CN104302803A - 基于铬的反射涂层 - Google Patents

基于铬的反射涂层 Download PDF

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Publication number
CN104302803A
CN104302803A CN201380012348.6A CN201380012348A CN104302803A CN 104302803 A CN104302803 A CN 104302803A CN 201380012348 A CN201380012348 A CN 201380012348A CN 104302803 A CN104302803 A CN 104302803A
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CN
China
Prior art keywords
chromium
alloy
dopant material
atom
coating
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CN201380012348.6A
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English (en)
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CN104302803B (zh
Inventor
D·R·埃文斯
K·朱伯
C·J·霍尔
S·D·菲尔德
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University of South Australia
SMR Patents SARL
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University of South Australia
SMR Patents SARL
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Priority claimed from AU2012900267A external-priority patent/AU2012900267A0/en
Application filed by University of South Australia, SMR Patents SARL filed Critical University of South Australia
Publication of CN104302803A publication Critical patent/CN104302803A/zh
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Publication of CN104302803B publication Critical patent/CN104302803B/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
    • B60R1/02—Rear-view mirror arrangements
    • B60R1/08—Rear-view mirror arrangements involving special optical features, e.g. avoiding blind spots, e.g. convex mirrors; Side-by-side associations of rear-view and other mirrors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60Q—ARRANGEMENT OF SIGNALLING OR LIGHTING DEVICES, THE MOUNTING OR SUPPORTING THEREOF OR CIRCUITS THEREFOR, FOR VEHICLES IN GENERAL
    • B60Q1/00—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor
    • B60Q1/26—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to indicate the vehicle, or parts thereof, or to give signals, to other traffic
    • B60Q1/2661—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to indicate the vehicle, or parts thereof, or to give signals, to other traffic mounted on parts having other functions
    • B60Q1/2665—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to indicate the vehicle, or parts thereof, or to give signals, to other traffic mounted on parts having other functions on rear-view mirrors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60Q—ARRANGEMENT OF SIGNALLING OR LIGHTING DEVICES, THE MOUNTING OR SUPPORTING THEREOF OR CIRCUITS THEREFOR, FOR VEHICLES IN GENERAL
    • B60Q1/00—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor
    • B60Q1/26—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to indicate the vehicle, or parts thereof, or to give signals, to other traffic
    • B60Q1/34—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to indicate the vehicle, or parts thereof, or to give signals, to other traffic for indicating change of drive direction
    • B60Q1/38—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to indicate the vehicle, or parts thereof, or to give signals, to other traffic for indicating change of drive direction using immovably-mounted light sources, e.g. fixed flashing lamps
    • B60Q1/381—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to indicate the vehicle, or parts thereof, or to give signals, to other traffic for indicating change of drive direction using immovably-mounted light sources, e.g. fixed flashing lamps with several light sources activated in sequence, e.g. to create a sweep effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
    • B60R1/02—Rear-view mirror arrangements
    • B60R1/06—Rear-view mirror arrangements mounted on vehicle exterior
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
    • B60R1/12—Mirror assemblies combined with other articles, e.g. clocks
    • B60R1/1207—Mirror assemblies combined with other articles, e.g. clocks with lamps; with turn indicators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C22C27/06—Alloys based on chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/20—Metallic material, boron or silicon on organic substrates
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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    • C—CHEMISTRY; METALLURGY
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    • F21S43/20—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by refractors, transparent cover plates, light guides or filters
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Abstract

本发明提供了一种用于聚合物型基材的基于铬的反射涂层，其中所述涂层具有200nm或更小的厚度，并且是铬与掺杂材料的合金，所述掺杂材料选自六方密堆积的过渡金属，所述合金具有主要的体心立方相与次要的Ω六方密堆积相共存的晶体结构。

Description

基于铬的反射涂层
本申请要求2012年1月24日提交的澳大利亚临时专利申请2012900267的优先权，该临时专利申请的内容视为以引用方式并入本文。
技术领域
本发明涉及用于聚合物型基材的反射涂层，特别是基于铬的涂层，所述涂层是能够提供良好的耐磨性与中性色的涂层。本发明既涉及所述涂层自身又涉及向聚合物型基材施加所述涂层的方法。
发明背景
与传统材料如玻璃相比，聚合物型材料在商业和工业应用二者中都具有许多优势。通常，它们为其使用者提供设计自由度以及有利的性质如减小的重量和降低的生产成本。聚合物型基材的表面工程的一个有趣的应用领域为设计超薄涂层供用于“日常”环境中，例如智能手机上的易清洁涂层到汽车工业中的镜和装饰性(彩色)涂层的。加长地暴露于这些“日常”环境条件要求这样的超薄涂层具有一定程度的抗以下因素的耐用性：例如酸性或碱性环境、从低到-80℃至高到+80℃的温度变化、相对湿度变化以及日常磨损造成的研磨条件。
另外，在几乎所有采用此类涂层的应用中，需要涂层在变化的环境条件下在长的工作时间内保持其完整性。也就是说，在此时间内，涂层不应显著改变反射率或颜色，也不应与下面的基材层离或脱离。
然而，向聚合物型材料施加适宜的涂层是特别困难，因为传统的涂布方法通常要求可以承受高温(常常>150℃)的基材。由于最常见的聚合物型材料具有较低的软化温度，故缺乏用于这些基材的适宜涂层。
迄今，关于开发耐用的耐磨超薄涂层的大多数工作因此聚焦于沉积硬质化合物如硼化物、碳化物和氮化物到硬质/耐热基材如金属和陶瓷上。然而，沉积技术中使用的高温不适宜用在聚合物型基材上。因此，需要可以被施加到具有较低软化温度的聚合物型基材的超薄涂层，所述涂层仍能够提供期望的物理性质如耐磨性、反射率(优选具有大于50％的R％)和中性(或期望的)颜色。
具体到颜色，整个本说明书中提及“中性”色是指由根据1976CIEL*a*b*空间(或CIELAB)颜色模型所测定的L*、a*和b*值所定义的颜色，该颜色模型是以立方体形式组织的大致均匀的色标。在正交的a*和b*色轴中，正a*值为红色，负a*值为绿色，正b*值为黄色，负b*值为蓝色，而亮度(或灰度)L*的垂直标度从0(黑色)变化到100(白色)，从而允许以三个点定位总颜色E。颜色的色度(C*)定义为√(a*2+b*2)，并用来量化色级而与其亮度无关。理想地，对于中性的颜色E，C*将小于或等于1并且颜色E将因此靠近中性L*轴。
引入上面的背景讨论是为了说明本发明的背景。其不应视为承认任何所提及的材料在任何一项权利要求的优先权日是出版的、已知的或是公知常识的一部分。
发明内容
本发明提供了用于聚合物型基材的基于铬的反射涂层，其中所述涂层具有200nm或更小的厚度并且是铬与掺杂材料的合金，所述掺杂材料选自六方密堆积的过渡金属，所述合金具有主要的体心立方相与次要的Ω六方密堆积相共存的晶体结构。在本发明的一个优选形式中，合金为铬与所述掺杂材料的二元合金。
本发明还提供了在聚合物型基材上形成基于铬的反射涂层的方法，所述方法包括通过物理气相沉积向聚合物型基材施加铬和掺杂材料，所述掺杂材料选自六方密堆积的过渡金属，以形成具有200nm或更小的厚度的合金涂层，所述合金涂层被施加以便具有主要的体心立方相与次要的Ω六方密堆积相共存的晶体结构。在本发明的一个优选形式中，所述合金被施加以便为铬与所述掺杂材料的二元合金。
铬为第6族过渡金属成员并具有体心立方(bcc)晶体结构。作为主要组分引入为两种主要金属组分的合金的本发明优选二元合金中，铬主要用以产生耐腐蚀的光泽硬表面，从而带给合金期望的光学反射率性质，优选R％大于50％，以便可接受地用于镜的形成中。其具有高熔点、稳定的结晶结构和中等的热膨胀，使得其为用于上述严苛环境条件中的理想主要组分。
所述优选的二元合金的次要组分为上面提到的掺杂材料，本文中所述掺杂材料常被称为M并选自六方密堆积(hcp)的过渡金属。所述hcp结构是过渡金属中最常见的，包括过渡金属锆(Zr)、钛(Ti)、钴(Co)、铪(Hf)、铷(Ru)、钇(Y)和锇(Os)。就此而言，这些hcp过渡金属中的一些，如Zr、Ti和Co，是实践上更容易操作的材料，故就本发明的目的而言，将为优选的掺杂材料。
虽然预计Zr将为最优选的hcp掺杂材料并因此本文主要参照Zr作为hcp掺杂材料来描述本发明，但这不应认为是对本发明的范围的限制。
在本发明的一个优选形式中，所述合金为二元合金并且所述二元合金中掺杂材料的原子百分率在约1.9原子％至约5.8原子％的范围内。然而，在此宽范围内，可以存在关于特定掺杂材料的更窄范围，这将在下文进一步描述。
现已发现，向铬(bcc过渡金属)中引入少量的hcp掺杂材料可以产生一系列具有金属间晶体结构的合金组合物，所述金属间晶体结构具有共存的bcc和Ω-hcp相，现已发现这将提供这些合金更有利的性质(超过单独的铬的那些性质)。实际上，现已发现，相对于铬的量，仔细选择hcp掺杂材料量可以产生在特别优选的那些范围内的合金组合物，其中期望的性质(如耐磨性)被最大化而不期望的性质(如非中性色的颜色)被最小化。
作为说明，现已发现，随着掺杂材料的元素组成增加，根据本发明的涂层将改变相组成，从仅bcc到bcc加Ω-hcp到bcc加非晶相。所观察到的所述涂层的光学和力学性质表现出与这些组成变化相配的变化，当相组成为bcc加Ω-hcp时出现优选的光学和力学性质。不希望受理论束缚，据信所观察到的变化归因于原子的电子结构及相对于彼此的结晶构象的改变。
具体而言，当相组成为bcc加Ω-hcp时，涂层的晶体结构展现出d-轨道跃迁，这产生了中性色和相对较低的反射率，且以良好有序的晶体结构产生较高的相对耐磨性。比较起来，当存在非晶相时，不再观察到d-轨道跃迁，表明相邻原子之间的轨道杂化部分地填充d-轨道，这对应于较不优选的较低反射率。此外，发现这样的非晶相中较低的原子堆积密度产生耐磨性降低的涂层，这当然也是较不期望的。
考虑到这一点并以通式CrMx中的M提及掺杂材料，当掺杂材料为Zr时，发现当x的值为约0.06(对应于约5.8原子％)时发生此从bcc加Ω-hcp到bcc加非晶相的相转变。对于Ti和Co，预期在大约相同的x值下发生相同的转变。
与反射率不同，发现本发明的涂层的颜色在相从bcc加Ω-hcp到bcc加非晶相的相转变时不表现出成趋势的变化。相反，在相从bcc到bcc加Ω-hcp的相转变时(对于Zr来说，发现在所述x(上面的通式中)为约0.05(对应于约4.5原子％的下限)值下发生)，发现本发明的涂层的颜色转变。这暗示在作为掺杂材料的Zr浓度接近约4.5原子％时电子结构中开始发生轨道杂化。然而，对于Co作为掺杂材料，发现相同的转变点为约1.9原子％。
作为说明，并再次使用Zr作为示例性的hcp掺杂材料，在低浓度下，当增加Zr的元素组成时，耐磨性将增加。在从bcc到bcc加Ω-hcp转变时观察到耐磨性的最大值，其后，增加Zr浓度将导致测得的磨损率的稳步减小。实际上，从CrZrx涂层的电子衍射分析确定了代表从一个相组成到另一个相组成变化的两个转变浓度。对于Zr作为掺杂材料，这些转变在约x＝0.05(bcc到bcc+Ω-hcp)和约0.06(bcc+Ω-hcp到bbc+非晶相)下。在这点上，Ω-hcp相被理解为是自bcc结构的位移型相变。
相应地，在本发明的一个形式中，合金为二元合金并且掺杂材料为Zr，其中所述二元合金中掺杂材料的原子百分率在约4.5原子％至约5.8原子％的范围内。
在本发明的另一个形式中，合金为二元合金并且掺杂材料为Co，其中所述二元合金中掺杂材料的原子百分率在约1.9原子％至约5.7原子％的范围内。
关于本发明人(基于所有hcp过渡金属的物理性质的相似性)能够从对Zr和Co以及一定程度上对Ti进行的实验工作(下文描述)得出的预测性结论，本领域技术人员会意识到：可以合理地预期在本发明中作为掺杂材料的其它hcp过渡金属的行为与用Zr、Co和Ti所看到的相同或相似。实际上，对在bcc过渡金属钼(Mo)(其中由于该过渡金属不同的物理性质而未预期(并且未看到)相似的行为)上进行的对比实验工作(同样参见下文)也倾向于确认这些关于hcp过渡金属的预测性结论。
实际上，假如其它hcp过渡金属的物理性质与Zr和Co二者相似，则预期Ti、Hf、Ru、Y和Os将在它们的浓度在约1.9原子％至约5.8原子％的范围内时在本发明的基于Cr的合金中表现出相同的结构形成能力。
本发明的涂层优选为超薄涂层，超薄涂层在本说明书中被定义为厚度为200nm或更小的涂层。预计优选的厚度在100nm或更小的范围内，或更优选在40nm至80nm的范围内，或更优选在50nm至70nm的更窄范围内。理想地，厚度为约60nm。
优选地，聚合物型基材通过注入压缩模塑，但本领域已知的任何其它方法如压塑、吹塑、反应模塑和片材流延也可采用并因此也落在本发明的范围内。
聚合物型基材可为任何已知类型的聚合物型基材材料，例如可为由选自以下的材料形成的基材：聚丙烯酸酯、聚酯、聚苯乙烯、聚乙烯、聚丙烯、聚酰胺、聚酰亚胺、聚碳酸酯、环氧树脂、酚醛树脂、丙烯腈-丁二烯-苯乙烯、丙烯腈-苯乙烯-丙烯酸酯、缩醛及其共混物。优选的基材材料包括聚碳酸酯、聚(2,2’-二羟基苯基丙烷)碳酸酯、聚二甘醇双(碳酸烯丙酯)、聚甲基丙烯酸甲酯和聚苯乙烯或其共混物。
另外，聚合物型基材可由已经预涂布有适宜的膜的聚合物型基材材料构成，这些膜提供基材以合适的性质以便沉积和粘附本发明的涂层。预涂布的膜包括硬涂层(如有机硅、丙烯酸类、氨酯、蜜胺或非晶SiOxCyHz)、无机氧化物(二氧化硅、二氧化钛、氧化铝)、薄金属膜(Cr等)，其中预涂布的基材已经制备为具有期望的表面能、残余应力、热膨胀系数、电导率、化学官能性等，如具体施加这样的基于Cr的合金涂层所需要。
以类似的方式，本领域技术人员会理解，出于机械强度、可润湿性、光学干涉滤光片、改变摩擦系数等目的，可以在本发明的涂层上方施加外涂层，所述外涂层可以包括透明涂层。外涂层功能的实例有疏水/亲水材料(二氧化硅、含氟聚合物)、硬涂层和无机氧化物(二氧化硅)。
在优选的形式中，本发明的方法中采用的物理气相沉积技术基于磁控溅射，其来自主要的合金靶或使用共溅射工艺，所述共溅射工艺涉及由合金的相应组分制成的两个靶。或者，应理解，优选的合金可以使用相应合金组分的热蒸发或电子束蒸发来沉积。
在转到描述本发明的各种优选实施方案的之前，应理解，由于聚合物型基材的性质，故不能采用常规温度加工(在沉积过程中或沉积后)来改变本发明的类型的合金涂层的性质。在本发明的涂层中，发明人已确定，随着掺杂材料(如Zr、Ti或Co)的元素组成增加，优选的合金将改变相组成：从仅bcc、到bcc加Ω-hcp、到bcc加非晶相。这些优选合金(作为超薄涂层)的光学和力学性质表现出与组成相配的变化并且观察到的变化与原子的电子结构及相对于彼此的结晶构象的改变有关。
实际上，这些结晶的超薄涂层展现出d-轨道跃迁，这产生中性色和相对较低的反射率，而以良好有序的晶体结构产生较高的相对耐磨性。当涂层中存在非晶材料时，不再观察到d-轨道跃迁，表明了d-轨道的部分填充。据信相邻原子之间的轨道杂化部分地填充d-轨道，这对应于黄色和较高的反射率。此外，非晶相中较低的原子堆积密度产生耐磨性降低的涂层。
具体实施方式
现在结合各种优选实施方案描述本发明，这些优选实施方案的一些方面由附图示意，其它方面由如汇总在下面的表中的下述实施例示意。在附图中：
图1示出了CrZrx涂层的相组成随其元素组成的变化-Ω-hcp的存在由用箭头突出的衍射表示；
图2示出了CrZrx涂层的明视反射率随元素组成的变化–涂层的光学反射率跟随其相组成改变；
图3示出了薄膜涂层的反射色度随CrZrx涂层的元素组成的变化–色度体现相对于中性而言的色级，但非观察到的具体颜色；相之间的转变在某个给定的浓度下不可能是离散的；
图4示出了CrZrx涂层的耐磨性随CrZrx涂层的元素组成的变化；
图5示出了根据本发明的实施方案(M＝Zr、Co和Ti)及用于对比目的(M＝W和Mo)的CrMx样品的透射电子显微镜衍射图案；和
图6示出了为实施例制备的基于铬的样品的晶格参数与耐磨性之间的关系。
实施例–物理性质
进行实验来在聚合物型基材上形成根据本发明的各种涂层。在这些实验中，采用专门制备的聚合物型基材，其自身包括直接施加于其上的涂层。实际上，该聚合物型基材为涂布了硬涂层树脂(来自MomentivePerformance Materials Inc.的PHC587B、来自SDC Technologies Inc.的TSR2626B或来自SDC Technologies Inc.的PR660/MP101)的聚碳酸酯材料(大约8cm×8cm正方形，厚0.5cm)，该硬涂层自身然后涂布以反应溅射的SiO2层。
聚合物型基材在11mm/s的撤离速度下浸涂或在300转每分钟(rpm)下旋涂5秒并按制造商规定的条件固化，从而在聚合物型基材上形成硬涂层树脂层。对于SiO2层，使用定制的反应器来在Ar+O2环境中溅射高纯度Si靶。如使用Filmetrics Inc.的F20薄膜分析仪所测得，硬涂层树脂层和SiO2层分别具有5μm和140nm的厚度。
随后在定制的反应器中通过磁控共溅射CrMx合金层(其中M＝hcp过渡金属Zr和Co)向此专门制备的聚合物型基材施加本发明的基于铬的反射涂层以形成一系列示例性样品。另外，制备其中M＝bcc过渡金属钼(Mo)的对比样品。
在反应室被抽空到大约1×10-4毫巴时在定制的反应器中使用红外灯将基材加热到85℃。使用采用两个溅射靶的共溅射工艺来沉积CrMx合金层。基材固定器在60rpm下旋转通过自5”×12”矩形高纯度Cr靶和3”圆盘掺杂材料靶生成的相应等离子体。选择60rpm的样品旋转速度是因为经计算每次通过等离子体将沉积大约4至6埃来自靶的组合材料，从而避免夹心型层结构并获得优选的二元合金涂层。
工作气体Ar以80标准立方厘米每分钟(sccm)的流率引入。对于沉积，将Cr靶设置在1kW的恒定功率下，同时将掺杂材料靶设置在25至100W的范围内来限定实验窗口以获得中性色耐磨合金涂层。如通过原子力显微镜成像所测得，样品的最终反射涂层具有约40至60nm的CrMx膜厚度。通过改变掺杂材料(M)相对于Cr的沉积速率来生成样品的涂层内不同的Cr:M比率，使用X-射线光电子能谱(XPS)分析(Kratos Axis Ultra DLD，Al-Kα单色光源)来确定获得的实际比率。
对每一个样品确定超薄CrMx膜由x限定的元素组成——所收集的数据参见表1(对于Zr)和表2(对于Co)。在使用Zr作为掺杂材料M时，随着施加到Zr靶和Cr靶的功率密度之间的比率增大，超薄膜中Zr浓度接近线性地增大。对于每一个Zr样品，使用TEM采集电子衍射图案(参见图1)，并然后分析膜内的主要组成成分。使电子束的束斑尺寸最小化以产生这些多晶超薄膜(相对于构成膜的小晶粒状/柱状结构而言是多晶的)可能的最清楚的衍射图案。
从CrZrx膜的电子衍射分析确定了代表从一个相组成到另一个变化的两个转变浓度。这些转变在x＝0.05(bcc到bcc+Ω-hcp)和0.06(bcc+Ω-hcp到bbc+非晶相)下。Ω-hcp相为自bcc结构的位移型相变。
使用HunterLab UltraScan Pro仪器测定每个样品的光学性质。这些光学测量通过a*和b*(如上面所提到)的CIELAB量度来量化，a*和b*体现所捕获的光(其为透射或反射的)的颜色或色度(C*＝√(a*2+b*2))。另外，测量涂层的总明视反射率(R％)。
参考表1和2以及图2，观察到反射率在所示的元素组成范围上变化。尤其是，光学响应更是跟随膜的相组成改变，在由电子衍射指认所确定的转变浓度下观察到反射率对元素组成的函数的不连续性。
进一步地，对于该反射率变化，在较低的Zr浓度下，在反射率对光子能量的函数中观察到最大值和最小值。实际上，在高达CrZrx＝0.11的浓度下，对于最大值和最小值，光子能量的测量值分别为2.5和2.2eV。在这些能量水平下，观察到的最大值被指认为从原子的填充了的d-轨道能带向空的d-轨道能带的跃迁，即3→5跃迁。从电子衍射图像可见，该浓度范围中的晶体结构代表Cr的bcc结构。
失去反射率的最大值和最小值对应于从完全结晶的合金膜(bcc和bcc+Ω-hcp)向结晶加非晶的转变。据信在非晶相中，较高的Zr浓度通过轨道杂化产生CrZrx结构的部分填充的d-轨道能带。增加的轨道填充消除了d-轨道能带间跃迁，因为它们当时被占据。因此在可见光谱之外的能量(>3.5eV)下发生在原子的电子结构中发生的电子跃迁。
随着d-轨道跃迁因增大Zr浓度而减少和消除，相对于其它能区而言，可见光谱的黄光部分(约2.15eV)反射率增大。因此，当Zr的元素组成增大时，样品的颜色强度(色度)从中性向黄色变化，如从图3明显可见。
实际上，与反射率不同，超薄膜的色度在结晶到结晶加非晶之间的转变浓度下不表现出成趋势的变化——参见图3。在其中观察到额外的Ω-hcp的转变浓度(x＝0.05)下，超薄膜的C*值有转变。这暗示在Zr浓度接近x＝0.05时电子结构中开始发生轨道杂化。
通过采用拜耳(Bayer)磨损测试测定每个样品的反射涂层的耐磨性。该测试在许多不同的行业中采用以考核涂层的耐磨性，这里采用的变化与用于测定飞机窗户和眼科透镜的耐磨性的ASTM F735标准相似。使用Taber振荡磨损测试仪(型号6100)使样品在0.5kg刚玉碎片(NortonCompany of Worcester MA,USA)的外加负荷下在100mm的行程长度上经受300个周期(150个周期/分钟)。在此测试中，耐磨性由拜耳比率量化，拜耳比率考虑了样品因磨损的雾度(或反射性基材的反射雾度)变化，以对参比样品观察到的雾度变化进行归一化(按SAE J964)。雾度通过下式确定：
雾度＝(R％SE/R％SI)×100
其中，R％SE和R％SI分别为排除和包括镜面反射光束的反射率。
使用用于颜色和反射率测量的相同HunterLab UltraScan Pro仪器对样品和参比二者测试雾度。在此研究中，使用相同类型的参比材料来测定拜耳比率(一片未经涂布的聚碳酸酯)。测得的拜耳比率越大，则相对于参比样品而言耐磨性越高。为对比本发明的涂层的性能，在其中存在各种预涂布膜作为聚合物型基材的一部分的情况下，将耐磨性与使用相同的预涂布基材的氮化铬(CrN)涂层的拜耳比率进行比较，其中将CrN涂层的耐磨性定义为可接受的耐磨性水平，然后将本发明的实施方案的可接受耐磨性水平以100％的耐磨性(％)表示。
再次具体参考具有Zr作为掺杂材料M的样品，通过耐磨性的测量表征超薄CrZrx膜的力学性质。重要的是认识到耐磨性不单由Cr:Zr比率表征，而是还受多层结构中的下覆层影响。因此，在此实验工作中，在给出的样品中不变地使用专门制备的基材，因此，力学性质的相对变化可以归于超薄CrZrx涂层的改变。
表1及图4和6中示出了通过上面提到的拜耳磨损测试对Zr作为掺杂材料测得的磨损率，表2及图6示出了对Co作为掺杂材料测得的磨损率。就对比分析的目的而言，使用bcc过渡金属Mo作为掺杂剂。
表1表明，在增加Zr的元素组成时，耐磨性增加。在从bcc到bcc+Ω-hcp转变之后马上观察到耐磨性的最大值，其后，增加Zr浓度导致测得的磨损率的稳步减小。表2表明，耐磨性与Co的元素组成的增加一致地增加，在从bcc+Ω-hcp到bcc+非晶结构转变之前观察到最大耐磨性。对于表1和2中示例的两种掺杂剂，当掺杂剂以产生bcc+Ω-hcp结构的浓度存在时(灰色栏)，耐磨性最大。
表1
表2
实施例–晶体结构
共溅射生成经另一金属(在这里描述的大多数情况下为Zr，但或者也可为Ti或Co，或较不优选地Hf、Ru、Y和Os)掺杂的Cr的薄膜涂层。如上面所提到，掺杂材料如这些将通过取代bcc晶格内的Cr原子而改变基于Cr的涂层的结构。观察到bcc Cr涂层的原子结构的这种改变并通过使用电子衍射测量晶体结构的晶格参数来对优选的Zr掺杂材料进行量化。观察到掺杂剂的引入和由此引起的晶格参数的改变与宏观耐磨性相关联。取决于室温下掺杂剂金属的类别(是bcc还是hcp)，发现可以控制bcc Cr晶格的改变程度。
通过使用Philips CM200透射电子显微镜(TEM)对样品进行电子衍射实验来本发明的反射涂层中形成的优选二元合金的原子结构进行了解。这些样品通过向NaCl晶体上直接溅射、在Milli-Q水中溶解掉晶体并然后将合金涂层漂浮到未经涂布的TEM铜网上来制备。样品包括另外的hcp过渡金属Ti外加bcc过渡金属Mo和W的使用，其为对比的目的而研究。
对来自每个样品的衍射图案进行分析以确定在结晶涂层的情况下的晶格参数a0，或者只是在未观察到结晶材料时确认非晶结构。基于每一掺杂材料获得的总体最大拜耳比率选择掺杂剂靶功率的实验窗口。该窗口在50至100W的范围内。对不同的合金混合物得到的受试功率为Mo和W＝100W；Co、Ti和Zr＝50W。
发现这些样品的固溶体中存在的主要相为bcc结构，然而，对于某些样品，观察到另外的相。CrCox、CrZrx和CrTix的衍射光谱表明存在不同于bcc的次要相，如由图5中的箭头所指示。经鉴别，该次要相为Ω-hcp相，一种自bcc相的位移型相变。进一步进行该分析，注意到在衍射图案的背景中存在非晶材料，对于CrTix合金来说，该相最显著(图5中的CrTix衍射图像中的模糊背景)。
原子结构与宏观耐磨性之间的关系在表1、2中明显可见。另外，并如图6中可见，在该系列样品的基于Cr的合金上，有着明显的趋势：随着晶格参数减小，耐磨性增加。耐磨性的此增加主要归因于原子的堆积密度的增大。
实际上，将掺杂材料的原子半径与Cr的原子半径进行比较强调了基于对堆积密度的尺寸约束，不能使CrMx合金的晶格参数的变化合理化(例如，W具有较大的原子半径，然而使用W作为掺杂材料的合金观察到晶格参数的减小)。实际上，对于过渡金属合金，被合金化的原子的电子态以及它们的电子相互作用通常对限定晶格参数起促进作用。Cr(4s1和3d5)与本发明的优选掺杂材料的价电子的比较表明，Mo是相当的(5S1和4d5)，而其它元素具有另外的s-轨道和不同的d-轨道价电子数。与Cr相比，具有不同的价电子数的掺杂材料产生合金中晶格参数的减小，而Mo(其不是理想地用作掺杂材料的优选hcp过渡金属之一)产生增大。
关于本发明的优选合金的力学性质，这些结果与当用第VI族金属Mo和W合金化时其中具有更大价电子数的掺杂材料的添加产生了固溶体软化的其它情况形成对比。
不希望受理论束缚，但据信具有额外的价电子的掺杂材料的轨道重叠将增加合金中的键合强度，从而产生减小的晶格参数。重要的是，如此沉积的Cr的bcc结构已在一定程度上被掺杂材料所改变，其中耐磨性与如此沉积的CrN涂层的耐磨性相匹敌(对于使用定制的反应器在专门制备的基材上如此沉积的CrN1.3涂层，拜耳磨损率为～7)。
最后，本实验工作中采用的优选掺杂材料还能够根据其室温平衡结构来分类。Mo和W在室温下为bcc，而Ti、Co和Zr在室温下为hcp。hcp掺杂材料比bcc掺杂材料获得更大的晶格参数减小。鉴于掺杂材料的电子结构影响键合强度的观察，据信hcp掺杂材料的电子结构产生更高的键合强度。另外，并如上面所提到，这些hcp掺杂材料产生具有bcc和Ω-hcp相二者的优选复合膜。
应理解，本文所述的组合物可有其它变化和修改，这些变化和修改也在本发明的范围内。

Claims (31)

1.用于聚合物型基材的基于铬的反射涂层，其中所述涂层具有200nm或更小的厚度，并且是铬与掺杂材料的合金，所述掺杂材料选自六方密堆积的过渡金属，所述合金具有主要的体心立方相与次要的Ω六方密堆积相共存的晶体结构。
2.根据权利要求1所述的基于铬的反射涂层，其中所述合金为铬与所述掺杂材料的二元合金。
3.根据权利要求1或权利要求2所述的基于铬的反射涂层，其中所述二元合金中所述掺杂材料的原子百分率在约1.9原子％至约5.8原子％的范围内。
4.根据权利要求1至3中任一项所述的基于铬的反射涂层，其中所述掺杂材料选自六方密堆积的过渡金属锆、钛、钴、铪、铷、钇和锇。
5.根据权利要求1至3中任一项所述的基于铬的反射涂层，其中所述掺杂材料选自六方密堆积的过渡金属锆、钛和钴。
6.根据权利要求1所述的基于铬的反射涂层，其中所述合金为二元合金，所述掺杂材料为锆，并且其中所述二元合金中所述锆的原子百分率在约4.5原子％至约5.8原子％的范围内。
7.根据权利要求1所述的基于铬的反射涂层，其中所述合金为二元合金，所述掺杂材料为钛，并且其中所述二元合金中所述钛的原子百分率在约1.9原子％至约5.8原子％的范围内。
8.根据权利要求1所述的基于铬的反射涂层，其中所述合金为二元合金，所述掺杂材料为钴，并且其中所述二元合金中所述钴的原子百分率在约1.9原子％至约5.7原子％的范围内。
9.根据权利要求1至8中任一项所述的基于铬的反射涂层，其中所述涂层的厚度为100nm或更小。
10.根据权利要求1至8中任一项所述的基于铬的反射涂层，其中所述涂层的厚度在40nm至80nm的范围内。
11.根据权利要求1至8中任一项所述的基于铬的反射涂层，其中所述涂层的厚度在50nm至70nm的范围内。
12.根据权利要求1至8中任一项所述的基于铬的反射涂层，其中所述涂层的厚度为约60nm。
13.在聚合物型基材上形成基于铬的反射涂层的方法，所述方法包括通过物理气相沉积向所述聚合物型基材施加铬和掺杂材料，所述掺杂材料选自六方密堆积的过渡金属，以形成具有200nm或更小的厚度的合金涂层，施加所述合金涂层以便具有主要的体心立方相与次要的Ω六方密堆积相共存的晶体结构。
14.根据权利要求13所述的方法，其中所述合金为铬与所述掺杂材料的二元合金。
15.根据权利要求13或权利要求14所述的方法，其中所述二元合金中所述掺杂材料的原子百分率在约1.9原子％至约5.8原子％的范围内。
16.根据权利要求13至15中任一项所述的方法，其中所述掺杂材料选自六方密堆积的过渡金属锆、钛、钴、铪、铷、钇和锇。
17.根据权利要求13至15中任一项所述的方法，其中所述掺杂材料选自六方密堆积的过渡金属锆、钛和钴。
18.根据权利要求13所述的方法，其中所述合金为二元合金，所述掺杂材料为锆，并且其中所述二元合金中所述锆的原子百分率在约4.5原子％至约5.8原子％的范围内。
19.根据权利要求13所述的方法，其中所述合金为二元合金，所述掺杂材料为钴，并且其中所述二元合金中所述钴的原子百分率在约1.9原子％至约5.7原子％的范围内。
20.根据权利要求13至19中任一项所述的方法，其中所述涂层的厚度为100nm或更小。
21.根据权利要求13至19中任一项所述的方法，其中所述涂层的厚度在40nm至80nm的范围内。
22.根据权利要求13至19中任一项所述的方法，其中所述涂层的厚度在50nm至70nm的范围内。
23.根据权利要求13至19中任一项所述的方法，其中所述涂层的厚度为约60nm。
24.根据权利要求13至23中任一项所述的方法，其中所述物理气相沉积通过磁控溅射进行。
25.根据权利要求24所述的方法，其中所述磁控溅射采用主要的合金靶或两个合金靶，所述两个合金靶中的每一个由所述铬或所述掺杂材料中之一形成。
26.根据权利要求13至23中任一项所述的方法，其中所述物理气相沉积通过使用热蒸发或电子束蒸发进行。
27.涂布了基于铬的反射涂层的聚合物型基材，所述基于铬的反射涂层为根据权利要求1至12中任一项所述。
28.根据权利要求27所述的涂布的聚合物型基材，其中所述聚合物型基材由选自以下的材料形成：聚丙烯酸酯、聚酯、聚苯乙烯、聚乙烯、聚丙烯、聚酰胺、聚酰亚胺、聚碳酸酯、环氧树脂、酚醛树脂、丙烯腈-丁二烯-苯乙烯、丙烯腈-苯乙烯-丙烯酸酯、缩醛及其共混物。
29.根据权利要求27所述的经涂布聚合物型基材，其中所述聚合物型基材由选自以下的材料形成：聚碳酸酯、聚(2,2’-二羟基苯基丙烷)碳酸酯、聚二甘醇双(碳酸烯丙酯)、聚甲基丙烯酸甲酯和聚苯乙烯或其共混物。
30.根据权利要求27至29中任一项所述的涂布的聚合物型基材，其中所述聚合物型基材包括呈硬涂层、无机氧化物或薄金属膜的形式的预涂布膜或所述预涂布膜的组合。
31.根据权利要求13至26中任一项所述的方法涂布的聚合物型基材。
CN201380012348.6A 2012-01-24 2013-01-24 基于铬的反射涂层 Active CN104302803B (zh)

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CN109844403A (zh) * 2016-06-01 2019-06-04 Smr专利责任有限公司 用于车辆的灯组件
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CN109844403A (zh) * 2016-06-01 2019-06-04 Smr专利责任有限公司 用于车辆的灯组件
CN109844403B (zh) * 2016-06-01 2021-06-11 Smr专利责任有限公司 用于车辆的灯组件
CN111094069A (zh) * 2017-03-13 2020-05-01 玛泽森创新有限公司 发光镜边框
CN111094069B (zh) * 2017-03-13 2023-03-24 玛泽森创新有限公司 发光镜边框
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