CN104053810A - 等离子喷涂工艺 - Google Patents

等离子喷涂工艺 Download PDF

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CN104053810A
CN104053810A CN201280051252.6A CN201280051252A CN104053810A CN 104053810 A CN104053810 A CN 104053810A CN 201280051252 A CN201280051252 A CN 201280051252A CN 104053810 A CN104053810 A CN 104053810A
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alloy
plasma
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L·施拉姆
C·M·韦尔波特
A·施文克
E·豪泽
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Ford Global Technologies LLC
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    • 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
    • C23C4/08—Metallic material containing only metal elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/0075—Nozzle arrangements in gas streams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • B05B7/22—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc
    • B05B7/222—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc
    • B05B7/224—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc the material having originally the shape of a wire, rod or the like
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • 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
    • 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
    • C23C4/131—Wire arc spraying
    • 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
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B13/00—Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00
    • B05B13/06—Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00 specially designed for treating the inside of hollow bodies
    • B05B13/0627—Arrangements of nozzles or spray heads specially adapted for treating the inside of hollow bodies
    • B05B13/0636—Arrangements of nozzles or spray heads specially adapted for treating the inside of hollow bodies by means of rotatable spray heads or nozzles

Abstract

本发明涉及一种用于通过热喷涂，特别是通过等离子喷涂产生涂层的工艺，其中用合金在内部涂覆部件，特别是汽缸套。提出的是，供给作为输送气体的氮气，喷涂添加剂是被引导到等离子流内的实心合金丝，并且在没有其他粉末的情况下进行涂覆。

Description

等离子喷涂工艺
技术领域
本发明涉及一种用于通过热喷涂，特别是通过等离子喷涂产生涂层的工艺，其中用合金，优选用铁合金涂覆部件，特别是例如由铝制造的内燃发动机的汽缸套。
背景技术
从EP1967601A2已知的是，通过进行金属丝电弧喷涂用铁合金涂覆例如铝汽缸体，特别是其汽缸支撑表面。在这方面，EP1967601A2提出了铁合金的使用，所述铁合金除其他外含有5至25％(按重量计)的铬。在EP1967601A2的示例中，向铁水供给其他粉末(准确地说碳化硼)是必不可少的。EP1967601A2的金属丝电弧喷涂工艺涉及所谓的TWAS工艺，其中以通过两根金属丝传输电力的方式向喷嘴供给两根金属丝。如果两根金属丝接触，通过持续短路来形成熔化金属丝的电弧。排出压缩空气或惰性气体(诸如氮气)的喷嘴位于所述喷嘴的下游。该气流使熔化的铁合金雾化，并将其与熔化的碳化硼一起供给至将要被涂覆的表面上。
DE4411296A1和DE4447514Al涉及通过等离子喷涂提供的涂层，然而其中金属粉末或填充金属丝被熔化，并且其中通过金属的氮化物向材料混合物供给氮以便硬化涂层。
目前的内燃发动机及其汽缸体可以由金属或铝铸造而成，铝汽缸体在其汽缸孔上特别具有铁或金属层。可以通过热工艺喷涂金属层。上述工艺被称为热喷涂工艺。
所谓的PTWA(等离子转移金属丝电弧)内涂层工艺也是已知的。在该工艺中，从内侧用丝状的喷涂添加剂涂覆孔(汽缸孔)。这里，因此，仅供应单个丝状的喷涂添加剂，使用填充金属丝或其他供应喷涂粉末是可能的。等离子撞击预先加热的丝状的喷涂添加剂。等离子气体通常是氩气-氮气混合气。在PTWA工艺中，空气或压缩空气被作用输送气体或雾化气体。通过该工艺产生的层表现低孔隙率的特点。迄今为止，已经证明PTWA内涂层工艺适合于汽缸孔的内涂层。
然而，已经发现，迄今为止，对于汽缸孔而言，通过涂层工艺产生的金属或铁涂层不能抵抗含有乙醇的燃料或乙醇燃料的特定腐蚀情况。特别是在相当长的时间内不使用机动车辆或内燃发动机(例如，这可以是当车辆或内燃发动机在假期期间被关闭时的情况)时会观察到这种情况。甚至含有17％(按重量计)的铬的合金对保护性涂层有少许的腐蚀作用。
发明内容
出于已认识到的汽缸孔的金属涂层上的由含有乙醇的燃料引起的腐蚀问题，本发明基于详述在引文中提到的那种工艺的目标，其使得形成在这方面得到改善的涂层成为可能。
根据本发明，通过具有权利要求1的特征的工艺来实现该目标。另外，在从属权利要求中描述了本发明的特别有利的改进。
应指出的是，在以下描述中逐个详述的特征可以以任何期望的技术上有意义的方式相互组合，并且公开了本发明的进一步改进。
本发明提出一种用于通过热喷涂，特别是通过等离子喷涂产生涂层的工艺，其中用合金涂覆部件，特别是由铝制造或铸造的内燃发动机的汽缸套，在此工艺中，至少供给作为输送气体的氮气，喷涂添加剂是被引导到等离子流内的实心合金丝，并且在没有其他粉末或没有粉末的情况下进行涂覆。在等离子喷涂是PTWA(等离子转移金属丝电弧)内涂层的情况下是有利的。
在本发明的背景下，术语“没有其他粉末”或“没有粉末”意味着既不使用充满粉末(金属)的填充金属丝也不使用单独供给的粉末(金属)。特别地，在本发明中，仅有利地利用了实心的(即同质的)或未填充的其他喷涂用的金属丝。用于涂层的合适的合金包含作为合金元素的铬和大部分的铁。在下文中进一步公开了优选的金属或铁合金。
由于作为输送气体的氮气的使用而非例如在已知的PTWA工艺中使用的空气或压缩空气，排除了迄今为止使用的由空气中的氧引起的铬的转变或退化，并且因此合金的全部铬部分能够被用来形成稳定的保护层。由于自由焓(或吉布斯自由能)的差异，主要形成氮化铝而不是氮化铬。这些氮化铝取代了在利用压缩空气的PTWA喷涂工艺过程中形成的现有抗磨损的金属氧化物。因此，本发明不仅产生抗磨损的涂层，而且产生抵抗特别是含有乙醇的燃料的腐蚀作用的保护(防腐蚀)层。在本发明的背景下，用于内燃发动机的含有乙醇的燃料可能含有作为乙醇的添加物的传统化石燃料(例如E5、E10或E85)，或可能以纯粹的形式(E100)使用。
在迄今为止已知的PTWA工艺，假设包含17％(按重量计)的Cr的合金特别适合于满足要求。与之相比，在本发明中有利地提供的是，其他喷涂用的金属丝包含具有12至35％(按重量计)的铬比例的铁合金。另外，合金成分可以是铝(2-10％(按重量计))、硅(0-1％(按重量计))、锰(0-1％(按重量计))、碳(0-1％(按重量计))以及其他成分，剩余物是铁，其他成分诸如为磷(0-1％(按重量计))、硫(0-0.09％(按重量计))、钼(0-5％(按重量计))、镍(0-1％(按重量计))、铜(0-0.5％(按重量计))、氮(0-0.5％(按重量计))。
在特别优选的实施例中，根据本发明的其他喷涂用的金属丝包含这样的铁合金，铁合金包含23％(按重量计)的Cr、5％(按重量计)的Al、少于0.5％(按重量计)的Si、少于0.2％(按重量计)的Mn、少于0.05％(按重量计)的C，剩余成分具有少于2％(按重量计)的比例，并且剩余物是铁。
不言而喻，根据本发明的工艺也能用于涂覆其他部件。
附图说明
图1示出了PTWA内涂层装置的喷嘴单元。
具体实施方式
图1示出了PTWA内部涂层装置的喷嘴单元1。PTWA(等离子转移金属丝电弧)涂层系统是用于涂覆孔，特别是内燃发动机的汽缸体中的汽缸的系统。喷嘴单元1由阴极2、等离子喷嘴3和作为阳极的导电的合金丝4组成，合金丝4被垂直地供给到等离子喷嘴3。例如，用于阴极2的材料优选钨，该材料也可以掺杂钍。通过在喷嘴主体6中制作并且切向地位于圆周的孔供给等离子气体5，例如氩气与氢气的混合气。阴极保持器7将阴极2与喷嘴主体6隔离。在金属丝供给装置15中引导合金丝4，以便它能够以转动的方式运动，并且能够被纵向地移动。
该工艺从高电压放电开始，高电压放电使合金丝4、喷嘴主体6与阴极2之间的等离子气体5电离并分离。因此产生的等离子以高速流过等离子喷嘴3。在该工艺中，朝向连续且垂直地供给至喷嘴3的合金丝4输送等离子气体5，因此完成电路。
此外，输送气体9或雾化气体9经由供给管道10和辅助喷嘴11供给至从导向喷嘴3中出来的等离子射流8。
在这种情况下，合金丝4的融化和雾化受两种现象影响。首先，金属丝4是被通常为65-90安培的大电流强度加热的电阻。等离子射流8对预先加热的金属丝4的影响确保后者在金属丝末端12处融化。换句话说通过高电压放电在等离子喷嘴3内部产生等离子。顺着排出路径的定向的氮气流，即输送气体9将等离子和融化的喷涂材料13输送到将要被涂覆的工件的表面14上。

Claims (4)

1.一种用于通过热喷涂，特别是通过等离子喷涂产生涂层的工艺，在所述工艺中，用合金涂覆部件，特别是汽缸支撑表面，
其中
供给氮气至少作为输送气体，喷涂添加剂是被引导到等离子流内的实心合金丝，并且在没有其他粉末的情况下进行涂覆。
2.根据权利要求1所述的工艺，其中所述等离子喷涂是PTWA涂层。
3.根据权利要求1或2所述的工艺，
其中
其他所述喷涂金属丝是这样的铁合金，所述铁合金包含在重量上12至35％的Cr、在重量上2-10％的Al、在重量上0-1％的Si、在重量上0-1％的Mn和在重量上0-1％的C以及其他成分，所述其他成分诸如为在重量上0-1％的P、在重量上0-0.09％的S、在重量上0-5％的Mo、在重量上0-1％的Ni、在重量上0-0.5％的Cu和在重量上0-0.5％的N，剩余物是Fe。
4.根据前述权利要求中任一所述的工艺，
其中
所述其他喷涂用的金属丝是这样的铁合金，所述铁合金包含在重量上23％的Cr、在重量上5％的Al、在重量上小于0.5％的Si、在重量上小于0.2％的Mn和在重量上小于0.05％的C，剩余成分具有在重量上少于2％的比例，并且剩余物是铁。
CN201280051252.6A 2011-10-17 2012-09-27 等离子喷涂工艺 Pending CN104053810A (zh)

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DE102011084608A DE102011084608A1 (de) 2011-10-17 2011-10-17 Plasmaspritzverfahren
DE102011084608.5 2011-10-17
PCT/EP2012/069021 WO2013056961A1 (de) 2011-10-17 2012-09-27 Plasmaspritzverfahren

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US (1) US20140186540A1 (zh)
EP (1) EP2768997A1 (zh)
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IN (1) IN2014CN02566A (zh)
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