质(例如，偏斜和强度)以及声性能(例如，穿透损耗)。The modulus of elasticity of the chemically strengthened glass sheet can be about 60-85 GPa (eg, 60, 65, 70, 75, 80, or 85 GPa). The modulus of elasticity of the glass sheet and polymeric interlayer can affect both the mechanical properties (eg, deflection and strength) and acoustic properties (eg, penetration loss) of the resulting glass laminate.
示例性玻璃片成形方法包括熔合拉制和狭缝拉制工艺，其例子分别是下拉法和浮法。化学强化的玻璃片以及非化学强化的玻璃片都可以用这些方法形成。熔合拉制工艺使用拉制容器，其具有用来接受熔融玻璃原料的通道。通道具有堰，其沿着通道的长度在通道两侧的顶部开放。当用熔融材料填充通道时，熔融玻璃从堰溢流。在重力的作用下，熔融玻璃从拉制容器的外表面流下。这些外表面向下且向内延伸，从而它们在拉制容器下方的边缘处结合。两个流动玻璃表面在该边缘处结合，从而熔合并形成单个流动片材。熔合拉制法的优点在于，由于从通道上流过的两块玻璃膜熔合在一起，因此所得到的玻璃片的任一外表面都没有与设备的任意部件相接触。因此，熔合拉制玻璃片的表面性质不受到此类接触的影响。Exemplary glass sheet forming methods include fusion draw and slot draw processes, examples of which are down-draw and float, respectively. Both chemically strengthened glass sheets as well as non-chemically strengthened glass sheets can be formed using these methods. The fusion draw process uses a draw vessel with channels for receiving molten glass feedstock. The channel has weirs that open at the top on both sides of the channel along the length of the channel. As the channel is filled with molten material, molten glass overflows the weir. Under the action of gravity, the molten glass flows down the outer surface of the drawing vessel. These outer surfaces extend downward and inward so that they join at the lower edge of the drawn container. The two flowing glass surfaces join at this edge, thereby fusing and forming a single flowing sheet. The advantage of the fusion draw method is that, since the two glass films flowing through the channel are fused together, neither outer surface of the resulting glass sheet comes into contact with any part of the apparatus. Therefore, the surface properties of the fusion drawn glass sheet are not affected by such contact.
狭缝拉制法与熔合拉制法不同。在此方法中，将熔融原料玻璃提供到拉制容器。拉制容器的底部具有开放狭缝，其具有沿着狭缝的长度延伸的喷嘴。熔融玻璃流过狭缝/喷嘴，以连续的片材下拉并进入退火区。狭缝拉制工艺可以提供比熔合拉制工艺更薄的片材，因为仅有单片被拉制通过狭缝，而不是将两片熔合在一起。Slot drawing is different from fusion drawing. In this method, molten raw glass is provided to a drawing vessel. The bottom of the draw vessel has an open slit with a nozzle extending the length of the slit. The molten glass flows through the slit/nozzle, is drawn down in a continuous sheet and enters the annealing zone. The slot draw process can provide thinner sheets than the fusion draw process because only a single sheet is drawn through the slot rather than two sheets being fused together.
下拉工艺生产具有均匀厚度和较原始加工表面的玻璃片。因为玻璃表面的强度受到表面瑕疵的量和尺寸的控制，因此接触程度最小的原始表面具有较高的初始强度。当随后对该高强度玻璃进行化学强化时，所得到的强度可高于已经进行过磨光和抛光的表面的强度。下拉玻璃可以被拉制成约小于2mm的厚度。此外，下拉玻璃具有非常平坦、光滑的表面，其可以不经高成本的研磨和抛光就用于最终应用。The down-draw process produces glass sheets with uniform thickness and a more pristine machined surface. Because the strength of a glass surface is controlled by the amount and size of surface imperfections, pristine surfaces with minimal contact have higher initial strength. When the high strength glass is subsequently chemically strengthened, the resulting strength can be greater than that of the ground and polished surface. Down-drawn glass can be drawn to a thickness of approximately less than 2mm. In addition, down-drawn glass has a very flat, smooth surface that can be used in the final application without costly grinding and polishing.
在浮法玻璃方法中，可通过使得熔融玻璃在熔融金属(通常是锡)床上浮动，来制造可表征为具有光滑表面和均匀厚度的玻璃片。在示例性过程中，将熔融玻璃进料到熔融锡床表面上，形成浮动带。随着玻璃带沿着锡浴流动，温度逐渐降低直至可以将固体玻璃片从锡上举起到辊上。一旦离开浴，可以对玻璃片进行进一步冷却并退火以降低内应力。In the float glass process, a sheet of glass that can be characterized as having a smooth surface and uniform thickness can be produced by floating molten glass on a bed of molten metal, usually tin. In an exemplary process, molten glass is fed onto the surface of a bed of molten tin, forming floating ribbons. As the glass ribbon flows along the tin bath, the temperature is gradually reduced until a solid sheet of glass can be lifted from the tin onto the rollers. Once out of the bath, the glass sheet can be further cooled and annealed to reduce internal stresses.
玻璃片可用于形成玻璃层叠体。如本文所限定，混合玻璃层叠体包括朝向外部的化学强化的玻璃片，朝向内部的非化学强化的玻璃片以及形成在玻璃片之间的聚合物中间层。聚合物中间层可包含整体式聚合物片、多层聚合物片或者复合聚合物片。聚合物中间层可以是，例如，塑化聚(乙烯醇缩丁醛)片。Glass sheets can be used to form glass laminates. As defined herein, a hybrid glass laminate includes outwardly facing chemically strengthened glass sheets, inwardly facing non-chemically strengthened glass sheets, and a polymer interlayer formed between the glass sheets. The polymeric interlayer may comprise a monolithic polymer sheet, a multilayer polymer sheet, or a composite polymer sheet. The polymeric interlayer can be, for example, a plasticized poly(vinyl butyral) sheet.
玻璃层叠体可适用于在建筑和汽车开口(例如汽车玻璃窗)中提供光学透明的阻隔。可以采用各种工艺形成玻璃层叠体。在示例性实施方式中，组装涉及敷设第一玻璃片，将聚合物中间层(例如PVB片)铺在其上，敷设第二玻璃片，以及随后裁剪超出玻璃片边缘的过量PVB。粘结步骤可包括从界面处排出大部分的空气，并使PVB与玻璃片部分粘合。通常在提升的温度和压力下进行的精整步骤完成了各块玻璃片与聚合物中间层的匹配。在前述实施方式中，所述第一片可以是化学强化的玻璃片，以及所述第二片可以是非化学强化的玻璃片，反之亦然。Glass laminates are suitable for providing optically clear barriers in architectural and automotive openings, such as automotive glass windows. Various processes can be used to form the glass laminate. In an exemplary embodiment, assembly involves laying down a first glass sheet, laying a polymer interlayer (eg, a PVB sheet) over it, laying down a second glass sheet, and then trimming excess PVB beyond the edge of the glass sheet. The bonding step may include evacuating most of the air from the interface and partially bonding the PVB to the glass sheet. A finishing step, usually at elevated temperature and pressure, completes the mating of the individual glass sheets to the polymer interlayer. In the foregoing embodiments, the first sheet may be a chemically strengthened glass sheet and the second sheet may be a non-chemically strengthened glass sheet, or vice versa.
可以将热塑性材料(例如PVB)用作预先形成的聚合物中间层。在某些实施方式中，热塑性层的厚度可以至少为0.125mm(例如，0.125、0.25、0.38、0.5、0.7、0.76、0.81、1、1.14、1.19或者1.2mm)。热塑性层的厚度可以小于或等于1.6mm(例如，0.4-1.2mm,，例如约0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.1或1.2mm)。热塑性层可以覆盖玻璃的两个相反主表面的大部分，或者优选地基本上全部覆盖。它还可覆盖玻璃的边缘面。可以将与热塑性层接触的玻璃片加热至高于热塑性材料的软化点，例如比软化点高至少5℃或10℃，以促进热塑性材料与各个玻璃片的粘结。可以在玻璃与热塑性层接触的情况下，在压力下进行加热。A thermoplastic material such as PVB may be used as a pre-formed polymeric interlayer. In certain embodiments, the thickness of the thermoplastic layer can be at least 0.125 mm (eg, 0.125, 0.25, 0.38, 0.5, 0.7, 0.76, 0.81, 1, 1.14, 1.19, or 1.2 mm). The thickness of the thermoplastic layer may be less than or equal to 1.6 mm (eg, 0.4-1.2 mm, such as about 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 or 1.2 mm). The thermoplastic layer may cover most, or preferably substantially all, of the two opposing major surfaces of the glass. It also covers the edge faces of the glass. The glass sheets in contact with the thermoplastic layers may be heated above the softening point of the thermoplastic material, for example at least 5°C or 10°C above the softening point, to promote bonding of the thermoplastic material to the respective glass sheet. Heating can be performed under pressure with the glass in contact with the thermoplastic layer.
选择市售可得的聚合物中间层材料总结见表1，其还提供每种产品样品的玻璃转化温度和模量。从供应商的技术数据页或者采用DSC200差示扫描量热仪(日本精工仪器公司(SeikoInstrumentsCorp.,Japan))或者通过用于玻璃转化和模量数据的ASTMD638方法，来分别确定玻璃转化温度和模量数据。用于ISD树脂的丙烯酸类/硅酮树脂材料的进一步描述见美国专利第5,624,763号，吸声改性的PVB树脂的描述见日本专利第05138840号，其全文通过引用结合入本文。A selection of commercially available polymeric interlayer materials is summarized in Table 1, which also provides the glass transition temperature and modulus for each product sample. Glass transition temperature and modulus were determined from the supplier's technical data sheet or using a DSC200 differential scanning calorimeter (Seiko Instruments Corp., Japan) or by the ASTM D638 method for glass transition and modulus data, respectively. Quantitative data. Acrylic/silicone resin materials for ISD resins are further described in US Patent No. 5,624,763 and acoustically modified PVB resins are described in Japanese Patent No. 05138840, the entire contents of which are incorporated herein by reference.
表1：示例性聚合物中间层材料Table 1: Exemplary polymer interlayer materials
可以在混合玻璃层叠体中结合一层或多层聚合物中间层。多层中间层可以提供互补或不同的功能性，包括促进粘附、控制吸声、控制UV透射率、调色、染色和/或控制IR透射率。One or more polymeric interlayers may be incorporated in a hybrid glass laminate. Multiple interlayers can provide complementary or different functionalities, including promoting adhesion, controlling sound absorption, controlling UV transmission, tinting, tinting, and/or controlling IR transmission.
聚合物中间层的弹性模量可以约为1-75MPa(例如，约为1、2、5、10、20、25、50或75MPa)。对于1Hz的负荷速率，标准PVB中间层的弹性模量可以约为15MPa，吸声等级PVB中间层的弹性模量可以约为2MPa。The modulus of elasticity of the polymeric interlayer can be about 1-75 MPa (eg, about 1, 2, 5, 10, 20, 25, 50, or 75 MPa). For a load rate of 1 Hz, the elastic modulus of the standard PVB interlayer can be about 15 MPa, and the elastic modulus of the sound-absorbing grade PVB interlayer can be about 2 MPa.
在层叠过程中，通常将中间层加热至实现中间层软化的温度，这促进了中间层与玻璃片的相应表面的共形匹配。对于PVB，层叠温度可以约为140℃。中间层材料中流动的聚合物链与玻璃表面建立键合，这促进了粘附。提升的温度还加速了残留的空气和/或水分从玻璃-聚合物界面扩散出去。During lamination, the interlayer is typically heated to a temperature that achieves softening of the interlayer, which promotes conformal matching of the interlayer to the corresponding surface of the glass sheet. For PVB, the lamination temperature may be about 140°C. The flowing polymer chains in the interlayer material establish bonds with the glass surface, which promotes adhesion. The elevated temperature also accelerates the diffusion of trapped air and/or moisture away from the glass-polymer interface.
施加压力同时促进了中间层材料的流动并抑制了气泡的形成，否则水的蒸汽压与界面处俘获的空气结合起来可能会导致气泡的形成。为了抑制气泡的形成，对高压釜中的组件同时加热和加压。The application of pressure simultaneously facilitates the flow of the interlayer material and inhibits the formation of air bubbles that might otherwise result from the combination of the vapor pressure of the water and the air trapped at the interface. To suppress the formation of air bubbles, the components in the autoclave are simultaneously heated and pressurized.
混合玻璃层叠体可提供有益的效果，包括噪声衰减、降低UV和/或IR光透射，和/或增加窗口的美观性。包含所揭示的玻璃层叠体的单片玻璃片以及所形成的层叠体可以用以下一个或多个属性进行表征，包括：组成、密度、厚度、表面形貌以及各种性质，包括光学性质、声衰减性质以及机械性质如抗冲性。本文描述了混合玻璃层叠体的各个方面。Hybrid glass laminates can provide beneficial effects including noise attenuation, reduced UV and/or IR light transmission, and/or increased window aesthetics. Individual glass sheets comprising the disclosed glass laminates, as well as resulting laminates, can be characterized by one or more of the following properties, including: composition, density, thickness, surface topography, and various properties, including optical properties, acoustic properties, Attenuation properties as well as mechanical properties such as impact resistance. Various aspects of hybrid glass laminates are described herein.
混合玻璃层叠体可用作例如窗户或者玻璃窗，并且构造成任意合适的尺寸和大小。在一些实施方式中，玻璃层叠体的长度和宽度可以独立地从10cm变化至1m或更大(例如，0.1、0.2、0.5、1、2或5m)。独立地，玻璃层叠体可具有大于0.1m2的面积，例如大于0.1、0.2、0.5、1、2、5、10或25m2。Hybrid glass laminates may be used, for example, as windows or glazing, and constructed in any suitable size and dimension. In some embodiments, the length and width of the glass laminate can independently vary from 10 cm to 1 m or greater (eg, 0.1, 0.2, 0.5, 1, 2, or 5 m). Independently, the glass laminate may have an area greater than 0.1 m2 , such as greater than 0.1, 0.2, 0.5, 1, 2, 5, 10 or 25 m2 .
玻璃层叠体可以是基本平坦的或者对于某些应用是具有形状的。例如，用于挡风玻璃或盖板的玻璃层叠体可以成形为弯曲或者具有形状的部件。具有形状的玻璃层叠体的结构可以是简单或复杂的。在某些实施方式中，具有形状的玻璃层叠体可以具有复杂曲率，其中，玻璃片在两个独立方向上具有不同的曲率半径。从而此类具有形状的玻璃片可以表征为具有“交叉曲率”，其中，玻璃沿着平行于给定维度的轴弯曲，还沿着垂直于该相同维度的轴弯曲。例如，通常测得的汽车天窗约为0.5mx1.0m，沿短轴的曲率半径为2-2.5m，沿长轴的曲率半径为4-5m。The glass laminate can be substantially flat or, for some applications, shaped. For example, a glass laminate for a windshield or cover may be formed as a curved or shaped part. The structure of the shaped glass laminate can be simple or complex. In certain embodiments, shaped glass laminates may have complex curvatures, wherein the glass sheets have different radii of curvature in two separate directions. Such shaped glass sheets may thus be characterized as having "cross-curvatures" in which the glass is curved along an axis parallel to a given dimension and also curved along an axis perpendicular to the same dimension. For example, the usual measured car sunroof is about 0.5mx1.0m, the radius of curvature along the minor axis is 2-2.5m, and the radius of curvature along the major axis is 4-5m.
根据某些实施方式，可以通过弯曲因子来定义具有形状的玻璃层叠体，其中，对于给定的部件，弯曲因子等于沿着给定轴的曲率半径除以该轴的长度。因此，对于沿0.5m和1.0m的各轴的曲率半径分别为2m和4m的示例性汽车天窗，沿各轴的弯曲因子是4。具有形状的玻璃层叠体的弯曲因子可以为2-8(2、3、4、5、6、7或8)。According to certain embodiments, a glass laminate having a shape may be defined by a bend factor, where, for a given component, the bend factor is equal to the radius of curvature along a given axis divided by the length of that axis. Thus, for an exemplary automotive sunroof with radii of curvature of 2 m and 4 m along respective axes of 0.5 m and 1.0 m, respectively, the bending factor along each axis is 4. The bend factor of the shaped glass laminate may be 2-8 (2, 3, 4, 5, 6, 7 or 8).
图2显示了示例性具有形状的玻璃层叠体200。具有形状的玻璃层叠体200包括在层叠体的凸表面上形成的外部(化学强化的)玻璃片110，以及在层叠体的凹表面上形成的内部(非化学强化的)玻璃片120。但是，应理解，非示例性实施方式的凸面可包括非化学强化的玻璃片，同时相对的凹面可包括化学强化的玻璃片。FIG. 2 shows an exemplary shaped glass laminate 200 . Shaped glass laminate 200 includes an outer (chemically strengthened) glass sheet 110 formed on a convex surface of the laminate, and an inner (non-chemically strengthened) glass sheet 120 formed on a concave surface of the laminate. However, it should be understood that the convex surface of a non-exemplary embodiment may comprise a non-chemically strengthened glass sheet, while the opposing concave surface may comprise a chemically strengthened glass sheet.
图3是本发明的其他实施方式的横截面图。图4是本发明的额外实施方式的透视图。参见图3和4以及上文段落中的讨论，示例性层叠结构10可以包括化学强化玻璃(例如玻璃)的内层16。该内层16可以经过热处理、离子交换和/或退火。外层12可以是非化学强化的玻璃片，例如常规钠钙玻璃或者经退火的玻璃等。层叠体10还可包括位于外玻璃层和内玻璃层之间的聚合物中间层14。玻璃的内层16的厚度可以小于或等于1.0mm，并且残留表面CS水平约为250-350MPa，DOL大于60微米。在另一个实施方式中，内层16的CS水平优选约为300MPa。在一个实施方式中，中间层14的厚度可以约为0.8mm。示例性中间层14可以包括但不限于聚乙烯醇缩丁醛或者本文所述的其他合适的聚合物材料。在额外的实施方式中，可以对外层12和/或内层16的任意表面进行酸蚀刻，以改善对于外部冲击事件的耐用性。例如，在一个实施方式中，外层12的第一表面13可以经过酸蚀刻和/或内层的另一表面17可以经过酸蚀刻。在另一个实施方式中，外层的第一表面15可以经过酸蚀刻和/或内层的另一表面19可以经过酸蚀刻。从而此类实施方式可以提供层叠构造，其明显比常规层叠结构更轻，并且其符合规定冲击要求。外层12和/或内层16的示例性厚度可以是0.5mm至1.5mm至2.0mm的厚度，或者更厚。Fig. 3 is a cross-sectional view of another embodiment of the present invention. Figure 4 is a perspective view of an additional embodiment of the invention. Referring to FIGS. 3 and 4 and the discussion in the preceding paragraphs, an exemplary laminated structure 10 can include chemically strengthened glass (e.g. The inner layer 16 of glass). The inner layer 16 may be heat treated, ion exchanged and/or annealed. The outer layer 12 may be a sheet of non-chemically strengthened glass such as conventional soda lime glass or annealed glass or the like. Laminate 10 may also include a polymeric interlayer 14 between the outer glass ply and the inner glass ply. The thickness of the inner layer 16 of glass may be less than or equal to 1.0 mm, and the residual surface CS level is about 250-350 MPa, and the DOL is greater than 60 microns. In another embodiment, the inner layer 16 preferably has a CS level of about 300 MPa. In one embodiment, the thickness of the intermediate layer 14 may be about 0.8 mm. Exemplary intermediate layers 14 may include, but are not limited to, polyvinyl butyral or other suitable polymeric materials described herein. In additional embodiments, any surface of the outer layer 12 and/or inner layer 16 may be acid etched to improve durability against external impact events. For example, in one embodiment, the first surface 13 of the outer layer 12 may be acid etched and/or the other surface 17 of the inner layer may be acid etched. In another embodiment, the first surface 15 of the outer layer may be acid etched and/or the other surface 19 of the inner layer may be acid etched. Such embodiments may thus provide a laminated construction that is significantly lighter than conventional laminated structures and that meets regulatory impact requirements. Exemplary thicknesses of the outer layer 12 and/or inner layer 16 may be a thickness of 0.5 mm to 1.5 mm to 2.0 mm, or thicker.
在优选的实施方式中，薄的化学强化内层16的表面应力可以约为250-900MPa，并且厚度可以是0.5-1.0mm。在该实施方式中，外层12可以是经过退火(非化学强化)的玻璃，厚度约为1.5-3.0mm或者更厚。当然，在各个层叠结构10中，外层12和内层16的厚度可以是不同的。示例性层叠结构的另一个优选实施方式可以包括0.7mm的化学强化玻璃的内层、约为0.76mm厚的聚乙烯醇缩丁醛层以及2.1mm的经退火玻璃的外层。In a preferred embodiment, the thin chemically strengthened inner layer 16 may have a surface stress of about 250-900 MPa and a thickness of 0.5-1.0 mm. In this embodiment, the outer layer 12 may be annealed (non-chemically strengthened) glass with a thickness of about 1.5-3.0 mm or greater. Of course, the thickness of the outer layer 12 and the inner layer 16 may be different in each laminated structure 10 . Another preferred embodiment of an exemplary laminate structure may include an inner layer of 0.7 mm chemically strengthened glass, an approximately 0.76 mm thick layer of polyvinyl butyral, and an outer layer of 2.1 mm annealed glass.
可以通过熔合拉制制造示例性玻璃层，其如上文一般所述，以及如美国专利第7,666,511号、第4,483,700号和第5,674,790号所述，其全文通过引用结合入本文，然后对此类拉制玻璃进行化学强化。示例性化学强化的玻璃层从而可以具有深的DOL的CS，并且可以具有高的挠曲强度、耐划痕性和抗冲击性。示例性实施方式还可包括酸蚀刻或闪耀表面，通过减少这些表面上的瑕疵的尺寸和严重性，以增加此类表面的抗冲击性和增加强度。如果紧接层叠之前进行蚀刻，则可以在与中间层粘结的表面上维持蚀刻或闪耀的强化益处。Exemplary glass layers can be fabricated by fusion drawing, as generally described above, and as described in U.S. Patent Nos. 7,666,511, 4,483,700, and 5,674,790, the entire contents of which are incorporated herein by reference, and then such drawing The glass is chemically strengthened. Exemplary chemically strengthened glass layers can thus have a CS of deep DOL, and can have high flexural strength, scratch resistance, and impact resistance. Exemplary embodiments may also include acid etching or blazing surfaces to increase impact resistance and increase strength of such surfaces by reducing the size and severity of imperfections on such surfaces. If etching is performed immediately prior to lamination, the enhancement benefits of etching or flare can be maintained on the surface bonded to the interlayer.
本发明的一个实施方式提供示例性玻璃层叠结构，其具有非化学强化的外部玻璃片、化学强化的内部玻璃片以及位于外部玻璃片和内部玻璃片之间的至少一层聚合物中间层。聚合物中间层可以是聚合物单片、多层聚合物片或者复合聚合物片。此外，聚合物中间层可以包括如下材料，例如但不限于，PVB、聚碳酸酯、吸声PVB、乙烯乙酸乙烯酯(EVA)、热塑性聚氨酯(TPU)、离聚物、热塑性材料，及其组合。内部玻璃片的厚度可以约为0.5-1.5mm，以及外部玻璃片的厚度可以约为1.5-3.0mm。在其他实施方式中，内部玻璃片的厚度可以约为0.5-0.7mm，聚合物中间层的厚度可以约为0.4-1.2mm，和/或外部玻璃片的厚度可以约为2.1mm。在另一个实施方式中，内部玻璃片可以包含一种或多种碱土氧化物，使得碱土氧化物的含量至少约为5重量％。内部玻璃片可以包含至少约6重量％的氧化铝。在额外实施方式中，外部玻璃片包括如下材料，例如但不限于，钠钙玻璃和经退火的玻璃。示例性层叠体的面积可以大于1m2，并且可以用作车辆挡风玻璃、天窗或盖板。在其他实施方式中，内玻璃层的表面压缩应力约为250-900MPa，或者在另一个实施方式中，表面压缩应力约为250-350MPa，压缩应力的DOL大于约20μm。一些实施方式可以对玻璃片的任意数量的表面或者部分表面进行酸蚀刻。One embodiment of the present invention provides an exemplary glass laminate structure having a non-chemically strengthened outer glass sheet, a chemically strengthened inner glass sheet, and at least one polymer interlayer between the outer glass sheet and the inner glass sheet. The polymeric interlayer may be a single polymer sheet, a multilayer polymer sheet or a composite polymer sheet. Additionally, the polymeric interlayer may include materials such as, but not limited to, PVB, polycarbonate, acoustic PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomers, thermoplastics, and combinations thereof . The thickness of the inner glass sheet may be about 0.5-1.5 mm, and the thickness of the outer glass sheet may be about 1.5-3.0 mm. In other embodiments, the thickness of the inner glass sheet may be about 0.5-0.7 mm, the thickness of the polymer interlayer may be about 0.4-1.2 mm, and/or the thickness of the outer glass sheet may be about 2.1 mm. In another embodiment, the inner glass sheet may comprise one or more alkaline earth oxides such that the alkaline earth oxide content is at least about 5% by weight. The inner glass sheet may comprise at least about 6% by weight alumina. In additional embodiments, the outer glass sheet includes materials such as, but not limited to, soda lime glass and annealed glass. Exemplary laminates may have an area greater than 1 m2 and may be used as a vehicle windshield, sunroof or cover. In other embodiments, the surface compressive stress of the inner glass layer is about 250-900 MPa, or in another embodiment, the surface compressive stress is about 250-350 MPa, and the DOL of the compressive stress is greater than about 20 μm. Some embodiments may acid etch any number of surfaces or portions of the surface of the glass sheet.
本发明的另一个实施方式提供了如下玻璃层叠结构，其具有非化学强化的外部玻璃片、化学强化的内部玻璃片以及位于外部玻璃片和内部玻璃片之间的至少一层聚合物中间层，其中，内玻璃层的表面压缩应力约为250-900MPa。在额外的实施方式中，内玻璃层的表面压缩应力可以约为250-350MPa，压缩应力的DOL可以大于约20μm。内部玻璃片的示例性厚度可以约为0.5-1.5mm，以及外部玻璃片的厚度可以约为1.5-3.0mm。示例性聚合物中间层可以包括如下材料，例如但不限于，PVB、聚碳酸酯、吸声PVB、EVA、TPU、离聚物、热塑性材料，及其组合，和/或可以具有约为0.4-1.2mm的厚度。Another embodiment of the present invention provides a glass laminate having a non-chemically strengthened outer glass sheet, a chemically strengthened inner glass sheet, and at least one polymer interlayer between the outer glass sheet and the inner glass sheet, Wherein, the surface compressive stress of the inner glass layer is about 250-900 MPa. In additional embodiments, the surface compressive stress of the inner glass layer may be about 250-350 MPa, and the DOL of the compressive stress may be greater than about 20 μm. Exemplary thicknesses of the inner glass sheet may be about 0.5-1.5 mm, and thicknesses of the outer glass sheet may be about 1.5-3.0 mm. Exemplary polymer interlayers may include materials such as, but not limited to, PVB, polycarbonate, acoustic PVB, EVA, TPU, ionomers, thermoplastics, and combinations thereof, and/or may have a thickness of about 0.4- 1.2mm thickness.
从而本发明的实施方式可以提供一种通过使用较薄的玻璃材料来降低汽车车窗的重量同时维持光学和安全要求的方式。常规层叠挡风玻璃可占据车辆玻璃窗总重的62％；但是，通过例如采用0.7-mm后的化学强化内层以及2.1-mm厚的非化学强化外层，可以使得挡风玻璃重量降低33％。此外，发现使用1.6-mm厚的非化学强化外层以及0.7-mm厚的化学强化内层，得到45％的整体重量节约。因此，根据本发明的实施方式使用示例性层叠结构可以允许层叠挡风玻璃符合所有规定的安全要求，包括来自内部和外部物体的穿透以及得到可接受的头部冲击标准(HIC)值的合适弯曲度。此外，包括经过退火的玻璃的示例性外层可以提供由外部物体冲击所导致的可接受的破裂图案，并且允许当由于冲击结果产生碎片或裂纹时通过挡风玻璃的连续操作可见性。研究还证实，采用化学强化玻璃作为不对称挡风玻璃的内表面提供了如下额外益处：相比于常规退火挡风玻璃的乘客冲击的情况，降低了破裂可能性。Embodiments of the present invention may thus provide a way to reduce the weight of automotive windows while maintaining optical and safety requirements by using thinner glass materials. Conventional laminated windshields can account for 62% of the total vehicle glazing weight; however, windshield weight can be reduced by 33% by using, for example, a 0.7-mm post-chemically strengthened inner layer and a 2.1-mm thick non-chemically strengthened outer layer %. Furthermore, it was found that using a 1.6-mm thick non-chemically strengthened outer layer and a 0.7-mm thick chemically strengthened inner layer resulted in an overall weight savings of 45%. Thus, use of the exemplary laminate structure in accordance with embodiments of the present invention may allow laminated windshields to comply with all regulatory safety requirements, including penetration from internal and external objects as well as achieving acceptable Head Impact Criterion (HIC) values. Curvature. Additionally, an exemplary outer layer comprising annealed glass may provide an acceptable pattern of fractures resulting from impact by foreign objects and allow for continued operational visibility through the windshield when chips or cracks are generated as a result of the impact. The study also confirmed that the use of chemically strengthened glass for the inner surface of the asymmetric windshield provides the added benefit of reducing the likelihood of cracking compared to the case of occupant impact with conventional annealed windshields.
玻璃层叠体的弯曲和/或成形方法可以包括重力弯曲、按压弯曲以及它们的混合方法。在将薄的平坦玻璃片重力弯曲成弯曲形状(例如车辆挡风玻璃)的常规方法中，将冷的、预切割的单片或多片玻璃片放在弯曲固定件的刚性、预成形的、周界支撑表面上。弯曲固定件可以用金属或耐火材料制造。在示例性方法中，可以使用活动连接的弯曲固定件。在弯曲之前，通常仅在数个接触点上支撑玻璃。通常通过在玻璃韧化炉中暴露于提升的温度，来加热玻璃，这使得玻璃软化，实现玻璃重力弯垂或跌落成与周围支撑表面一致。通常，进而基本上整个支撑表面会与玻璃周界接触。Bending and/or shaping methods for the glass laminate may include gravity bending, press bending, and hybrids thereof. In the conventional method of gravity bending a thin, flat sheet of glass into a curved shape, such as a vehicle windshield, a cold, pre-cut sheet or sheets of glass are placed in a rigid, pre-formed, Perimeter support surface. Curved fixtures can be fabricated from metal or refractory materials. In an exemplary approach, an articulating curved fixture may be used. Before bending, the glass is usually only supported at a few points of contact. The glass is heated, typically by exposure to elevated temperatures in a glass tempering furnace, which softens the glass, allowing the glass to gravitationally sag or fall into conformity with the surrounding support surface. Typically, and thus substantially the entire support surface will be in contact with the glass perimeter.
一种相关技术是按压弯曲，其中，将单块平坦玻璃片加热至基本对应于玻璃软化点的温度。然后在具有互补成形表面的阳模和阴膜元件之间，将经过加热的玻璃片压制或者成形为所需曲率。模具元件成形表面可包括真空或空气喷嘴，以与玻璃片啮合。在一些实施方式中，成形表面可构造成基本上与相应的整个玻璃表面接触。或者，相对成形表面中的一个或两个可以在离散区域或离散接触点分别与玻璃表面接触。例如，阴模表面可以是环形表面。在一些实施方式中，可以使用重力弯曲和按压弯曲技术的组合。A related technique is press bending, in which a single flat sheet of glass is heated to a temperature substantially corresponding to the softening point of the glass. The heated glass sheet is then pressed or formed to the desired curvature between male and female film elements having complementary forming surfaces. The mold element forming surface may include vacuum or air nozzles to engage the glass sheet. In some embodiments, the forming surface can be configured to contact substantially the entire corresponding glass surface. Alternatively, one or both of the opposed forming surfaces may each be in contact with the glass surface at discrete areas or discrete contact points. For example, the female mold surface may be an annular surface. In some embodiments, a combination of gravity bending and press bending techniques may be used.
玻璃层叠体的总厚度范围可以约为2-5mm，其中，外部化学强化的玻璃片和/或内部化学强化的玻璃片的厚度小于或等于1mm(例如，0.5-1mm，例如0.5、0.6、0.7、0.8、0.9或者1mm)。此外，内部非化学强化玻璃片和/或外部非化学强化玻璃片的厚度可以小于或等于2.5mm(例如，1-2mm，例如1、1.5、2或者2.5mm)，或者厚度可以大于或等于2.5mm。在一些实施方式中，玻璃层叠体中的玻璃片的总厚度小于3.5mm(例如，小于3.5、3、2.5或者2.3mm)。The total thickness of the glass laminate may range from about 2-5 mm, wherein the outer chemically strengthened glass sheet and/or the inner chemically strengthened glass sheet has a thickness less than or equal to 1 mm (e.g., 0.5-1 mm, e.g., 0.5, 0.6, 0.7 , 0.8, 0.9 or 1mm). Additionally, the inner non-chemically strengthened glass sheet and/or the outer non-chemically strengthened glass sheet may have a thickness less than or equal to 2.5 mm (e.g., 1-2 mm, such as 1, 1.5, 2, or 2.5 mm), or may have a thickness greater than or equal to 2.5 mm. mm. In some embodiments, the total thickness of the glass sheets in the glass laminate is less than 3.5 mm (eg, less than 3.5, 3, 2.5, or 2.3 mm).
表2显示了示例性玻璃层叠结构，其中，缩写GG指的是化学强化的铝硅酸盐玻璃片，术语“玻璃”指的是非化学强化的钠钙(SL)玻璃片，以及PVB指的是聚(乙烯醇缩丁醛)，其可任选的是声学级别的PVB(A-PVB)。Table 2 shows exemplary glass laminate structures, where the abbreviation GG refers to a sheet of chemically strengthened aluminosilicate glass, the term "glass" refers to a sheet of non-chemically strengthened soda-lime (SL) glass, and PVB refers to a sheet of Poly(vinyl butyral), optionally an acoustic grade PVB (A-PVB).
表2：示例性玻璃层叠结构Table 2: Exemplary glass laminate structures
申请人已经显示本文所揭示的玻璃层叠结构具有优异的耐用性、抗冲击性、韧性和耐划痕性。正如本领域技术人员所熟知的那样，玻璃片或层叠体的强度和抗机械冲击性能受到玻璃中的缺陷(包括两个表面和内部的缺陷)的限制。当玻璃层叠体受到冲击时，冲击点受到压缩，同时冲击点周围的环或者“环带”以及受到冲击的玻璃片的相对表面处于拉伸状态中。通常，会从裂纹处开始发生破坏，这常常位于玻璃表面上的最高张力点或者最高张力点附近。这可能发生在相对表面上，但是也可能发生在环内。如果在冲击事件中，玻璃中的裂纹处于拉伸，则裂纹可能会扩展，玻璃通常会破裂。因此，高量级和深度的压缩应力(层深度)是优选的。Applicants have shown that the glass laminate structures disclosed herein have excellent durability, impact resistance, toughness, and scratch resistance. As is well known to those skilled in the art, the strength and mechanical impact resistance of a glass sheet or laminate is limited by defects in the glass, both surface and internal. When the glass laminate is impacted, the point of impact is compressed while the ring or "ring" around the point of impact and the opposing surface of the impacted glass sheet is in tension. Typically, failure begins at the crack, which is often at or near the point of highest tension on the glass surface. This can happen on opposing surfaces, but it can also happen inside the ring. If a crack in the glass is in tension during an impact event, the crack may propagate and the glass will usually break. Therefore, high magnitudes and depths of compressive stress (layer depth) are preferred.
因为化学强化作用，所揭示的混合玻璃层叠体中使用的化学强化玻璃片的一个或两个表面处于压缩状态。在玻璃的近表面区域结合压缩应力，可抑制玻璃片的裂纹扩展和失效。为了使裂纹扩展以及失效发生，来自冲击的拉伸张力必须在裂纹尖端处超过表面压缩应力。在一些实施方式中，化学强化玻璃片的高压缩应力和高层深度允许使用比非化学强化玻璃的情况下更薄的玻璃。Because of chemical strengthening, one or both surfaces of the chemically strengthened glass sheets used in the disclosed hybrid glass laminates are in compression. Incorporating compressive stresses in the near-surface region of the glass inhibits crack growth and failure of the glass sheet. For crack growth and failure to occur, the tensile tension from the impact must exceed the surface compressive stress at the crack tip. In some embodiments, the high compressive stress and high layer depth of the chemically strengthened glass sheet allows the use of thinner glass than would be the case with non-chemically strengthened glass.
在混合玻璃层叠体的情况下，层叠结构在响应机械冲击时，与更厚的整体式非化学强化玻璃，或者更厚的非化学强化玻璃层叠体相比，可更进一步偏转而不发生断裂。这种增加的偏转实现了将更多的能量转移到层叠体中间层，这可以降低到达玻璃的相对侧的能量。因此，与具有相似厚度的整体式非化学强化玻璃或者非化学强化玻璃层叠体相比，本文所揭示的混合玻璃层叠体可以经受更高的冲击能量。In the case of hybrid glass laminates, the laminate structure can deflect further without fracture in response to mechanical impact than thicker monolithic non-chemically strengthened glass, or thicker non-chemically strengthened glass laminates. This increased deflection enables more energy to be transferred to the laminate interlayer, which can reduce the energy reaching the opposite side of the glass. Thus, the hybrid glass laminates disclosed herein can withstand higher impact energies than monolithic non-chemically strengthened glass or non-chemically strengthened glass laminates of similar thickness.
本领域技术人员应理解，除了它们的机械性能以外，层叠结构还可用于削弱声波。本文所揭示的混合玻璃层叠件虽然使用较薄(且较轻)的结构，但是可以显著地降低声波传输，所述较薄(且较轻)的结构还拥有许多窗用玻璃应用所必需的机械性质。Those skilled in the art will understand that, in addition to their mechanical properties, laminated structures can also be used to attenuate sound waves. The hybrid glass laminates disclosed herein can significantly reduce acoustic wave transmission while using thinner (and lighter) structures that also possess the mechanical properties necessary for many glazing applications. nature.
层叠体和玻璃窗的吸声性能通常受到玻璃窗结构的挠性振动的影响。不希望受到理论的显示，人体声响应峰通常为500-5000Hz，对应于空气中约0.1-1m的波长以及玻璃中1-10m的波长。对于厚度小于0.01m(<10mm)的玻璃窗结构，主要通过振动以及声波与玻璃窗的挠曲振动的耦合产生透过。层叠玻璃窗结构可以设计成将能量从玻璃窗挠曲模式转化为聚合物中间层中的剪切应变。在采用较薄玻璃片的玻璃层叠体中，较薄玻璃的较大顺应性允许较大的振动幅度，这进而赋予中间层较大的剪切应变。大多数粘弹性聚合物中间层材料的低抗剪切性意味着中间层会通过高剪切应变来促进阻尼衰减，所述高剪切应变会在分子链滑动和松弛影响下转化成热量。The sound absorption performance of laminates and glazing is often affected by the flexural vibrations of the glazing structure. Without wishing to be bound by theory, the human acoustic response peaks typically at 500-5000 Hz, corresponding to wavelengths of about 0.1-1 m in air and 1-10 m in glass. For glazing structures with a thickness of less than 0.01 m (<10 mm), transmission occurs mainly through vibration and coupling of sound waves with the flexural vibration of the glazing. Laminated glazing structures can be designed to convert energy from the glazing deflection mode to shear strain in the polymer interlayer. In glass laminates employing thinner glass sheets, the greater compliance of the thinner glass allows for greater vibration amplitudes, which in turn imparts greater shear strain to the interlayer. The low shear resistance of most viscoelastic polymer interlayer materials means that the interlayer promotes damping attenuation through high shear strain, which is converted into heat under the influence of molecular chain slip and relaxation.
除了玻璃层叠体厚度，构成层叠体的玻璃片的特性也会影响声衰减性质。例如，在化学强化的玻璃片和非化学强化的玻璃片之间，可能在玻璃-聚合物中间层界面处存在小的、但是明显的差异，这导致聚合物层中较高的剪切应变。同样地，除了它们的明显组成不同之外，铝硅酸盐玻璃和钠钙玻璃具有不同的物理和机械性质，包括模量、泊松比、密度等，这可能导致不同的声响应。In addition to the thickness of the glass laminate, the properties of the glass sheets making up the laminate can also affect the sound attenuation properties. For example, there may be small, but significant differences at the glass-polymer interlayer interface between chemically strengthened glass sheets and non-chemically strengthened glass sheets, which result in higher shear strains in the polymer layer. Likewise, in addition to their apparent compositional differences, aluminosilicate and soda-lime glasses have different physical and mechanical properties, including modulus, Poisson's ratio, density, etc., which may lead to different acoustic responses.
实施例Example
使用常规的单轴强度测试，例如3点或4点弯曲测试来测量玻璃和陶瓷材料的强度。但是，因为所测强度取决于边缘效应和本体材料，对单轴强度测试结果的解释是具有挑战性的。Measure the strength of glass and ceramic materials using conventional uniaxial strength tests such as 3-point or 4-point bend tests. However, the interpretation of uniaxial strength test results is challenging because the measured strength depends on edge effects and bulk material.
在另一方面，双轴弯曲试验可用于提供强度评估，而不依赖于边缘诱导的现象。在双轴弯曲试验中，将玻璃层叠体支撑在靠近其周界且与其中心等距的3或更多点上，随后在中心位置对层叠体施加负载。因此，最大拉伸应力的位置出现在层叠体表面的中心处，且优选地，与其边缘条件无关。On the other hand, biaxial bending tests can be used to provide strength assessments that do not rely on edge-induced phenomena. In a biaxial bend test, a glass laminate is supported on 3 or more points near its perimeter and equidistant from its center, and then a load is applied to the laminate at the central location. Thus, the location of maximum tensile stress occurs at the center of the laminate surface, and preferably, independent of its edge conditions.
示例性平坦混合玻璃层叠体进行标准化双轴弯曲试验(附录7/3中细化的ECER43人头模型测试)。如下文所进一步解释，当在非化学强化玻璃(钠钙玻璃)侧上冲击本发明的玻璃层叠件(样品1)时，两玻璃片都断裂。但是，当在化学强化侧冲击样品1的玻璃层叠体时，非化学强化玻璃片断裂，但在所测试的样品中有50％的化学强化玻璃片保持完好。Exemplary flat hybrid glass laminates were subjected to a standardized biaxial bending test (ECER43 head phantom test detailed in Appendix 7/3). As explained further below, when impacting the inventive glass laminate (Sample 1 ) on the non-chemically strengthened glass (soda lime glass) side, both glass sheets fractured. However, when the glass laminate of Sample 1 was impacted on the chemically strengthened side, the non-chemically strengthened glass sheets fractured, but 50% of the chemically strengthened glass sheets in the samples tested remained intact.
在一个测试中，将高负载速率冲击直接导向内部(非化学强化的)玻璃片120。作为响应，内部玻璃片120的内部表面124和外部玻璃片110的外部表面112都处于拉伸状态。由于外部表面112上的拉伸应力的大小大于内部表面124处的拉伸应力，在该构造中，内部表面124上更为中等的拉伸应力足以使非化学强化的玻璃片120断裂，同时外部表面112上提升的拉伸应力足以使化学强化玻璃片的110也发生破裂。当玻璃片破裂时，PVB中间层变形，但是阻止人头模型冲击装置穿透玻璃层叠体。这是满足ECER43头型要求的响应。In one test, a high load rate impact was directed towards the inner (non-chemically strengthened) glass sheet 120 . In response, both the inner surface 124 of the inner glass sheet 120 and the outer surface 112 of the outer glass sheet 110 are placed in tension. Since the magnitude of the tensile stress on the outer surface 112 is greater than the tensile stress at the inner surface 124, in this configuration, a more moderate tensile stress on the inner surface 124 is sufficient to fracture the non-chemically strengthened glass sheet 120, while the outer The elevated tensile stress on surface 112 is sufficient to crack 110 of the chemically strengthened glass sheet as well. When the glass sheet breaks, the PVB interlayer deforms but prevents the dummy impact device from penetrating the glass laminate. This is a response that meets the ECER43 headform requirements.
在相关测试中，冲击相反地导向外部(化学强化的)玻璃片110。作为响应，外部玻璃片110的内部表面114经受中等拉伸应力，内部玻璃片120的外部表面122经受了较高量级的应力。在该构造中，在内部非化学强化玻璃片120的外部表面122上提升的应力导致非化学强化的玻璃片破裂。但是，外部玻璃片110的内部表面114上的中等拉伸应力，可能不足以克服在化学强化玻璃的近表面区域中的离子交换所诱发的压缩应力。在实验室实验中，高负载速率冲击只导致所测试的6个样品中的2个化学强化玻璃片110发生破裂。在余下的4个样品中，非化学强化的玻璃片120断裂，但是，化学强化的玻璃片110保持完好。本发明的所有样品都超过ECER43人头模型要求所述的用于非挡风玻璃的冲击要求。In a related test, the impact was directed instead towards the outer (chemically strengthened) glass sheet 110 . In response, the interior surface 114 of the outer glass sheet 110 is subjected to a moderate tensile stress and the exterior surface 122 of the inner glass sheet 120 is subjected to a higher magnitude of stress. In this configuration, elevated stress on the exterior surface 122 of the interior non-chemically strengthened glass sheet 120 causes the non-chemically strengthened glass sheet to fracture. However, the moderate tensile stress on the interior surface 114 of the outer glass sheet 110 may not be sufficient to overcome the compressive stress induced by ion exchange in the near-surface region of the chemically strengthened glass. In laboratory experiments, high loading rate impacts resulted in fractures in only 2 of the 6 samples tested of the chemically strengthened glass sheets 110 . In the remaining 4 samples, the non-chemically strengthened glass sheet 120 fractured, however, the chemically strengthened glass sheet 110 remained intact. All samples of the invention exceeded the impact requirements for non-windshields as described in the ECER 43 Human Head Model requirements.
对比样品A和B也进行双轴弯曲测试。比较样品A包括1mm的化学强化玻璃片/0.76mm标准PVB/1mm化学强化玻璃片对称构造，没有发生破裂，因此不符合ECER43关于玻璃层叠体必须破裂的要求。Comparative Samples A and B were also subjected to biaxial bending testing. Comparative sample A includes a symmetrical structure of 1 mm chemically strengthened glass sheet/0.76 mm standard PVB/1 mm chemically strengthened glass sheet, and no cracking occurs, so it does not meet the requirement of ECER43 that glass laminates must be cracked.
比较样品B包括1.5mm的钠钙璃片/0.76mm标准PVB/1.5mm钠钙玻璃片对称构造。在双轴弯曲试验中，2块玻璃片都断裂，因此比较样品B通过了ECER43标准(附录7/3)。但是，无论冲击哪块玻璃片，比较样品B玻璃层叠体的2块玻璃片都断裂，因此无法提供应对外部冲击的牢固的机械抗拒性，而这在混合层叠件中是能够实现的。还应指出，在测试过程中，比较样品B中的人头模型的反弹(即，弹跳)大于样品1的情况，表明比较构型没有像本发明的实施例那样有效地耗散能量。Comparative Sample B included a 1.5mm soda-lime glass sheet/0.76mm standard PVB/1.5mm soda-lime glass sheet symmetrical configuration. In the biaxial bending test, both glass sheets were broken, so the comparative sample B passed the ECER43 standard (Appendix 7/3). However, no matter which glass sheet was impacted, both glass sheets of the comparative sample B glass laminate were fractured, so strong mechanical resistance against external impact, which can be achieved in a hybrid laminate, could not be provided. It should also be noted that during testing, the bounce (ie, bouncing) of the human head model in Comparative Sample B was greater than that of Sample 1, indicating that the comparative configuration did not dissipate energy as efficiently as the embodiments of the present invention.
头部伤害标准(HIC)是可用于评估玻璃层叠体的安全性的常规标准。HIC值是无量纲的量值，与遭受因冲击而带来的伤害的可能性相关。对于内部冲击事件，更低的HIC值是合乎希望的。The Head Injury Criteria (HIC) is a conventional standard that can be used to assess the safety of glass laminates. The HIC value is a dimensionless quantity related to the probability of suffering injury due to impact. For internal shock events, lower HIC values are desirable.
对于示例性平坦混合玻璃层叠体，对于1.6mmSL/0.8mmA-PVB/0.7mmGG堆叠的非化学强化侧上的冲击的HIC平均值为175，但是，对于0.7mmGG/0.8mmA-PVB/1.6mmSL堆叠的化学强化侧上的冲击而言，HIC平均值为381。对于汽车玻璃窗应用，对于化学强化(外部)侧上的冲击的HIC平均值优选大于非化学强化侧上的冲击的HIC平均值。例如，化学强化侧的HIC值可大于或等于400(例如，大于或等于400、450或500)，而非化学强化侧的HIC值可小于或等于400(例如，小于或等于400、350、300、250、200、150或100)，从而使得化学强化侧的HIC值比非化学强化侧的HIC值至少大50(例如，至少大50、100、150或200)。For the exemplary flat hybrid glass laminate, the HIC average for impact on the non-chemically strengthened side of the 1.6mmSL/0.8mmA-PVB/0.7mmGG stack was 175, however, for the 0.7mmGG/0.8mmA-PVB/1.6mmSL stack In terms of impact on the chemically strengthened side, the HIC average was 381. For automotive glazing applications, the average HIC for impact on the chemically strengthened (external) side is preferably greater than the average HIC for impact on the non-chemically strengthened side. For example, the HIC value on the chemically strengthened side can be greater than or equal to 400 (e.g., greater than or equal to 400, 450, or 500), while the HIC value on the non-chemically strengthened side can be less than or equal to 400 (e.g., less than or equal to 400, 350, 300 , 250, 200, 150, or 100), such that the HIC value on the chemically strengthened side is at least 50 greater (eg, at least 50, 100, 150, or 200 greater) than the HIC value on the non-chemically strengthened side.
虽然本文可包含许多具体情况，但是它们不应该理解为对本发明的范围的限制，而是对于具体的特定实施方式的特征的描述。在本说明书的单独的实施方式中描述的某些特征也可以组合起来在单个实施方式中实现。反之，在单一实施方式的内容中描述的各种特征也可以在多个实施方式中独立地或者以任何适当次级组合的形式实现。而且，虽然上述特征被描述成以某些组合的形式起作用，而且甚至最初也是这样要求权利的，但所要求权利的组合中的一种或多种特征在一些情况下可以从该组合中去除，所要求权利的组合可以针对次级组合或者次级组合的变化。While many specifics may be contained herein, these should not be construed as limitations on the scope of the invention, but rather as descriptions of features specific to particular implementations. Certain features that are described in this specification in separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments independently or in any suitable sub-combination. Moreover, although the above features have been described as functioning in certain combinations, and even initially claimed as such, one or more features in a claimed combination may in some cases be removed from that combination , the claimed combination may be directed to a sub-combination or a variation of a sub-combination.
类似地，虽然在图中或附图中以特定的顺序来描述操作，但是这不应理解为要求此类操作以所示特定顺序或者连续顺序进行，或者进行所有所示的操作，以实现所需的结果。在某些情况下，多任务化和平行操作可能是有利的。Similarly, while operations are described in a particular order in the figures or drawings, this should not be understood as requiring that such operations be performed in the particular order shown, or in sequential order, or that all illustrated operations be performed, to achieve the described desired result. In some cases, multitasking and parallel operation may be advantageous.
本文中，范围可以表示为从“约”一个具体值和/或到“约”另一个具体值的范围。当表述这种范围时，例子包括自某一具体值始和/或至另一具体值止。类似地，当使用先行词“约”表示数值为近似值时，应理解，具体数值构成另一个方面。还应理解的是，每个范围的端点值在与另一个端点值有关和与另一个端点值无关时，都是有意义的。Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, examples include from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It should also be understood that the endpoints of each range are meaningful in relation to and independent of the other endpoint.
还要注意的是，本文关于将本发明的组件“配置成”或“使其适于”以特定的方式起作用的描述。这方面而言，对这样一个组件进行“配置成”或“使其适于”是为了具体表现特定的性质，或者以特定的方式起作用，其这样的描述是结构性的描述，而不是对预定期应用的描述。更具体地，本文所述的将组件“构造成”或“使其适于”的方式表示该组分现有的物理条件，因此可以将其看作该组件的结构特征的限定性描述。Note also that descriptions herein refer to components of the invention being "configured" or "adapted" to function in a particular manner. In this regard, a description of such a component as "configured to" or "adapted to" to embody a particular property, or to function in a particular manner, is a structural description rather than a description of A description of the scheduled application. More specifically, the manner in which a component is "constructed" or "adapted" as described herein represents the existing physical condition of the component and can therefore be considered a limiting description of the structural characteristics of the component.
如附图所示的各种构造和实施方式所示，描述了各种轻量化混合玻璃层叠体。Various lightweight hybrid glass laminates are described, as shown in various configurations and embodiments shown in the drawings.
虽然已经描述了本发明的优选实施方式，但是应理解的是，所述的实施方式仅仅是示意性的，本发明的范围仅由所附权利要求书以及在阅读本发明的基础上本领域技术人员自然获得的等价形式、许多变形和改进的全部范围所限定。While preferred embodiments of the present invention have been described, it should be understood that the described embodiments are illustrative only and that the scope of the invention is limited only by the appended claims and by the skill of the art upon reading this disclosure. The full range of equivalents, numerous modifications and improvements naturally occurring to man is defined.
| Application Number | Priority Date | Filing Date | Title |
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| CN201811031882.2ACN109016739B (en) | 2013-07-09 | 2014-07-07 | Lightweight hybrid glass laminate |
| CN201810083266.5ACN108127998A (en) | 2013-07-09 | 2014-07-07 | Lightweight hybrid glass laminated body |
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| US13/937,707US9616641B2 (en) | 2011-06-24 | 2013-07-09 | Light-weight hybrid glass laminates |
| US13/937,707 | 2013-07-09 | ||
| PCT/US2014/045554WO2015006201A1 (en) | 2013-07-09 | 2014-07-07 | Light-weight hybrid glass laminates |
| Application Number | Title | Priority Date | Filing Date |
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| CN201810083266.5ADivisionCN108127998A (en) | 2013-07-09 | 2014-07-07 | Lightweight hybrid glass laminated body |
| CN201811031882.2ADivisionCN109016739B (en) | 2013-07-09 | 2014-07-07 | Lightweight hybrid glass laminate |
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| CN105377551Atrue CN105377551A (en) | 2016-03-02 |
| CN105377551B CN105377551B (en) | 2019-03-08 |
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| CN201480039262.7ACeasedCN105377551B (en) | 2013-07-09 | 2014-07-07 | Lightweight Hybrid Glass Laminate |
| CN201810083266.5APendingCN108127998A (en) | 2013-07-09 | 2014-07-07 | Lightweight hybrid glass laminated body |
| CN201811031882.2ACeasedCN109016739B (en) | 2013-07-09 | 2014-07-07 | Lightweight hybrid glass laminate |
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| CN201810083266.5APendingCN108127998A (en) | 2013-07-09 | 2014-07-07 | Lightweight hybrid glass laminated body |
| CN201811031882.2ACeasedCN109016739B (en) | 2013-07-09 | 2014-07-07 | Lightweight hybrid glass laminate |
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| CN109016739B (en) | 2022-01-04 |
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