CN100591798C - 涂覆金属涂层的不锈钢带 - Google Patents
涂覆金属涂层的不锈钢带 Download PDFInfo
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- CN100591798C CN100591798C CN200480031712A CN200480031712A CN100591798C CN 100591798 C CN100591798 C CN 100591798C CN 200480031712 A CN200480031712 A CN 200480031712A CN 200480031712 A CN200480031712 A CN 200480031712A CN 100591798 C CN100591798 C CN 100591798C
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- stainless steel
- steel
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- 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
- 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
- C23C28/02—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 only coatings only including layers of metallic material
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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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
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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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- 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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- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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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
- 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
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- C23C28/021—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 only coatings only including layers of metallic material including at least one metal alloy layer
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- 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
- 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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
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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
- 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
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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
- 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
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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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- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
本发明提供一种具有涂层的高强度不锈钢带(2)产品，所述的钢带的一侧或两侧涂覆有致密且均匀分布的金属涂层(1、3)。所述的涂层基本由纯的金、铜、镍、钴、钼、银、锡或钨或由这些金属中至少两种的合金组成，所述涂层的厚度优选的为至多15微米，所述涂层厚度的公差至多为涂层厚度的+/-30%，钢带基体的铬含量至少为10%，由于涂层良好的附着性，因此通过抗拉测试中钢带能够被单轴拉断而不会出现涂层的剥落、脱落或类似现象。金属涂层的钢带产品适合用于承担负载和必须能够在输送电流到接触表面时不会在表面之间的接触面产生电流传导率下降的应用。
Description
技术领域
本发明涉及一种用于在卷对卷(roll-to-roll)工序中制造具有金属涂层的钢带产品的方法，特别是适合制造高强度不锈钢产品的有涂层的金属基体材料的制造方法。这通过对金属带涂覆导电涂层来实现，如权利要求1所述。
背景技术
在许多例如电话、遥控器、计算机等的电子设备中，为了不同的功能使用了弹簧和其他形状的金属部件。因此，为了电磁屏蔽(EMS)的目的，在屏蔽盒的可除去部分中，弹簧用在被称为“金属弹簧弹片(finger stocks)”的衬垫内。在多数此类产品中，目前存在对材料的几种不同的需求。对于弹簧，这种需求通常与力学特性有关，例如承载力、松弛强度和抗疲劳强度。然而，如先前通常提及的，材料必须能够成形为所需形状而不出现任何裂化。此外，在本领域内的持续小型化趋势也提高了对电子设备的组件和零件的严格几何公差的需求。除上述以外，有时这些部件和零件的良好限定的电性能特征是至关重要的。这可涉及与设备内接触面的电导率和接触电阻率等有关的特殊性能。通常，当出现此类需求后，选择的解决方案是选择传导材料，比如铜或铜合金，或可选的在钢上涂上导电涂层。铜和铜合金通常具有的特性为良好的电导率和优秀的可成形性，但是大多数铜和铜合金具有低机械强度，这意味着它们不适用于在高度受压下的应用，例如用作弹簧。铜和铍的合金可以硬化到具有高达约1400MPa的抗拉强度，但是这个抗拉强度级别限制了弹簧应用中实现的弹簧力、松弛强度和疲劳强度。此外，铍为有毒金属，出于健康的考虑在制造和使用中具有限制。最后，铜一铍合金比较贵重，因此，许多应用中要求廉价的产品。
可以通过不同的方法实现涂覆，这些方法可以分为机械方法和化学方法。也可以细分为高温和低温方法。例如，机械方法可以为金属包层法，高温方法为喷涂或涂刷等。在本文中，采用辊轧接合代表金属包层法，即，通过辊轧接合工艺将两种(或更多)不同的材料接合，所述辊轧接合相对简单并且可以通过不同的基体和涂层组合来进行。然而，金属包层法具有一些技术性的不足，这些不足与厚度公差和涂层的不良附着性有关。这经常需要在接合后进行热处理以得到涂层间的扩散区。如果一个(或几个)涂层为不锈钢，由于不锈钢表面的钝化膜，将更加难以得到良好的附着性。此外，辊轧接合为低速处理过程，并受限于基体和涂层的可能组合。
同样存在许多基于喷涂方法的不同的沉积技术，其具有不同的名称，例如热喷涂技术、高速火焰喷涂技术(HVOF)、等离子喷涂技术、燃烧化学汽相沉积技术(CCVD)等；然而其根本方法是相同的。涂层被喷涂到基体上，涂层材料以任一的杆状、线状、块状、粉状材料，液态或气态的形式，被充入喷嘴或“火焰”内。喷涂技术最通常用于涂覆小零件，并不适合卷对卷涂覆，并对紧公差和高生产率存在很高的要求。
另一种在基体上进行涂覆的方法是将产品浸入金属熔液的热浸方式。热浸通常利用低熔点金属涂覆，比如锌等。为涂覆高熔点的金属，比如镍和铜，金属熔液的温度过高，对基体产生不利的影响。此外，难以在此类金属熔液中进行精确的处理控制以允许涂层厚度的紧公差。
电镀技术是一种电化学加工，其中，通过在含有溶解的金属离子和待镀金属物体的溶液中导入电流来实现涂覆。金属基体作为电化电池的阴极，从溶液中吸附金属离子。铁或非铁的金属基体被镀上各种的金属，包括铝、黄铜、青铜、镉、铜、铬、铁、铅、镍、锡和锌，以及贵金属，如金、铂和银。
由于基体在处理过程中作为阴极并吸附溶液中的离子，对于扁平的产品将难以获得均匀的涂层分布。电流密度的局部差别将导致沉积速率不均。众所周知的问题是“狗骨”效应，这意味着涂层的厚度通常朝向涂覆带的边缘变厚。此外，这种方法的特征在于，由于涉及电解液和废水处理，对环境容易产生污染。如果需要单面涂覆，电化学方法和浸渍方法也具有不利之处，在涂覆之前不需要涂覆的表面需要以某种方式被遮盖。涂覆处理结束后需要移除遮盖物。
还有一些能够用于沉积金属的汽相沉积方法。多数方法为分批处理，但是也具有一些持续处理方法。WO 98/08986中公布了一个卷对卷工艺卷对卷方法的示例，其利用电子束沉积，描述了制造铁素体FeCrAl不锈钢带的方法，通过卷对卷工艺卷对卷方法处理中使基体材料上涂覆铝涂层。然而，这个专利申请中描述的是适合高温腐蚀性环境的产品的最佳方法，因此需要材料具有良好的高温强度和高温耐腐蚀性，即耐氧化性。此外，这个专利申请建议在温度为950-1150摄氏度进行与涂覆有关的均质化退火，以使铝能够均匀分布在铁素体上。这意味这这个示例中的最终产品不是表面上具有铝涂层的涂覆产品。因此，这更是一种合金元素均匀分布的FeCrAl带材，其中也包括铝。此外，这意味着其对不含氧化物的接触面和涂层的良好附着性没有特殊的要求。
因此，这些传统的方法都具有不同的不足，这意味着存在对开发一种整合了良好的机械特性、优秀的导电特性和小的几何公差的新产品的需求。
基于批量生产的全部处理过程总会提高生产成本，因此采取卷对卷工艺处理降低生产成本是关键的。
因此，本发明的首要目的是提供一种挠性金属产品，该产品具有特定的物理和机械特性，适合进一步处理，例如但不限于冲切、弯曲、钻孔及热处理等。
然而本发明的另一目的是提供一种挠性条带产品，用于弹簧或其他产品，其需要良好的电导率，由单层或多层金属条带制成，所述条带成本低廉并通过卷对卷工艺生产。
通过制造带有涂层的钢产品，所述钢产品具有根据权利要求1的特征条款的特性，这些和其他目的已经以令人惊讶的方式达到。进一步优选的实施例在附属权利要求中被限定。
发明内容
因此，通过在作为基体的不锈金属带的上部施加一个或多个薄的、连续的、均匀的导电金属层实现上述目的和进一步优势，所述导电金属例如为镍、银、锡、钼、铜、钨金或钴。涂覆可以可在基体带的一侧或两侧上进行。金属层应当是致密和平滑的并具有良好的附着性，以允许进一步处理而没有剥落、脱落的风险。最终产品的形式是具有一个或两个导电表面的高强度带钢，适合用于电子设备中，在电磁屏蔽的衬垫内，或用于其他目的，其中在根据本发明的产品和接触点之间的接触面具有低接触电阻的高强度材料即是所要求的材料。
通过先前所知的电子束蒸发方法，在卷对卷工艺中沉积涂层，涂层为优选的低于15微米厚度的均匀分布涂层。基体材料是铬含量(重量)高于10％和条带厚度通常低于3毫米的不锈钢。基体材料应该至少具有1300MPa的抗拉强度，这可以通过冷变形或热处理完成，热处理例如为高温硬化或低温析出硬化。最初的步骤中，卷对卷工艺也可以包括蚀刻反应室，以去除通常在不锈钢上出现的氧化层。
附图说明
图1示出了本发明的第一实施例的示意性截面图，即，在一个或两个表面涂有导电涂层1、3的基体带2。如果基体在两个表面都有涂层，则涂层可具有同样的成分，或者如果需要可具有不同的成分。两个表面的涂层厚度也可以相同或不同。
图2示出了本发明的第二实施例的示意性截面图，即基体带2在一个或两个表面上涂有多个涂层(分别为涂层1、3、4和5、6)。
图3示出了用于制造根据本发明的具有涂层的金属带材料的生产线的示意图。
具体实施方式
最终产品，形式为具有金属涂层的条带材料，适合用于承载部件，并在接触面具有低接触电阻。这种应用的实施例为连接器和开关。通过在弹簧上施加一定的推力，弹簧将与表面相接触并闭合电路。在传送电流的接触点，低接触电阻是重要的。不锈钢是弹簧应用中使用日益增加的材料。这是由于其吸引人的结合了高机械强度和良好的可成形性，容许成形为相当复杂的弹簧形状。高强度不锈弹簧钢与非铁材料对比通常具有优越的机械特性。在关于弹簧特性的上文中，尤其是高强度不锈钢的松弛强度和抗疲劳强度，对于具有贯穿使用寿命的恒力的耐久弹簧是至关重要的。然而，不锈钢的特征在于表面上的钝化膜。这层膜由铬氧化物组成并相比钢本身具有显著降低的电导率。作为参考数值，取决于其抗拉强度，不锈钢电阻率为80-90x10-8Ωm。然而在其表面，氧化物(Cr2O3)电阻率大约为1.3x1011Ωm。如果氧化膜出现在两个传导表面之间的接触面，将导致传导率的下降。这将降低电路中电流循环的效率从而降低性能。
为消除高强度不锈钢的低传导率问题，至少条带的一个表面被涂有金属涂层，所述涂层的表面不太倾向于形成氧化膜。因此涂层容许在接触点产生无氧化物的表面，由此接触面电导率的下降被避免。根据需求，涂层可以具有不同的金属。银、铜、镍、钴、金、钨、锡和钼都是具有良好的电导率的金属，这些金属可以通过根据本发明的方法沉积在表面上。同样至关重要的是，涂层均匀分布在表面上，并且与基体的厚度相比涂层不是过厚。过厚或不均匀的涂层将影响弹簧的性能，因为弯曲力与引起第三种力的直角区域的厚度成正比。因此优选的涂层厚度最大为基体厚度的10％。此外，每个涂层的厚度优选的最大为15微米，典型的为0.05-15微米，优选的为0.05-10微米，并且更加优选的为0.05-5微米。如果沉积了多个涂层，涂层的总厚度不应超过带有涂层的条带的总厚度的20％。根据本发明的涂层的厚度公差非常良好。每个涂层厚度的变化和每个涂层内厚度的变化不应超过所述涂层标称厚度的+/-20％。更加优选的，每个涂层内厚度变化的最大为标称厚度的+/-10％。
涂层将显示出对基体良好的附着能力并因此使后续的加工成为可能。根据本发明的产品在涂层和基体之间展示了极佳的附着性。这通过在涂层沉积基体之前，在真空中对不锈钢带进行离子蚀刻的预处理操作实现。这容许了金属与金属进行无氧化物接触面的接触，这将使产品可以够被弯曲、冲切、切割或深拉，唯一设定的限制是基体材料的延展性。
将被涂覆的基体带
将要被涂覆的材料应具备良好的整体耐腐蚀性。这意味着材料必须具有至少按重量，10％的铬含量，优选为最少12％或更加优选的13％或最优选的15％的铬。此外，材料必须以允许至少1300MPa的高抗拉强度的方式铸成合金，更优选的是至少1500MPa，或最优选的至少1700MPa。可以通过对例如ASTM 200和300系列钢冷变形获得机械强度，或通过可硬化马氏体铬钢的热硬化获得机械强度。其他适合的基体材料为析出硬化型(PH)钢，类型为13-18PH、15-5PH、17-4PH或17-7PH。然而另一组适合的基体材料为马氏体不锈钢，其特征在于低碳、低氮，包含马氏体基体，其通过例如铜、铝、钛、镍等替代原子析出实现硬化。
导电涂层
以薄膜形式涂覆在基体表面的材料，其特征应该是在室温下具有良好的电导率，抗氧化物形成的热动力稳定性和适合的弹性模量。适合的元素特性如以下所列。
银具有非常低的电阻率，室温下大约为1.47x10-8Ωm。室温下氧化形成Ag2O的自由能大约为ΔG＝-10.7kj，这使得对比不锈钢中形成Cr2O3，银具有显著更加稳定的抗氧化性。作为参考值，室温下Cr2O3的自由能大约为ΔG＝-1050kj。银的弹性模量为79000MPa，能够与不同类型钢的180,000-220,000MPa相比较。然而银是相对贵重的金属并且有时需要廉价的替代物。
铜具有低电阻率，大约为1.58x10-8Ωm，弹性模量大约为210,000MPa，形成Cu2O和Cu2O的各自的自由能为ΔG＝-145kj和ΔG＝-127kj。该综合特性也使得铜适合涂覆根据本发明的产品。
镍具有低电阻率，大约为6.2x10-8Ωm，弹性模量为200,000MPa，形成NiO的自由能大约为ΔG＝-213kj。
金的电阻率大约为2x10-8Ωm，弹性模量为80,000MPa。金也具有极度稳定的抗氧化性。这使得金成为许多应用中最适合用作导电涂层的元素。然而，金是昂贵的金属并且由于高熔铸成本及回收费用，总是寻找其替代物。
钼具有低电阻率，大约为5.3x10-8Ωm，弹性模量为329,000MPa，形成MoO3的自由能大约为ΔG＝-668kj，形成MoO2自由能为ΔG＝-533kj。
钴具有低电阻率，大约为6.24x10-8Ωm，弹性模量为209,000MPa，形成CoO的自由能大约为ΔG＝-241kj。
钨具有低电阻率，大约为5.3x10-8Ωm，弹性模量为360,000MPa，形成WO2和WO3的自由能分别为ΔG＝-534kj和ΔG＝-764kj。
锡具有低电阻率，大约为10x10-8Ωm，弹性模量为50,000MPa，室温下形成SnO的自由能大约为ΔG＝-534kj。锡也是一种相对软的金属并且在接触点易于发生变形，可以通过这点在接触面产生更大的接触区域。这可以利用在例如用于电磁屏蔽的金属垫圈弹簧。
涂覆方法的描述
有利的，涂覆方法被整合到卷对卷条带生产线上。在这种卷对卷生产线上，生产的第一个步骤是金属带表面的离子辅助蚀刻，以获得第一涂层的良好附着性。在卷对卷工艺中通过电子束蒸发(EB)沉积导电层。多个涂层的成型可以通过在生产线上整合几个EB沉积室完成。
本发明的优选的实施例
现在将就更多的细节描述本发明的两个实施示例。一个示例基于ASTM301类型的钢上涂覆银，所述的钢化学成分为：至多0.12％的碳、至多1.5％的硅、至多2％的锰，16-18％的铬和6-8％的镍，及平衡铁和根据使用的冶金方法出现的残留元素。第二示例是在改良的ASTM301类型的钢上涂覆镍，所述钢的化学成分为：至多0.12％的碳、至多1.5％的硅、至多2％的锰，16-18％的铬和6-8％的镍、0.5-1.0％的钼，及平衡铁和根据使用的冶金方法出现的残留元素。
首先，通过普通的冶金炼钢得到含有上述示例化学成分的基体材料。之后将基体材料热轧到中等尺寸，之后通过几个步骤冷轧，所述的轧制步骤之间包括多个再结晶步骤，直至获得最终厚度大约为0.02-1毫米，宽度为至多1000毫米。然后通过恰当的方式去除轧制过程中所有的残油，清洁基体材料的表面。
之后，在连续生产线上进行涂覆处理，从开卷装置开始。在卷对卷工艺处理线上的第一步骤可以是在真空室或进入真空锁进行处理，接着是在蚀刻室进行处理，在所述蚀刻室内发生离子辅助蚀刻以去除不锈基体材料表面的氧化物薄层。条带随后进入电子束蒸发室，在蒸发室内发生所需涂层的沉积。取决于应用中的优选厚度，金属涂层通常沉积到0.05到15微米。此处描述的两个示例中，通过使用一个电子束蒸发室沉积的涂层厚度为0.2-1.5微米。
电子束蒸发之后，涂覆后的条带材料在被卷取机卷上之前通过退出真空室或退出真空锁。如果需要，涂覆过的条带现在可以进行进一步处理，例如通过轧制或切割获得用于部件制造的最终优选尺寸。
这两个示例的最终产品可描述为：0.05毫米厚、单面涂有1.5微米银涂层的ASTM301条带，和0.07毫米厚、单面涂有0.2微米镍涂层的改良ATSM301条带，涂覆的涂层具有非常好的附着性，因此适合用于高强度应用的部件，例如弹簧的后续加工。根据标准抗拉测试检验涂层的良好附着性。在不锈钢条带的基体材料上涂覆覆盖薄层，以生产根据本发明的被涂覆的条带产品，取自所述条带产品的抗拉测试样品根据标准生产。对4个样品进行抗拉测试，例如根据EN 10002-1，对其进行测试直到断裂。测试后，在光学显微镜下以50倍的放大倍率分析样品的断裂部分。除了测试中的真实断裂，没有在任何样品上发现所附涂层的剥落、脱离或其他任何损害的迹象。测试结果如表1所示。
表1涂层的机械特性和附着性
| 样品 | 厚度毫米 | 极限强度Pπ0.05％，MΠα | 极限强度Pπ0.2％，MΠα | 抗拉强度Pμ，MΠα | 50倍放大率下视觉检查 |
| 301型+镍 | 0.07 | 1659 | 2108 | 2120 | 无剥落或脱离 |
| 301改良型+银 | 0.05 | 1445 | 1920 | 1945 | 无剥落或脱离 |
上文提到的卷对卷电子束蒸发处理过程如图3中所示。这种生产线的第一部分为真空室14内的开卷机13，然后是与之排成一列的离子辅助蚀刻室15，接着是一系列电子束(EB)蒸发室16，所需的电子束蒸发室的数量可从1到10变化，这样得到了多重涂层的结构，如果需要的话。所有的EB蒸发室16都配备电子束发射枪17和适当的用于蒸发的坩埚18。这些蒸发室之后，为退出真空室19和用于涂覆后的条带材料的卷取机20，卷取机位于真空室19内。真空室14和19也可以被进入真空锁系统和退出真空锁系统分别取代。在后例中，开卷机13和卷取机20位于敞开空气中。
Claims (12)
1.一种被涂覆的不锈钢带产品，所述的钢带的一侧或两侧具有致密和均匀分布的涂层，其特征在于，所述的涂层基本由金属金、铜、镍、钼、钴、银、锡或钨中的一种或多种组成，所述涂层的厚度为至多15微米，所述涂层的公差至多为涂层厚度的+/-30％，钢带基体的铬含量至少为10％，钢带基体在冷轧或热处理条件下的抗拉强度至少为1300MPa，并且涂层具有良好的附着性，从而使得在抗拉测试中被涂覆的钢带能够被单轴向的拉断，而不会出现任何的剥落、脱落趋势。
2.根据权利要求1的产品，其特征在于，钢带基体的厚度在0.015毫米和3.0毫米之间。
3.根据权利要求1或2的产品，其特征在于，所述产品由奥氏体不锈钢、或双相不锈钢、或可硬化马氏体铬钢、或可析出硬化不锈钢、或马氏体时效钢的基体制成。
4.根据权利要求1所述的产品，其特征在于，具有多重涂层结构的涂层至多为10层。
5.根据权利要求4的产品，其特征在于，每个单独的涂层的厚度在0.05到15微米之间。
6.根据权利要求4的产品，其特征在于，每个单独的涂层的厚度在0.05到11微米之间。
7.根据权利要求4的产品，其特征在于，每个单独的涂层的厚度在0.05到5微米之间。
8.根据权利要求5的产品，其特征在于，所述涂层具有这样的多重涂层结构，所述的多重涂层结构的各个涂层由不同的金属涂覆，所述金属包括银、镍、铜、钴、金、钼、钨，和/或锡。
9.根据权利要求8的产品，其特征在于，涂层由根据权利要求1的至少2种元素的合金组成。
10.根据权利要求1所述的产品，其特征在于，所述产品适合用于承担负载的应用，在所述应用中，表面具有低接触电阻是有利的。
11.根据权利要求1所述的产品，其特征在于，所述产品适合用于生产和使用的弹簧部件为开关、连接器、金属拱顶。
12.根据前述任一项权利要求所述的被涂覆的不锈钢带产品的制造方法，其特征在于，在包括钢带生产线的连续的卷对卷工艺中生产所述的产品，其中使用电子束蒸发沉积涂层，之前对基体表面进行离子辅助蚀刻处理。
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| US20090068494A1 (en) * | 2005-05-31 | 2009-03-12 | Petersen Finn T | Metal Strip Product, Such as an Electrical Contact Spring, and the Manufacturing Thereof |
| SE0601058L (sv) * | 2006-05-09 | 2007-11-10 | Sandvik Intellectual Property | Bladventilmaterial, tillverkning och användning därav |
| SE0700476L (sv) * | 2007-02-23 | 2008-08-24 | Sandvik Intellectual Property | Kontaktelement med låg elektrisk impedans för drift i korrosiva miljöer |
| SE0700978L (sv) * | 2007-04-23 | 2008-10-24 | Sandvik Intellectual Property | Kontaktelement hos ett alkaliskt batteri |
| KR101136488B1 (ko) * | 2009-11-06 | 2012-04-20 | (주)알오호일 | 메탈 돔용 알루미늄층 금속박판 제조방법 |
| KR20120026201A (ko) * | 2010-09-09 | 2012-03-19 | (주)엠에스테크비젼 | 반복형 퓨즈 |
| CN102294485B (zh) * | 2011-08-25 | 2013-01-30 | 哈尔滨东大高新材料股份有限公司 | 复合电接触材料及其制备方法 |
| CN103753871A (zh) * | 2013-12-31 | 2014-04-30 | 苏州米达思精密电子有限公司 | 一种表面局部镀金的金色不锈钢卷带及其制备工艺 |
| CN103847162B (zh) * | 2014-02-21 | 2016-01-27 | 苏州米达思精密电子有限公司 | 一种表面镀金的金色补强片及其制备工艺 |
| JP6014199B2 (ja) * | 2015-04-28 | 2016-10-25 | 日本発條株式会社 | 積層体の製造方法 |
| DE102015220230A1 (de) | 2015-10-16 | 2017-04-20 | Thyssenkrupp Ag | Beschichtete Feder |
| WO2017154981A1 (ja) * | 2016-03-09 | 2017-09-14 | 日立金属株式会社 | マルテンサイト系ステンレス鋼箔およびその製造方法 |
| WO2019239185A1 (en) * | 2018-06-13 | 2019-12-19 | Arcelormittal | Vacuum deposition facility and method for coating a substrate |
| WO2019239184A1 (en) | 2018-06-13 | 2019-12-19 | Arcelormittal | Vacuum deposition facility and method for coating a substrate |
| WO2019239186A1 (en) | 2018-06-13 | 2019-12-19 | Arcelormittal | Vacuum deposition facility and method for coating a substrate |
| CN109435362B (zh) * | 2018-09-25 | 2021-01-15 | 首钢集团有限公司 | 一种抗锈蚀冷轧钢板及其制造方法 |
| HUE055332T2 (hu) * | 2019-02-26 | 2021-11-29 | Bekaert Sa Nv | Mûködtetõ szerkezet egy autó ajtajának vagy csomagtér ajtajának nyitására és zárására |
| CN113481471B (zh) * | 2021-07-10 | 2023-08-04 | 如皋市凯源电器设备有限公司 | 高性能导电条用金属材料制备工艺 |
| CN115679268B (zh) * | 2022-11-15 | 2024-10-18 | 上海大学 | 一种真空蒸镀试验装置及其方法 |
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| JPS6372869A (ja) * | 1986-09-16 | 1988-04-02 | Nippon Steel Corp | 熱伝導性に優れたステンレスフオイル |
| JPS6379955A (ja) | 1986-09-20 | 1988-04-09 | Nippon Steel Corp | ろう付け性に優れたステンレス鋼帯の製造方法 |
| JPH02122064A (ja) * | 1988-10-28 | 1990-05-09 | Sumitomo Metal Ind Ltd | 耐銹性に優れたステンレス鋼材及びその製法 |
| US5429843A (en) * | 1991-11-21 | 1995-07-04 | Nisshin Steel Co., Ltd. | Vapor deposition for formation of plating layer |
| EP0570618B1 (en) * | 1992-05-21 | 1996-11-06 | Nissin Electric Company, Limited | Film forming method and apparatus |
| SE508150C2 (sv) | 1996-08-30 | 1998-09-07 | Sandvik Ab | Förfarande för att tillverka band av ferritiskt, rostfritt FeCrAl-stål |
| SE527180C2 (sv) * | 2003-08-12 | 2006-01-17 | Sandvik Intellectual Property | Rakel- eller schaberblad med nötningsbeständigt skikt samt metod för tillverkning därav |
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| SE0302902D0 (sv) | 2003-11-04 |
| CN1875128A (zh) | 2006-12-06 |
| SE0302902L (sv) | 2005-05-05 |
| JP4819688B2 (ja) | 2011-11-24 |
| EP1682691A1 (en) | 2006-07-26 |
| KR20060115380A (ko) | 2006-11-08 |
| EP1682691B1 (en) | 2017-01-11 |
| SE527385C2 (sv) | 2006-02-21 |
| KR101141573B1 (ko) | 2012-07-12 |
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