CN108138328A - 基于轻金属的多层基板 - Google Patents

基于轻金属的多层基板 Download PDF

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Publication number
CN108138328A
CN108138328A CN201580082409.5A CN201580082409A CN108138328A CN 108138328 A CN108138328 A CN 108138328A CN 201580082409 A CN201580082409 A CN 201580082409A CN 108138328 A CN108138328 A CN 108138328A
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polymer
layer
light metal
ceramic
substrate
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张吉昊
吴冠霆
林倩婷
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Hewlett Packard Development Co LP
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Hewlett Packard Development Co LP
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Publication of CN108138328A publication Critical patent/CN108138328A/zh
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    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used

Abstract

本申请公开了基板，其包括轻金属层、形成在轻金属层上的氧化层以及形成在氧化层上的聚合物杂化层；并公开了用于形成该基板的方法。

Description

基于轻金属的多层基板
背景技术
电子设备包括放置于外壳中的各种相互连接的组件。外壳可使用多个由塑料或金属制成的部件形成。如果外壳部件由金属制成，则通常使用基于轻金属的基板。基于轻金属的基板可以在轻重量下赋予耐久性。基于轻金属的基板可由例如镁、铝、钛、锂、锌或它们的合金制成。
附图说明
附图说明了本文描述的原理的各种实例，并且是说明书的一部分。
图1A和1B示出根据本文描述的原理的各种实例的基于轻金属的多层基板。
图2和3示出根据本文描述的原理的各种实施方式的基于轻金属的多层基板的实例。
图4～6示出根据本文描述的原理的各种实例的形成基于轻金属的多层基板的方法的示例性流程图。
具体实施方式
基于轻金属的基板由于其强度与重量比高和吸引人的美感而越来越多地被视为形成电子设备用外壳部件的选择的基板。然而，它们可能具有差的颜色稳定性、硬度和化学耐性。可能要在基于轻金属的基板上进行各种表面处理工艺以使它们适合使用。然而，这可能导致生产周期时间较长。这种工艺还可能影响产品的质地和外观，并可能导致大量挥发性有机碳(VOC)排放，使其不太环保。
本发明主题的方面涉及基于轻金属的多层基板和用于形成该基板的方法。为了便于讨论，基于轻金属的多层基板在下文中可互换地被称为基板。
在一个实例中，基板包括轻金属层、形成在轻金属层上的氧化层以及形成在氧化层上的陶瓷-聚合物杂化层。氧化层的存在大大提高了轻金属层的化学耐性，并且还提供了耐磨保护，并起到热绝缘和电绝缘的作用。陶瓷-聚合物杂化层进一步使基板更耐用和耐腐蚀。陶瓷-聚合物杂化层可另外为基板提供颜色稳定性和绝缘性。
在一个实例中，氧化层通过诸如等离子体电解氧化(PEO)的电化学方法整体地形成在轻金属层上。因此，该氧化层比沉积的氧化金属涂层对轻金属层具有更大的粘附力。在一个实例中，氧化层形成在轻金属层的两个相对面上。此外，陶瓷-聚合物杂化层可同时形成在轻金属层的两个相对面上的氧化层上。
在一个实例中，基板可进一步具有外层。外层可提供在基板的一面上。在一个实施方式中，外层为饰面层(finishing layer)。在另一实施方式中，外层可由饰面层包覆的屏障层构成。饰面层可用来向基板提供各种纹理饰面和其它特性，例如防指纹、耐污渍、防溅和抗菌等。因此，饰面层可形成为热固化层或紫外(UV)光固化层。屏障层可作为用于保护基板的附加屏障而提供。
根据本发明主题的不同方面，基板可用来形成诸如手提电脑、平板电脑、移动通信设备、便携式硬盘和便携式音乐播放器等的电子设备用外壳部件。
在以下说明中，为了解释的目的，阐述许多具体细节以便提供对本发明的系统和方法的理解。然而，显而易见的是，本发明的仪器、系统和方法仅为示例。在附图中，相同的附图标记用来表示相同的组件，但他们可能不完全相同。
图1A和1B示出根据本文描述的原理的各种实例的基于轻金属的多层基板100。基板100包括轻金属层102、形成在轻金属层102上的氧化层104以及形成在氧化层104上的陶瓷-聚合物杂化层106。在一个实例中，轻金属选自镁、铝、锌、钛、锂和它们的合金。
在一个实例中，具有陶瓷-聚合物杂化层106的氧化层104可形成在轻金属层102的一个表面上，如图1A所示。在另一实例中，具有陶瓷-聚合物杂化层106的氧化层104可形成在轻金属层102的两个相对表面上，如图1B所示。
在一个实例中，为了形成基板100，轻金属片可经过电化学氧化，例如等离子体电解氧化，从而形成轻金属片的暴露表面上的氧化层104。轻金属片的非氧化部分可形成轻金属层102。在一个实例中，轻金属片可具有范围在约0.4至2.0毫米内的厚度。
对于氧化，轻金属片可放置在包含电解质的电解溶液中，电解质选自硅酸钠、金属磷酸盐、氟化钾、氢氧化钾、氢氧化钠、氟锆酸盐、六偏磷酸钠、氟化钠、草酸铁铵、磷酸盐、石墨粉末、二氧化硅粉末、氧化铝粉末、分散剂、金属粉末、聚环氧乙烷烷基酚醚(polyethylene oxide alkylphenolic ether)和它们的组合。电解质可以以加水量的0.05至15wt％的浓度存在。可在电解溶液上通过范围在150至450V内的电压，在电解溶液中放置有轻金属片以形成氧化层104。在一个实例中，可施加电压约3至20分钟。在一个实例中，由此形成的氧化层104可具有范围在约1至15微米内的厚度。
此外，陶瓷-聚合物杂化层106可为由溶胶-凝胶聚合形成的溶胶-凝胶聚合物杂化层。溶胶-凝胶聚合包括在氧化层104上涂布溶胶-凝胶涂层并干燥该涂层。在一个实例中，涂层可为通过在氧化层104上喷涂溶胶-凝胶而形成的喷射涂层。在另一实例中，涂层可为通过将包含轻金属层102和氧化层104的基板浸渍在溶胶-凝胶中而形成的浸渍涂层。
溶胶为聚合物前体颗粒在液体介质(例如水)中的胶状悬浮液。在一个实例中，溶胶可包括以重量计约30％聚合物前体颗粒。前体颗粒经过诸如水解和缩合聚合的反应以在活化时形成凝胶。例如，根据所用的前体，可在酸性、碱性或中性条件下通过添加水来进行活化。在一个实例中，0.1M盐酸(HCI)溶液可用于活化溶胶从而形成凝胶。由此形成的凝胶为稀释的交联聚合物体系，当其处于稳定状态时不表现出流动。例如可通过喷涂或浸涂将凝胶涂覆在氧化层104上并随后干燥。
干燥后，会得到坚硬的玻璃状膜，其具有陶瓷状外观，并因此被称为陶瓷涂层。在一个实例中，除了前体之外，还可将各种聚合物加入溶胶中使得在干燥时形成包含陶瓷和聚合物的基质。该基质可被称为陶瓷-聚合物杂化层或溶胶-凝胶聚合物杂化层。在一个实例中，由此形成的陶瓷-聚合物杂化层106可具有范围在约2至15毫米内的厚度。
在一个实例中，陶瓷溶胶-凝胶包括选自下列的前体：原硅酸四乙酯(TEOS)、缩水甘油醚氧基丙基三乙氧基硅烷(GPTMS)、3-氨丙基三乙氧基硅烷(APTES)、乙基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲基硅氧烷(VTMS)、二苯基二甲氧基硅烷(DPhDMS)、异丙醇锆(TPZ)和金属醇盐。在一个实例中，用于陶瓷溶胶-凝胶悬浮液中的聚合物选自聚丙烯酸酯、环氧树脂、丙烯腈丁二烯苯乙烯(ABS)、聚碳酸酯、聚氨酯、氟代聚合物和它们的组合。
在各种实施方式中，聚合物、聚合物-金属杂化物或聚合物-微粒杂化物的外层可另外提供在基于轻金属的多层基板100的两面的至少一面上，如下所述。
图2和3示出根据本文描述的原理的各种实施方式的基于轻金属的多层基板200和300。除了氧化层104和陶瓷-聚合物杂化层106之外，基板200和300还包括外层。
在一个实施方式中，如图2所示，基板200的外层为形成在陶瓷-聚合物杂化层106上的饰面层202。在一个实例中，饰面层202可具有范围在约5至20微米内的厚度。饰面层202可为热固化的聚合物-颗粒层和紫外(UV)光固化的聚合物-颗粒层中的一个。
在一个实例中，具有微粒(例如金属薄片、滑石或石墨)的氨基甲酸酯丙烯酸酯聚合物可用来形成UV固化的饰面层202。在一个实例中，具有微粒(例如珍珠粉末或诸如铝、银、镍、铬或不锈钢的粉末的金属粉末)的热塑性或热固性聚合物可用来形成热固化的饰面层202。
在另一实施方式中，如图3所示，基板300的外层包括介于饰面层202与陶瓷-聚合物杂化层106之间的屏障层302。屏障层302可为含有微粒或不含微粒的干燥或固化的聚合物层。在一个实例中，屏障层302具有范围在约3至15微米内的厚度。
在一个实例中，含有微粒或不含微粒(例如石墨烯、碳纳米管、滑石、粘土)的热塑性或热固性聚合物可用来形成屏障层302。
基板200和300的外层可提供所期望的具有美感的外观(例如纹理饰面)和其它特性(例如防指纹、耐污渍，防溅和抗菌等)。此外，基于轻金属的多层基板200或300的不具有外层的面可固定到电子设备的下层外壳部件或组件，而多层基板200或300的具有外层的面可形成外壳部件或组件的外盖。图4至6示出根据本文描述的原理的各种实例的形成基于轻金属的多层基板的方法的示例性流程图。
参照流程图说明和/或根据本文描述的原理的实例的方法的框图，本文描述了方法的各方面。流程图说明和框图的一些或全部框，以及流程图说明和框图中的框的组合可通过计算机可用程序代码来实现。可将计算机可用程序代码提供给通用计算机、专用计算机的处理器或其它可编程数据处理设备而生产机器，以使计算机可用程序代码在例如通过处理器或其他可编程数据处理设备执行时，实现流程图和/或框图的框或多个框中指定的功能或动作。在一个实例中，计算机可用程序代码可体现在计算机可读存储介质中；计算机可读存储介质为计算机程序产品的一部分。在一个实例中，计算机可读存储介质为非暂时性计算机可读介质。
参见图4，在框402处，通过等离子体电解氧化，在轻金属片的表面上形成氧化层。PEO方法为其中将可控高压交流电施加至浸没在电解槽中的金属部件的电化学方法。该方法将碱性电解质中的电化学氧化和高压火花处理结合起来，致使在金属表面上形成物理保护氧化膜，从而增强耐磨性和耐腐蚀性并且延长下层轻金属层的寿命。由于高电压和电流，在金属表面上产生强烈的等离子体。该等离子体氧化部件的表面并从基板材料生长纳米结构的陶瓷状氧化层。因此氧化层(例如氧化层104)整体地产生在轻金属层(例如轻金属层102)上。这种整体产生的氧化层比沉积的金属氧化层对下层金属层具有更大的粘附力。因此，由此产生的氧化层104更耐用。
在一个实例中，轻金属片可由例如镁、铝、钛、锂、锌或它们的合金制成。在一个实例中，轻金属片可放置在电解溶液中并且可在轻金属层上施加范围在150至450伏特内的电压从而氧化轻金属片的暴露表面。因此形成的氧化层(例如，基板100、200或300的氧化层104)可具有范围在约1至15微米内的厚度。为了在轻金属片的一个表面上形成氧化层，例如可由惰性材料暂时保护相对的表面。
在框404处，通过溶胶-凝胶聚合在氧化层上提供陶瓷-聚合物杂化层，例如，基板100、200或300的陶瓷-聚合物杂化层106。在一个实例中，具有氧化层104的轻金属层102可被浸渍在溶胶-凝胶和聚合物的悬浮液中以涂布陶瓷-聚合物杂化涂层，并且可将浸渍涂层干燥以形成陶瓷-聚合物杂化层。在另一实例中，可通过喷涂将溶胶-凝胶和聚合物的悬浮液涂布在氧化层104上以形成陶瓷-聚合物杂化涂层，并且可将该涂层干燥以形成陶瓷-聚合物杂化层。
在框406处，可在陶瓷-聚合物杂化层上提供外层以提供各种纹理和功能饰面。在一个实例中，外层可为饰面层，例如饰面层202。在另一实例中，外层可为被饰面层202覆盖的屏障层302。
由此形成的基于轻金属的多层基板更加耐用。氧化层的存在提高了轻金属层的化学耐性，并且还提供了耐磨保护并起到热绝缘和电绝缘的作用。陶瓷-聚合物杂化层进一步提高基板的强度和耐腐蚀性，并为基板提供颜色稳定性和绝缘性。此外，该工艺比传统的表面处理工艺更快并且使用更少的能量。另外，根据本发明主题形成的基板可具有包括饰面层的外层，如以下参照图5和6进一步所讨论的。
在一个实施方式中，图5中所示的方法可用来制备基板200，并且图6中所示的方法可用来制备基板300。
参见图5，在框502处，将轻金属片放置在电解溶液中用于PEO。在一个实例中，电解质选自硅酸钠、金属磷酸盐、氟化钾、氢氧化钾或氢氧化钠、氟锆酸盐、六偏磷酸钠、氟化钠、草酸铁铵、磷酸盐、石墨粉末、二氧化硅粉末、氧化铝粉末、分散剂、金属粉末、聚环氧乙烷烷基酚醚和它们的组合。在一个实例中，以范围在加水量的约0.05至15％内的剂量添加电解质。
在框504处，在具有轻金属片的电解质上施加电压以氧化轻金属片的暴露表面并形成氧化层，例如氧化层104。在一个实例中，可施加范围在150至450伏特内的电压，持续时间约3至20分钟，以形成1至15微米厚的氧化层。要理解的是，通过改变PEO的条件，例如电压、时间和电解质浓度，可以改变氧化层的厚度。
在框506处，用陶瓷溶胶-凝胶和聚合物的悬浮液涂覆具有氧化层的轻金属层。可通过例如浸涂或喷涂来涂布涂层。在一个实例中，陶瓷溶胶-凝胶包括选自下列的前体：原硅酸四乙酯(TEOS)、缩水甘油醚氧基丙基三乙氧基硅烷(GPTMS)、3-氨丙基三乙氧基硅烷(APTES)、乙基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲基硅氧烷(VTMS)、二苯基二甲氧基硅烷(DPhDMS)、异丙醇锆(TPZ)和金属醇盐。在一个实例中，用于陶瓷溶胶-凝胶悬浮液中的聚合物选自聚丙烯酸酯、环氧树脂、丙烯腈丁二烯苯乙烯(ABS)、聚碳酸酯、聚氨酯、氟代聚合物和它们的组合。
在框508处，干燥涂层以形成陶瓷-聚合物杂化层，例如陶瓷-聚合物杂化层106。在一个实例中，可在60至140℃的范围内的温度下通过风干来干燥涂层。
在框510处，在陶瓷-聚合物杂化层上提供聚合物-颗粒悬浮液涂层。在一个实例中，将聚合物-颗粒悬浮液涂层喷涂在陶瓷-聚合物杂化层上。
在框512处，通过热固化和UV固化中的一种来固化聚合物-颗粒悬浮液涂层以形成饰面层，例如饰面层202。在一个实例中，具有微粒(例如金属薄片、滑石或石墨烯)的氨基甲酸酯丙烯酸酯聚合物可用来形成UV固化的饰面层。在一个实例中，具有微粒(例如珍珠粉末或诸如铝、银、镍、铬或不锈钢的粉末的金属粉末)的热塑性或热固性聚合物可用来形成热固化的饰面层。
在一个实例中，对于UV固化，将聚合物-颗粒悬浮液涂层在60℃下烘烤5至10分钟并随后暴露于UV照射约3至60秒。在另一实例中，对于热固化，将聚合物-颗粒悬浮液涂层暴露于约60至140℃的范围内的温度约20至40分钟以形成饰面层。
参见图6，形成具有轻金属层、氧化层和氧化层上的陶瓷-聚合物杂化层的框602至608类似于图5的框502至508。因此，在框602处，轻金属片被放置在电解溶液中。在框604处，在轻金属片上施加电压以氧化轻金属片的暴露表面。在框606处，在陶瓷溶胶-凝胶和聚合物的悬浮液中涂覆具有氧化层的轻金属层。在框608处，将该涂层干燥以形成陶瓷-聚合物杂化层。
此外，在框610处，在陶瓷-聚合物杂化层上喷涂屏障涂层并干燥以形成屏障层。在一个实例中，含有或不含微粒(例如石墨烯、碳纳米管、滑石、粘土)的热塑性或热固性聚合物可用来形成屏障层。在一个实例中，可在约60至140℃的范围内的温度下干燥屏障涂层。
用于形成饰面层的框612和614分别类似于框510和512。因此，在框612处，在屏障层上喷涂聚合物-颗粒悬浮液，并且在框614处，通过热固化和UV固化中的一种来固化聚合物-颗粒悬浮液以形成饰面层。
已经介绍了前面的描述，以说明和描述所述的原理的实例。该描述并非旨在为详尽无遗的或将这些原理限制为所公开的任何精确形式。根据以上教导，许多修改和变化都是可能的。

Claims (15)

1.一种基板，包括：
轻金属层；
形成在所述轻金属层上的氧化层，其中所述氧化层为等离子体电解氧化层；和
形成在所述氧化层上的陶瓷-聚合物杂化层。
2.如权利要求1所述的基板，进一步包括形成在所述陶瓷-聚合物杂化层上的饰面层，其中所述饰面层为热固化的聚合物-颗粒层和紫外(UV)光固化的聚合物-颗粒层中的一种。
3.如权利要求2所述的基板，进一步包括介于所述饰面层与所述陶瓷-聚合物杂化层之间的屏障层。
4.如权利要求1所述的基板，其中所述轻金属选自镁、铝、锌、钛、锂和它们的合金。
5.如权利要求1所述的基板，其中所述氧化层具有范围在约1微米至15微米内的厚度。
6.一种方法，包括：
通过等离子体电解氧化在轻金属片的表面上形成氧化层；
通过溶胶-凝胶聚合在所述氧化层上提供陶瓷-聚合物杂化层；和
在所述陶瓷-聚合物杂化层上提供外层。
7.如权利要求6所述的方法，其中提供所述陶瓷-聚合物杂化层包括：
用溶胶-凝胶和聚合物的悬浮液涂覆所述氧化层，其中所述涂覆为喷涂和浸涂中的一种；和
干燥涂层以形成所述陶瓷-聚合物杂化层。
8.如权利要求7所述的方法，其中
所述溶胶-凝胶包括选自下列的前体：原硅酸四乙酯(TEOS)、缩水甘油醚氧基丙基三乙氧基硅烷(GPTMS)、3-氨丙基三乙氧基硅烷(APTES)、乙基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲基硅氧烷(VTMS)、二苯基二甲氧基硅烷(DPhDMS)、异丙醇锆(TPZ)、金属醇盐和它们的组合；并且
所述聚合物选自聚丙烯酸酯、环氧树脂、丙烯腈丁二烯苯乙烯(ABS)、聚碳酸酯、聚氨酯、氟代聚合物和它们的组合。
9.如权利要求6所述的方法，其中提供所述外层包括：
在所述陶瓷-聚合物杂化层上喷涂聚合物-颗粒悬浮液；和
通过热固化和UV固化中的一种来固化所述聚合物-颗粒悬浮液。
10.如权利要求6所述的方法，其中提供所述外层包括：
通过喷雾干燥在所述陶瓷-聚合物杂化层上形成屏障层；
在所述屏障层上喷涂聚合物-颗粒悬浮液；和
通过热固化和UV固化中的一种来固化所述聚合物-颗粒悬浮液。
11.如权利要求6所述的方法，其中所述等离子体电解氧化包括：
将所述轻金属片放置在电解溶液中；和
施加范围在150伏特至450伏特内的电压以氧化所述轻金属片的暴露表面。
12.一种基板，包括：
轻金属层；
电化学地形成在所述轻金属层上的氧化层；
形成在所述氧化层上的溶胶-凝胶聚合物杂化层；和
沉积在所述溶胶-凝胶聚合物杂化层上的外层，其中所述外层包括下列中的一个：
饰面层；和
被所述饰面层覆盖的屏障层。
13.如权利要求12所述的基板，其中所述饰面层为UV固化的聚合物-颗粒层，其中所述聚合物为氨基甲酸酯丙烯酸酯聚合物，并且其中所述颗粒选自金属薄片、滑石、石墨烯和它们的组合。
14.如权利要求12所述的基板，其中所述饰面层为热固化的聚合物-颗粒层，
其中所述聚合物选自聚丙烯酸酯、赛璐珞、聚乙烯、聚丙烯(PP)、聚氯乙烯(PVC)、氯化聚氯乙烯(CPVC)、聚苯乙烯(PS)、环氧树脂、丙烯腈丁二烯苯乙烯(ABS)、聚碳酸酯、聚氨酯、聚丁烯(PB)、聚偏氟乙烯(PVDF)、氟代聚合物、尼龙、聚四氟乙烯、特氟隆、聚乙炔、聚吡咯、聚噻吩、聚呋喃、聚对亚苯、聚苯胺、聚亚乙基二氧噻吩、聚(亚苯)亚乙烯、聚二烷基芴和它们的组合；并且
其中所述颗粒选自珍珠粉末、铝粉、银粉、镍粉、铬粉、不锈钢粉和它们的组合。
15.如权利要求12所述的基板，其中所述屏障层包括：
选自石墨烯、碳纳米管、滑石、粘土和它们的组合中的颗粒；和
选自聚丙烯酸酯、赛璐珞、聚乙烯、聚丙烯(PP)、聚氯乙烯(PVC)、氯化聚氯乙烯(CPVC)、聚苯乙烯(PS)、环氧树脂、丙烯腈丁二烯苯乙烯(ABS)、聚碳酸酯、聚氨酯、聚丁烯(PB)、聚偏氟乙烯(PVDF)、氟代聚合物、尼龙、聚四氟乙烯、特氟隆、聚乙炔、聚吡咯、聚噻吩、聚呋喃、聚对亚苯、聚苯胺、聚亚乙基二氧噻吩、聚(亚苯)亚乙烯、聚二烷基芴和它们的组合中的聚合物。
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