WO2013086805A1 - 一种多层铝铬复合金属电缆涂层及其制备方法 - Google Patents

一种多层铝铬复合金属电缆涂层及其制备方法 Download PDF

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WO2013086805A1
WO2013086805A1 PCT/CN2012/071933 CN2012071933W WO2013086805A1 WO 2013086805 A1 WO2013086805 A1 WO 2013086805A1 CN 2012071933 W CN2012071933 W CN 2012071933W WO 2013086805 A1 WO2013086805 A1 WO 2013086805A1
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layer
aluminum
chromium
cable
composite
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PCT/CN2012/071933
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French (fr)
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吴炳锋
丁忠海
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飞洲集团有限公司
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Priority to KR1020147014271A priority Critical patent/KR20140091720A/ko
Publication of WO2013086805A1 publication Critical patent/WO2013086805A1/zh

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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
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating

Definitions

  • the invention patent relates to a multi-layer aluminum-chromium composite cable coating and a treatment method thereof,
  • the coating is applied to the surface of the cable metal materials such as copper, carbon steel, stainless steel, and hard alloy, and is resistant to corrosion and corrosion, and the metal texture effect is increased. It belongs to the field of metal surface treatment, metal corrosion and protection and machining.
  • the electroplating technology basically uses the substrate as the anode, and the material to be plated is the cathode, and the voltage is applied to uniformly deposit the material to be plated on the surface of the substrate, thereby increasing the wear resistance, the light reflection property of the substrate, and the aesthetic effect of the metal effect. Corrosion resistance can also be achieved to some extent by selecting different coatings.
  • the plating material is not environmentally friendly, and there is a problem that the environment is polluted during the process.
  • Some vacuum plating techniques partially solve the problem of emissions to some extent, but the adhesion between the coating and the substrate is poor.
  • Another type of method is to directly spray the metal paint on the substrate to achieve the anti-corrosion effect, but the surface hardness is low, and it is easy to wear. Once worn, it can no longer play the role of corrosion resistance.
  • the invention combines the advantages of different methods, and in the process of treating the substrate, a composite coating which is wear-resistant and corrosion-resistant is adhered to the surface. It also increases the reflective properties of the substrate, has a metallic aesthetic effect, and is environmentally friendly during processing, reducing costs.
  • the object of the present invention is to provide a wear-resistant and corrosion-resistant aluminum-chromium composite coating for copper or hard cable alloy, and a preparation method and application thereof; the coating has a metallic aesthetic effect and does not pollute during processing. Environment, reduce costs; the first use of aluminum-chromium combined composite sub-nano structure design, reasonable ratio, and environmentally friendly processing technology, suitable for large-scale production.
  • Multi-layer aluminum-chromium composite cable coating and preparation method thereof characterized in that: the structure of the aluminum-chromium composite coating is: the bottom layer is an adhesive layer, the middle is an aluminum-chromium composite metal layer, and the upper layer is organic anti-layer Corrosion layer.
  • the composite metal layer mainly contains aluminum and chromium, and the content of aluminum chromium is in mass ratio: 85-90:15-10
  • the coating is applied to the surface of a copper substrate, a carbon steel, a stainless steel or a hard alloy cable metal substrate.
  • the structure of each layer reaches the sub-nano structure, the intermediate aluminum-chromium composite metal layer is 0.5-0.6 ⁇ m, and the upper organic anti-corrosion layer is 0.2-0.3 ⁇ m.
  • the underlying adhesive layer is 0.2-0.3 ⁇ m and the aluminum content is 20-40%. Wherein the underlying adhesive layer further comprises methyl ether in an amount of 10-20% .
  • the composite metal coating base layer has an adhesive layer, and the main component is silica and a polymer resin, and the mass ratio thereof is: 40-55: 65-75
  • the adhesive layer bonds the composite metal layer and the substrate to increase adhesion.
  • the organic anti-corrosion layer is mainly composed of modified acrylic acid.
  • the method for preparing the cable aluminum-chromium composite coating is sequentially performed as follows
  • the purity of the aluminum target needs to be 99.99%, and the purity of the chromium target needs to be 99.8%.
  • the substrate obtained in the step (1) is placed in the coating machine, and the vacuum is 1.3 ⁇ 10 -3 Pa, heated to 450-500 degrees Celsius, hold for 40 minutes, pass 99.99% mixed gas into the coating machine, release 1200v voltage arc, bombard for about 20 minutes, fill with nitrogen, reduce the pressure to about 2pa, cool to 100 Boiled below Celsius;
  • step (2) The obtained substrate hoisting is statically placed in a 100,000-class dust-free space in which a spray-like solution is uniformly filled with an anti-corrosion layer in a mist, and the substrate is exposed to a misty solution for 10 minutes.
  • Leveling 10min at 70 Curing in the environment of Celsius for 10 min, drying at room temperature for 10 min, drying at room temperature and in a clean space.
  • the raw material composition and preparation of the adhesive layer spray solution are as follows:
  • the raw material does not require processing, and includes processes such as conventional polishing by those skilled in the art.
  • the invention has the beneficial effects that the bottom layer of the coating layer is an adhesive layer, the middle layer is a metal layer, and the surface layer is an anti-corrosion layer; the adhesion between the coating layer and the metal substrate is strong; the hardness of the surface layer can reach 4H. It has a metallic luster and is reflective. The effect is consistent with the ordinary plating effect; the corrosion resistance is consistent with that of ordinary electroplated products; the composite layer is an aluminum-chromium alloy.
  • Multi-layer aluminum-chromium composite cable coating and preparation method thereof characterized in that: the structure of the aluminum-chromium composite coating is: the bottom layer is an adhesive layer, the middle is an aluminum-chromium composite metal layer, and the upper layer is organic anti-layer Corrosion layer.
  • the composite metal layer mainly contains aluminum and chromium, and the content of aluminum chromium is in mass ratio: 85-90:15-10
  • the coating is applied to the surface of a copper, carbon steel, stainless steel or carbide cable metal substrate.
  • the structure of each layer reaches the sub-nano structure, the intermediate aluminum-chromium composite metal layer is 0.5-0.6 ⁇ m, and the upper organic anti-corrosion layer is 0.2-0.3 ⁇ m.
  • the underlying adhesive layer is 0.2-0.3 ⁇ m and the aluminum content is 20-40%. Wherein the underlying adhesive layer further comprises methyl ether in an amount of 10-20% .
  • the composite metal coating base layer has an adhesive layer, and the main component is silica and a polymer resin, and the mass ratio thereof is: 40-55: 65-75
  • the adhesive layer bonds the composite metal layer and the substrate to increase adhesion.
  • the organic anti-corrosion layer is mainly composed of modified acrylic acid.
  • the method for preparing the cable aluminum-chromium composite coating is sequentially performed as follows
  • the purity of the aluminum target needs to be 99.99%, and the purity of the chromium target needs to be 99.8%.
  • the substrate obtained in the step (1) is placed in the coating machine, and the vacuum is 1.3 ⁇ 10 -3 Pa, heated to 450-500 degrees Celsius, hold for 40 minutes, pass 99.99% mixed gas into the coating machine, release 1200v voltage arc, bombard for about 20 minutes, fill with nitrogen, reduce the pressure to about 2pa, cool to 100 Boiled below Celsius;
  • step (2) The obtained substrate hoisting is statically placed in a 100,000-class dust-free space in which a spray-like solution is uniformly filled with an anti-corrosion layer in a mist, and the substrate is exposed to a misty solution for 10 minutes.
  • Leveling 10min at 70 Curing in the environment of Celsius for 10 min, drying at room temperature for 10 min, drying at room temperature and in a clean space.
  • the raw material composition and preparation of the adhesive layer spray solution are as follows:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Insulated Conductors (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

一种多层铝铬复合电缆涂层及其制备方法，其中所述涂层的结构为：底层为粘合层，中间为铝铬复合金属层，最上层为有机防腐蚀层。涂层通过粘合层溶液喷涂和固化、金属层溅射、有机防腐层溶液喷涂和固化等工序来制备。

Description

一种多层铝铬复合金属电缆涂层及其制备方法
技术领域
本发明专利涉及一种多层铝铬复合电缆涂层及其处理方法 , 该涂层应用于铜、普碳钢、不锈钢、硬质合金等电缆金属材料表面的耐磨、耐腐蚀，并增加金属质感效果。属于金属表面处理、金属腐蚀和防护及机械加工领域。
背景技术
传统对电缆金属基材进行表面处理，起到抗腐蚀、同时达到耐磨的效果，是使用电镀技术将一种或复合耐腐蚀材料附着在基材表面来实现。电镀技术基本是以基材为阳极，待镀材料为阴极，施以电压，使待镀材料均匀地沉积在基材表面，增加基材的耐磨性、反光性、增进金属效果的美观。通过选择不同的镀层也可以一定程度上做到耐腐蚀的作用。但在电镀过程中镀层材料不环保，存在工艺过程中排放污染环境的问题。一些真空电镀技术在某种程度上部分解决了排放的问题，但镀层与基材间附着力差。
另外一类方法是直接对基材进行金属漆喷涂，来达到抗腐蚀的效果，但表面硬度低，极易磨损，一旦磨损后就无法再起到耐腐蚀的作用。本发明综合不同方法的优点，在对基材的处理过程中，使其表面附着一种即耐磨又耐腐蚀的复合涂层。同样增加了基材的反光性，有金属美观效果，同时加工过程中环保，降低成本。
发明内容
本发明的目的在于对铜或硬质电缆合金提供一种耐磨、耐腐蚀的铝铬复合涂层及其制备方法与应用；使涂层具有金属美观效果的同时，在加工过程中不会污染环境，降低成本；首次采用了铝铬结合的复合亚纳米结构设计，合理的配比、以及环保的加工工艺，适合大规模生产。
一种多层铝铬复合电缆涂层及其制备方法，其特征在于：所述的铝铬复合涂层的结构为：底层为粘合层，中间为铝铬复合金属层，最上层为有机防腐蚀层。
所述的复合金属层中主要含有物质为铝和铬，铝铬含量按质量份比为： 85-90:15-10 ；该涂层使用于铜墙、普碳钢、不锈钢或硬质合金电缆金属基材表面。各层结构均达到亚纳米结构 , 中间铝铬复合金属层为 0.5-0.6 μ m ，上层有机防腐蚀层为 0.2-0.3 μ m 。其中底层粘合层为 0.2-0.3 μ m ，铝含量为 20-40% 。其中底层粘合层还包括甲醚，其含量为 10-20% 。所述的复合金属涂层基层具有一层粘合层，主要成分为二氧化硅和高分子树脂，二者质量份比为： 40-55:65-75 ；该粘合层粘合复合金属层及基材，增加附着力。所述的有机防腐蚀层以改性丙烯酸为主要成份。
所述的电缆铝铬复合涂层的其制备方法，该方法按以下步骤依次进行
（ 1 ）将基材吊装静置于十万级无尘空间内，在该空间内呈雾状均匀充满粘合层的喷涂溶液，将基材暴露于雾状喷涂溶液中 3min ，流平 8min ，在 70 摄氏度的环境下固化 10min ，在常温下干燥 8min ；
（ 2 ）用离子真空镀膜机，铝靶纯度需达到 99.99% ，铬靶纯度需达到 99.8% ，将步骤（ 1 ）中的得到的基材放入镀膜机内，抽真空指 1.3 × 10-3pa ，加热至 450-500 摄氏度，保持 40 分钟，向镀膜机中通入 99.99% 的混合气体，释放 1200v 的电压弧，轰击 20 分钟左右，充入氮气，将压力降至 2pa 左右，冷却至 100 摄氏度以下出炉；
（ 3 ）将步骤（ 2 ）中的得到的基材吊装静置于十万级无尘空间内，在该空间内呈雾状均匀充满防腐蚀层喷涂溶液，将基材暴露于雾状溶液中 10min 。流平 10min ，在 70 摄氏度的环境下固化 10min ，在常温下干燥 10min 在常温下并洁净空间下干燥。
所述的粘合层喷涂溶液的原料组成及制备为：
将 50-100 目的纯铝粉与改性丙烯酸、聚氨酯、环氧树脂调和成的缓冲溶剂调和，并加入含有甲醚、丁醚和丁醇等材料的稀释融合剂加以调配；加入适量水后，进行调色；铝粉与缓冲剂的质量调配比例应为 1 ： 3.45 - 1 ： 8.4 之间，稀释融合剂与缓冲剂的质量调配比例应在 2 ： 1 - 3.45 ： 1 之间；
（ 2 ）电缆铝铬复合金属层的铝铬质量比例为： 40-55:65-75 ；
（ 3 ）防腐蚀层喷涂溶液的原料组成质量比例为：改性丙烯酸 1-2 ：聚氨酯 1-3 ：：环氧树脂 0.5-1 及水调配而成。
所述原材不需要进行处理之前的还包括本领域技术人员的常规抛光等工艺。
本发明的有益效果是：涂层底层为粘合层，中间为金属层，表层为防腐蚀层；涂层与金属基材之间的附着力强；表层硬度可达 4H ；呈金属光泽，有反射性，效果可与普通电镀效果一致；防腐蚀能力与普通电镀制品性能一致；复合层为一种铝铬合金。
具体实施方式 ：
为了使本发明的技术手段、创作特征与达成目的易于明白理解，以下结合具体实施例进一步阐述本发明。
实施例 1 ：
一种多层铝铬复合电缆涂层及其制备方法，其特征在于：所述的铝铬复合涂层的结构为：底层为粘合层，中间为铝铬复合金属层，最上层为有机防腐蚀层。
所述的复合金属层中主要含有物质为铝和铬，铝铬含量按质量份比为： 85-90:15-10 ；该涂层使用于铜、普碳钢、不锈钢或硬质合金电缆金属基材表面。各层结构均达到亚纳米结构 , 中间铝铬复合金属层为 0.5-0.6 μ m ，上层有机防腐蚀层为 0.2-0.3 μ m 。其中底层粘合层为 0.2-0.3 μ m ，铝含量为 20-40% 。其中底层粘合层还包括甲醚，其含量为 10-20% 。所述的复合金属涂层基层具有一层粘合层，主要成分为二氧化硅和高分子树脂，二者质量份比为： 40-55:65-75 ；该粘合层粘合复合金属层及基材，增加附着力。所述的有机防腐蚀层以改性丙烯酸为主要成份。
所述的电缆铝铬复合涂层的其制备方法，该方法按以下步骤依次进行
（ 1 ）将基材吊装静置于十万级无尘空间内，在该空间内呈雾状均匀充满粘合层的喷涂溶液，将基材暴露于雾状喷涂溶液中 3min ，流平 8min ，在 70 摄氏度的环境下固化 10min ，在常温下干燥 8min ；
（ 2 ）用离子真空镀膜机，铝靶纯度需达到 99.99% ，铬靶纯度需达到 99.8% ，将步骤（ 1 ）中的得到的基材放入镀膜机内，抽真空指 1.3 × 10-3pa ，加热至 450-500 摄氏度，保持 40 分钟，向镀膜机中通入 99.99% 的混合气体，释放 1200v 的电压弧，轰击 20 分钟左右，充入氮气，将压力降至 2pa 左右，冷却至 100 摄氏度以下出炉；
（ 3 ）将步骤（ 2 ）中的得到的基材吊装静置于十万级无尘空间内，在该空间内呈雾状均匀充满防腐蚀层喷涂溶液，将基材暴露于雾状溶液中 10min 。流平 10min ，在 70 摄氏度的环境下固化 10min ，在常温下干燥 10min 在常温下并洁净空间下干燥。
所述的粘合层喷涂溶液的原料组成及制备为：
将 50-100 目的纯铝粉与改性丙烯酸、聚氨酯、环氧树脂调和成的缓冲溶剂调和，并加入含有甲醚、丁醚和丁醇等材料的稀释融合剂加以调配；加入适量水后，进行调色；铝粉与缓冲剂的质量调配比例应为 1 ： 3.45 - 1 ： 8.4 之间，稀释融合剂与缓冲剂的质量调配比例应在 2 ： 1 - 3.45 ： 1 之间；
（ 2 ）电缆铝铬复合金属层的铝铬质量比例为： 40-55:65-75 ；
（ 3 ）防腐蚀层喷涂溶液的原料组成质量比例为：改性丙烯酸 1-2 ：聚氨酯 1-3 ：：环氧树脂 0.5-1 及水调配而成。

Claims (1)

1. 一种多层铝铬复合电缆涂层及其制备方法，其特征在于：所述的铝铬复合涂层的结构为：底层为粘合层，中间为铝铬复合金属层，最上层为有机防腐蚀层。
2. 如权利要求 1 所述的电缆铝铬复合涂层，其特征在于：所述的复合金属层中主要含有物质为铝和铬，铝铬含量按质量份比为： 85-90:15-10 ；该涂层使用于铜、普碳钢、不锈钢或硬质合金电缆金属基材表面。
3. 如权利要求 2 所述的电缆铝铬复合涂层，其特征在于：各层结构均达到亚纳米结构 , 中间铝铬复合金属层为 0.5-0.6 μ m ，上层有机防腐蚀层为 0.2-0.3 μ m 。
4. 如权利要求 3 所述的电缆铝铬复合涂层，其特征在于：其中底层粘合层为 0.2-0.3 μ m ，铝含量为 20-40% 。
5. 如权利要求 4 所述的电缆铝铬复合涂层，其特征在于：其中底层粘合层还包括甲醚，其含量为 10-20% 。
6. 如权利要求 5 所述的电缆铝铬复合涂层，其特征在于：所述的复合金属涂层基层具有一层粘合层，主要成分为二氧化硅和高分子树脂，二者质量份比为： 40-55 ： 65-75 ；该粘合层粘合复合金属层及基材，增加附着力。
7. 如权利要求 6 所述的电缆铝铬复合涂层，其特征在于：所述的有机防腐蚀层以改性丙烯酸为主要成份。
8. 如根据权利 1-7 之一所述的电缆铝铬复合涂层的其制备方法，其特征在于：该方法按以下步骤依次进行
（ 1 ）将基材吊装静置于十万级无尘空间内，在该空间内呈雾状均匀充满粘合层的喷涂溶液，将基材暴露于雾状喷涂溶液中 3min ，流平 8min ，在 70 摄氏度的环境下固化 10min ，在常温下干燥 8min ；
（ 2 ）用离子真空镀膜机，铝靶纯度需达到 99.99% ，铬靶纯度需达到 99.8% ，将步骤（ 1 ）中的得到的基材放入镀膜机内，抽真空指 1.3 × 10-3pa ，加热至 450-500 摄氏度，保持 40 分钟，向镀膜机中通入 99.99% 的混合气体，释放 1200v 的电压弧，轰击 20 分钟左右，充入氮气，将压力降至 2pa 左右，冷却至 100 摄氏度以下出炉；
（ 3 ）将步骤（ 2 ）中的得到的基材吊装静置于十万级无尘空间内，在该空间内呈雾状均匀充满防腐蚀层喷涂溶液，将基材暴露于雾状溶液中 10min ；流平 10min ，在 70 摄氏度的环境下固化 10min ，在常温下干燥 10min 在常温下并洁净空间下干燥；
所述的粘合层喷涂溶液的原料组成及制备为：
将 50-100 目的纯铝粉与改性丙烯酸、聚氨酯、环氧树脂调和成的缓冲溶剂调和，并加入含有甲醚、丁醚和丁醇等材料的稀释融合剂加以调配；加入适量水后，进行调色；铝粉与缓冲剂的质量调配比例应为 1 ： 3.45 - 1 ： 8.4 之间，稀释融合剂与缓冲剂的质量调配比例应在 2 ： 1 - 3.45 ： 1 之间；
（ 2 ）电缆铝铬复合金属层的铝铬质量比例为： 40-55:65-75 ；
（ 3 ）防腐蚀层喷涂溶液的原料组成质量比例为：改性丙烯酸 1-2 ：聚氨酯 1-3 ：：环氧树脂 0.5-1 及水调配而成。
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