CN110225986A - 新产品及其用途 - Google Patents

新产品及其用途 Download PDF

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CN110225986A
CN110225986A CN201880008470.9A CN201880008470A CN110225986A CN 110225986 A CN110225986 A CN 110225986A CN 201880008470 A CN201880008470 A CN 201880008470A CN 110225986 A CN110225986 A CN 110225986A
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S·迪兹达尔
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Hoganas AB
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/05—Light metals
    • B22F2301/052—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/35—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/40—Carbon, graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2303/00—Functional details of metal or compound in the powder or product
    • B22F2303/20—Coating by means of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2303/00—Functional details of metal or compound in the powder or product
    • B22F2303/30—Coating alloy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/05—Submicron size particles
    • B22F2304/058—Particle size above 300 nm up to 1 micrometer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/15—Millimeter size particles, i.e. above 500 micrometer

Abstract

本发明涉及新型预合金化金属基粉末，其旨在用于金属部件的表面涂覆。使用例如激光熔覆或等离子转移电弧焊(PTA)或热喷涂(例如HVOF)沉积该粉末。该粉末可用于减少摩擦和改进沉积涂层的减磨损性质。这样的涂层还可改进机械加工性。作为减摩擦或减磨损组分，可以使用在预合金化粉末中的硫化锰或硫化钨的夹杂物。

Description

新产品及其用途
发明领域
本发明涉及三种不同的预合金化金属基粉末的粉末混合物，其旨在用于金属部件的表面涂覆。使用例如激光熔覆(laser cladding)或等离子转移电弧焊(plasma transferarc welding，PTA)或热喷涂(thermal spray)(例如HVOF)沉积该粉末混合物。该粉末混合物可用于减少摩擦和改进沉积涂层的减磨损性质。这样的涂层还可改进机械加工性。作为减摩擦或减磨损组分，可以使用在预合金化粉末中的硫化锰或硫化钨的夹杂物(inclusion)。
背景
热表面处理，即热喷涂和焊粉(welding powder)等级(grade)广泛用于涂覆组件表面以抗磨损和腐蚀。基于Fe，Ni和Co的等级已知从根本上改进暴露于磨损和/或腐蚀的组件的使用寿命。但是，仍有大量的用途需要改进组件使用寿命。此外，Ni和Co在全球市场上的高价格和有限供应量也要求更长的使用寿命改进。最后，新的涂覆沉积法，如激光熔覆、冷喷涂和高速喷涂的发展开启了合金化、更精确的涂覆工艺控制和更高自动化的可能性，因此需要更多类型的粉末。
改进摩擦和磨损性质的一种方法可能是将固体润滑剂并入热表面处理等级(thermal surfacing grade)中以使沉积的涂层包括减摩擦和减磨损物质，同时保持可接受的耐腐蚀性和硬度水平。
固体润滑剂是能够减少互相贴着滑动的两个表面之间的摩擦和磨损而不需要液体介质的软固相材料。被考虑为固体润滑剂的材料需要满足至少下列标准：附着于接触表面–粘性；低剪切强度-低固有摩擦；低硬度–低磨蚀度(abrasivity)和对预期环境的热化学稳定性。固体润滑剂的实例是滑石、石墨、硫化锰(MnS)、二硫化钼(MoS2)或二硫化钨(WS2)。固体润滑剂的使用可在下列方面提供优点：在极低或极高温度下的稳定性；在极端环境，如冷或热环境或具有高辐射水平的环境中的稳定性；机械设计问题(更轻的设计、降低的临界速度)或能够承载极端负荷。
长期以来，固体润滑剂在热表面处理中的使用是困难的命题，原因在于许多固体润滑剂是金属硫化物并且焊缝中的甚至痕量的硫也会造成开裂和/或腐蚀。
Skarvelis等人；ASME J.Tribol.132(2010)031302-1–031302-8Surf.&Coat.Techn.203(2009)1384–1394和Trib.Int.42(2009)1765–1770描述了将MnS粉末与金属粉末混合并在例如PTA(等离子转移电弧焊)中使用所得粉末混合物。
在Senad等人；WO2014090922中公开了与作为固体润滑剂的MnS联合使用金属粉末的另一实例。
但是，固体润滑剂可能具有与油或油脂相比高的摩擦系数；当不可能更新时固体润滑剂膜的磨损寿命有限；与油或油脂相比没有冷却能力或冷却能力有限，或具有由碎屑和残留粒子造成的堵塞倾向。
发明概述
有可能作为金属粉末中的独立组分，即作为分开的粉末粒子加入例如锰和硫。这些组分随后(当金属粉末熔融时)形成所谓的固体润滑剂(在这种情况下是MnS)。但是，存在具有例如Mn和S作为独立组分的缺点，如严重成尘(dusting)和在最终表面涂层中形成MnS的不均匀夹杂物。
本发明人的发明人现在已经发现，可以有利地将固体润滑剂的各组分添加到分开的金属粉末中，然后在进行表面涂覆程序的同时或在进行表面涂覆程序之前混合金属粉末。简言之，混合三种粉末：一种含锰或钨的金属粉末；一种含硫的金属粉末；和一种铁基粉末以实现各种组分之间的适当比率。Mn、W和S在它们各自的粉末粒子中预合金化。然后将这三种金属粉末混合在一起并用于表面涂覆程序，其中将金属粒子熔融，并在熔体(也称为熔池(melt pool))中形成MnS或WS夹杂物。
在MnS的情况下，由于在熔池中形成MnS，不容易从熔体顶部除去熔渣。熔渣留在表面涂层如堆焊焊缝(overlay welding seam)的顶部或侧面。如果在侧面，下一焊缝会覆盖熔渣并且熔渣没有足够的时间移到焊缝顶部。因此，所产生的硬表面的微结构既包括细分散的MnS，又包括熔渣MnS。
令人惊讶地，本发明人已经注意到根据本发明的粉末混合物可用于对表面质量(如表面光洁度、熔渣形成或尺寸变异性)具有高宽容度的用途。所产生的硬表面因此适合用于重型户外设备，如轨道、铁路和电车轨道中的轮子、采矿、农业、采油、采气和施工工具。
附图
图1 S-粉末包覆销(pin)和碳钢销在500 MPa的Hert ian最大接触压力下的磨损率vs.滑动速度。
图2 S-粉末包覆销和碳钢销在1000 MPa的Hertzian最大接触压力下的磨损率vs.滑动速度。
图3 S-粉末包覆(S-powder clad)的SEM显微照片，显微照片的顶部是磨损试验表面。
图4 S-粉末包覆(clad)的SEM显微照片，显微照片的顶部是磨损试验表面。
详述
本文中和权利要求书中的所有百分比是重量％。
本发明是一种粉末混合物，其含有：
i)具有下列组成的雾化金属粉末：C，0.05-0.5％；Si，2.0-4.0％；B，0.8-1.3％；Cr，2-10％；Fe，3-15％；Al，0.3-0.5％；Mn，5-15％；余量是Ni；
ii)具有下列组成的雾化金属粉末：C，0.05-0.2％；Si，2.2-2.9％；B，0.8-1.3％；Cr，2.8-3.45％；Fe，1.4-2.3％；Al，0.3-0.5％；S，3-13％；余量是Ni；
iii)具有下列组成的雾化金属粉末：C，0.2-0.27％；Si，3.5％；B，1.6；Fe，2.5；Cr，7.5；余量是Ni。
本发明还是根据上文的粉末混合物，其中粉末之间的比率使得MnS的量为4-15％。
本发明还是根据上文的金属粉末，其中所述预合金化粉末的粒度为45μm至200mm，或50-150μm。
本发明还是一种通过激光熔覆或PTA(等离子转移电弧)用根据上文的金属粉末表面涂覆金属部件由此生产金属涂覆组件的方法。
之前已知的是，固体润滑剂如MnS或WS可用于表面涂覆领域，由此在基底表面上形成硬相。MnS或WS充当所谓的固体润滑剂。本发明人已经表明，金属粉末的混合物可用于表面涂覆程序，如等离子转移电弧，并且通过选择各金属粉末中的恰当组分，可在所得表面涂层或硬相中形成固体润滑剂。该金属粉末可以是镍、钴或铁基的。
在根据本发明的混合物中使用三种雾化金属粉末：
在一个实施方案中，粉末M可具有下列组成：C，0.05-0.5％；Si，2.0-4.0％；B，0.8-1.3％；Cr，2-10％；Fe，3-15％；Al，0.3-0.5％；Mn，5-15％；余量是Ni。该粉末通过含有所述量的上述元素的熔体的雾化制备。所得粉末含有Mn作为金属合金基质中的夹杂物。这一粉末在本文中称为“粉末M”；
粉末S可具有下列组成：C，0.05-0.2％；Si，2.2-2.9％；B，0.8-1.3％；Cr，2.8-3.45％；Fe，1.4-2.3％；Al，0.3-0.5％；S，3-13％；余量是Ni。该粉末通过含有所述量的上述元素的熔体的雾化制备。所得粉末含有S作为金属合金基质中的夹杂物。这一粉末在本文中称为“粉末S”；且第三种粉末是1540–标准等级。这一粉末在本文中称为“粉末MP”。
混合粉末S、粉末Mn和粉末P以在下文提到的包覆法中形成的最终熔池中实现4-15％MnS。这一粉末混合物在本文中称为“混合物PM”。
混合物PM尤其适用于包覆焊接(weld cladding)法，如激光熔覆或PTA。此外，热喷涂，例如火焰喷涂、HVOF、HVAF、冷喷涂、等离子体喷涂等也是合适的用途。
预合金化的镍、铁或钴基粉末优选通过包括Mn，W或S和选自C、Si、B、Cr、Fe、Al、Ni、Co和V的其它合金元素的熔体的水或气体雾化制成。
预合金化的粉末合金的粒度通常为10μm至800μm、或10μm至200μm、或优选15-150μm、或50-150μm。
在一个方面中，本发明提供一种通过沉积技术，如激光熔覆或PTA(等离子转移电弧)；热喷涂法，如HVOF(高速氧燃料喷涂)、HVAF(高速乙炔燃料喷涂)或等离子体喷涂；或通过淤浆法，如离心浇铸用上文提到的金属粉末表面涂覆金属部件的方法。
在另一方面中，本发明还提供通过上述制成的金属部件，其适合被根据本发明的粉末涂覆，用于机械中的干摩擦接触，例如工业阀门、金属板成形(SMF)工具、铁工厂中的运输辊、裁纸刀和玻璃模具。
实施例
实施例1
预合金化粉末的制备
具有下列组成的金属粉末：C，0.05-0.5％；Si，2.0-4.0％；B，0.8-1.3％；Cr，2-10％；Fe，3-15％；Al，0.3-0.5％；Mn，5-15％；余量是Ni通过含有所述量的上述元素的熔体的雾化制备。所得粉末含有Mn作为金属合金基质中的夹杂物。这一粉末在本文中称为“粉末M”。
具有下列组成的另一金属粉末：C，0.05-0.2％；Si，2.2-2.9％；B，0.8-1.3％；Cr，2.8-3.45％；Fe，1.4-2.3％；Al，0.3-0.5％；S，3-13％；余量是Ni通过含有所述量的上述元素的熔体的雾化制备。所得粉末含有S作为金属合金基质中的夹杂物。这一粉末在本文中称为“粉末S”。
1540–标准等级，这一粉末在本文中称为“粉末MP”。
混合粉末S、粉末Mn和粉末P，3MA粉末混合物，以实现4-15％MnS。
实施例2
通过使用PTA沉积而施加粉末
如下将预合金化或预混粉末施加到试验样品上：通过PTA(等离子转移电弧)用设定为实现5-15％稀释的参数将粉末A沉积到S235JRG(基础结构钢)基板上。
实施例3
在与基底熔结前将粉末S以粉末形式手动铺展在基底上。该粉末如何fuwed？
实施例4
也通过激光熔覆将根据本发明的粉末施加到基底上。来自粉末S的涂层看起来产生比通过PTA施加时细的MnS夹杂物尺寸。
实施例5
进行环块(block on ring)磨损测试，并且显示3MA粉末混合物在金属表面涂层或包覆层中的有益作用。试样是矩形块10x10x 50mm，其中基础金属是常用的低碳结构钢(ENS235 JRG，ASTM A570 Gr.36)且在完工状态测量(as finished measure)中表面层为至少0.5mm厚。试验表面具有通过研磨制备的表面粗糙度Ra为0.3-0.4μm的磨光表面(groundfinish)。相对的环(counter ring)由UIC 900A钢轨钢制成。该试验无润滑，即干燥，并在测试前小心清洁试样，然后用乙醇去脂。作为磨损机制映射试验(wear mechanism mapping trial)进行该试验。试验法向载荷为5和42 N，相当于500或1000 MPa的最大Hertzian接触压力。滑动速度为0.045、0.13、0.37、1.1和2.9m/s。总滑动距离为800米。在500或1000 MPa的接触压力下的结果显示在图1和图2中。图3和图4图解S-粉末激光熔覆的微结构。

Claims (4)

1.一种粉末混合物，其含有：
i)具有下列组成的雾化金属粉末：C，0.05-0.5％；Si，2.0-4.0％；B，0.8-1.3％；Cr，2-10％；Fe，3-15％；Al，0.3-0.5％；Mn，5-15％；余量是Ni；
ii)具有下列组成的雾化金属粉末：C，0.05-0.2％；Si，2.2-2.9％；B，0.8-1.3％；Cr，2.8-3.45％；Fe，1.4-2.3％；Al，0.3-0.5％；S，3-13％；余量是Ni；
iii)具有下列组成的雾化金属粉末：C，0.2-0.27％；Si，3.5％；B，1.6；Fe，2.5；Cr，7.5；余量是Ni。
2.根据权利要求1的粉末混合物，其中粉末之间的比率使得MnS的量为4-15％。
3.根据权利要求1或2的金属粉末，其中所述预合金化粉末的粒度为45μm至200mm，或50-150μm。
4.通过激光熔覆或PTA(等离子转移电弧)用根据权利要求1-3任一项的金属粉末表面涂覆金属部件、由此生产金属涂覆组件的方法。
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