CN105431624A - 产生内燃机中使用的活塞的氧化保护层的方法和具有氧化保护层的活塞 - Google Patents
产生内燃机中使用的活塞的氧化保护层的方法和具有氧化保护层的活塞 Download PDFInfo
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- CN105431624A CN105431624A CN201480033058.4A CN201480033058A CN105431624A CN 105431624 A CN105431624 A CN 105431624A CN 201480033058 A CN201480033058 A CN 201480033058A CN 105431624 A CN105431624 A CN 105431624A
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- Prior art keywords
- piston
- protective layer
- oxide protective
- oxide
- aluminium
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
- F02F3/00—Pistons
- F02F3/10—Pistons having surface coverings
- F02F3/12—Pistons having surface coverings on piston heads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- 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
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
- 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
- C23C14/08—Oxides
- C23C14/085—Oxides of iron group metals
-
- 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
- C23C14/22—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
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of 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
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- C23C4/131—Wire arc spraying
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- 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
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- C23C8/14—Oxidising of ferrous surfaces
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
- F02F3/00—Pistons
- F02F3/10—Pistons having surface coverings
- F02F3/12—Pistons having surface coverings on piston heads
- F02F3/14—Pistons having surface coverings on piston heads within combustion chambers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
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- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
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- Pistons, Piston Rings, And Cylinders (AREA)
- Coating By Spraying Or Casting (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
本发明涉及一种活塞(1)，特别是内燃机的钢制活塞，所述活塞具有是燃烧室(3)的部分的活塞底(2)，其中至少活塞底(2)具有氧化保护层；以及涉及一种产生氧化保护层的方法。
Description
本发明涉及根据独立权利要求的各个上位概念涉及产生用于至少内燃机的钢制活塞的活塞底的区域的氧化保护层的方法，以及具有氧化保护层的活塞。
例如在DE10311150A1中公开了锻造的活塞。在此文献中描述了由第一管件和圆柱形的第二管件构成的活塞，其中第一管件具有至少一个平坦的端面，该端面由耐氧化的钢构成，以及第二管件具有至少一个平坦的端面，所述端面由可热锻造的钢构成。这两个管件通过锻造成型为活塞毛坯。制成的活塞因此在活塞头部的区域直至第一活塞环形槽中由耐氧化的钢构成。
现有技术公开了耐氧化的钢用于活塞的燃烧室区域的用途。
本发明的任务是确保钢制活塞的燃烧室区域在氧化过程之前的保护或至少明显改善所述保护。该任务通过根据具有独立权利要求的特征的方法和活塞来解决。
通过根据本发明的氧化保护层实现了避免发动机运行中的氧化过程和改善了耐热冲击性。形式近似整体的活塞。
氧化保护层例如通过从气相物理沉积涂层材料(物理气相沉积PVD)产生。在此情况下，涂层材料通过物理方法转变为气相，稍后所述涂层材料从气相沉积到基底上。在根据PVD技术将氧化保护层沉积在内燃机的活塞的表面上的方法中，涂层材料通常以固态形式并且任选地通过热输送蒸发，而在CVD技术中在气相中进行输送。
可替代地或补充地，作为将氧化保护层沉积到活塞的表面上的方法可以使用化学气相沉积(ChemicalVapourDeposition-CVD)。在表面涂层技术的方法中，涂层材料借助化学方法被转变为汽相，随后将该涂层材料从汽相沉积到基底上。作为基底的燃烧室区域的涂层例如可以事先利用无连接层的气体氮化或等离子氮化来实现。在此情况下追求3到20μm的层厚度，优选追求5μm的层厚度。此外，可以使用层材料Al-Cr-Ti氮化物(铝-铬-钛氮化物)或碳化物，其具有高的耐热冲击性。通过从气相或汽相将涂层材料沉积到活塞表面上可以产生均匀限定的氧化保护层。
氧化保护层在活塞表面上的沉积可替代地也可以借助脉冲激光沉积(PLD-PulsedLaserDeposition)来进行。在该方法中，使用高能的且短波的(UV)光，以便将初始材料(固态靶标)置于气相中并且由此以层的形式施加到要涂层的活塞表面(基底)上。激光沉积也算作物理气相涂覆法(PVD方法)的类别。
将氧化保护层施加到活塞表面上可替代地也可以通过方法进行。该方法使用高能粒子和高压脉冲技术对表面进行三维改性和涂覆。Plasmaimpax方法能够实现在真空中经由等离子体源从气相进行层沉积。在此，其为由等离子体激活的低温CVD和离子注入构成的混合技术。为了提高表面硬度以及耐磨损性和耐腐蚀性，可以用此种环保的技术实施离子注入过程以及离子辅助的涂覆过程。在此，已较低的涂覆温度足以成功地实施层沉积和表面改性。
利用Plasmaimpax技术可以施加基于类金刚石的碳(DLC-DiamondLikeCarbon)的保护层，而另一方面也可以通过等离子体注入实施表面改性，用以提高表面硬度。类金刚石的碳层具有高的化学耐受性(耐腐蚀性)。
氧化保护层沉积在活塞表面上可替代地也可以通过等离子体辅助的化学气相沉积(PECVD或PACVD-PlasmaAssisted(Enhanced)PhysicalVapourDeposition(等离子体辅助(增强)物理气相沉积))来进行。例如，为了产生碳涂层可以输送乙炔(C2H2)，或为了产生含硅的层可以输送HMDSO(六甲基二硅氧烷)，其在等离子体中被裂解并且由此被提供用于涂覆。在PACVD技术中，低的加工温度是可能的。
在本申请的范围内，下述的在内燃机的活塞的表面上产生氧化保护层的方法概述为从气相沉积涂层材料的物理方法(PhysicalVapourDeposition-PVD)，典型的是PVD以及脉冲激光沉积(PLD-PulsedLaserDeposition)。
在本申请的范围内，下述的在内燃机的活塞的表面上产生氧化保护层的方法概述为化学汽相沉积的方法(ChemicalVapourDeposition-CVD)，方法和等离子体辅助化学气相沉积。
可替代地或补充地，使用具有镍、镍基合金、铬、铬基合金、抗氧化性的Fe基合金(铁基合金)或钨合金和钼合金的电镀涂层构建氧化保护层。在电镀涂层中，在基底上沉积5-100μm的层厚度，优选5-20μm的厚度。
利用在内燃机的活塞的表面上产生氧化保护层的电镀技术的方法，将金属沉积物(覆盖物)电化学地沉积到基底(对象)上，在活塞或活塞表面上形成电镀涂层。电镀技术的方法属于电化学金属沉积(ECD-ElectrochemicalDeposition)的方法。ECD方法可替代地适用于在内燃机的活塞表面上产生氧化保护层。通过电化学金属沉积可以在活塞表面上产生工艺安全的金属层作为氧化保护层。电镀方法由于设备成本相对低而适于构建氧化保护层。
可替代地或补充地，镀覆方法可以用于在内燃机的活塞的表面上产生氧化保护层的方法。在镀覆时，通过在压力下塑性形变将至少两种材料连接。至少一种材料在活塞表面上形成氧化保护层。
可替代地或补充地，氧化保护层通过借助热喷涂(等离子体工艺、HVOF工艺、火焰喷涂工艺)涂覆层将氧化保护层构建在基底上，该氧化保护层根据需要(粘附性、气密性)借助电子束、WIG方法来致密地并且冶金地接合(类似电镀涂层的材料组)。具有高的铬、硅和铝含量(Cr-、Si-和Al-含量)的钢形成非常致密的氧化物层，其保护材料免受进一步氧化。
热喷涂的方法可替代地可以用于在内燃机的活塞的表面上产生氧化保护层。
热喷涂是通用的表面涂覆方法，其中将通常为粉末状或丝线状的涂层材料以高的热能和/或动能离心涂布到部件表面上并且在那里构建层。利用多种可供使用的工艺变型方案，可以将宽范围的材料如金属和陶瓷，以及高性能聚合物加工成工程涂层。层厚度从大约30μm到数毫米。
热喷涂包括下述的在内燃机的活塞的表面上产生氧化保护层的方法：丝线或杆火焰喷涂、粉末火焰喷涂、塑料火焰喷涂、高速火焰喷涂(HVOF-HighVelocityOxygenFuel)、爆炸喷涂或火焰振动喷涂、等离子体喷涂、激光喷涂、光弧喷涂、冷气喷涂和等离子体涂覆焊接(PTA-PlasmaTransferArc)。
热喷涂的方法可以使用不同的涂层材料，使得可以短时使活塞底上的氧化保护层变化，满足相应的要求。
在丝线喷涂或杆喷涂中，喷涂添加材料在乙炔氧气火焰的中心连续地被熔融。借助雾化气体例如压缩空气或氮气从熔融区域中分离小液滴状的喷涂颗粒并且被涂布到预备的活塞表面上。
在粉末火焰喷涂中，粉末状的喷涂添加物在乙炔氧气火焰中熔化或熔融，并且借助膨胀的燃烧气体涂布到预备的活塞表面上。
如果需要，也还可以使用附加的气体例如氩气或氮气来涂布粉末颗粒。各种喷涂添加材料在远远超过100种材料的粉末的情况下分布非常广。
粉末被区分为自流动的和自粘附的粉末。自流动的粉末通常附加地需要热后处理。通常利用乙炔氧气燃烧器进行此种“熔化”。只要进行热后处理，则涉及在内燃机的活塞的表面上产生氧化保护层的多级方法。
通过热过程，极大地提高了喷涂层在基体材料上的粘附性，喷涂层变为气密的和液密的。
塑料火焰喷涂与其他火焰喷涂方法区别在于，塑料添加物并不直接与乙炔氧气火焰接触。在火焰喷枪的中心中是粉末输送喷嘴。该输送喷嘴通过两个环状的喷嘴出口包围，其中内环用于空气或惰性气体而外环用于热能量载体，即乙炔氧气火焰。
塑料的熔融过程因此并不直接通过火焰，而是通过被加热的空气和辐射热来进行。
通过火焰喷涂或粉末火焰喷涂例如可以处理金属粉末、金属粉末合金、陶瓷粉末和塑料粉末。
NiCrBSi涂层(镍-铬-硼-硅涂层)是通过火焰喷涂所施加的以提高活塞表面的氧化耐受性的表面改良。由NiCrBSi合金构成的涂层是非常耐腐蚀的。
在涂层中的镍含量为40％到90％之间。在涂层中的铬含量在3％到26％之间并且赋予这些层其硬度。
NiCrBSi涂层例如通过粉末火焰喷涂连带之后的熔化/烧结来施加。
作为基体材料处理钢和不锈钢。部件例如被消除应力退火、粗略辐照并且紧接着被涂覆以避免下面腐蚀。
NiCrBSi粉末用火焰喷涂枪来喷涂并且随后用气焊手持燃烧器感应地或在真空炉中在大约1000摄氏度的情况下熔化。
作为“湿外观”可看到在熔化过程中的NiCrBSi涂层。此种“湿外观”在大约1000摄氏度的情况下塑性非常好并且如此实施以使得熔融物并不从部件流下或滴落而使NiCrBSi涂层有缺陷。
NiCrBSi涂层的高涂层技术是唯一的在无需附加密封技术的情况下是气密的热喷涂的喷涂层并且由于扩散到所有火焰喷涂涂层的基体材料中而最为适合抵抗冲击负荷。
用添加物WC/Ni，硬质金属涂层(NiCrBSi涂层)变得明显更为耐腐蚀，其中WC/Co具有更高的耐热性。
PTFE或石墨也可以混合成合金。由此，此种硬质金属涂层实现了改善了的抗粘附性和滑动特性。
在高速火焰喷涂(HVOF)中，在燃烧室内以高压进行连续气体燃烧，在该燃烧室的中心轴线中输送粉末状的喷涂添加物。在燃烧室中产生的燃烧气体氧气混合物的高压力和通常设置在后的膨胀喷嘴产生期望的高流动速度的气体束。由此，喷涂颗粒被加速至高颗粒速度，这导致极致密的喷涂层，其具有出色的粘附特性。通过充分但适度地传入热，喷涂添加材料通过喷涂过程在冶金学上仅略微改变，例如最小地形成混合碳化物。在该方法中，可以以高尺寸精度产生极薄的层。
作为燃烧气体可以使用丙烷、丙烯、乙烯、乙炔和氢气。
碳化材料例如可以利用高速火焰喷涂(HVOF)作为在内燃机的活塞的表面上产生氧化保护层的方法来施加。在活塞表面上形成的层非常致密。由于碳层的硬度高，所以其是活塞的极好的抗磨损和耐氧化保护。例如使用如下材料：碳化铬(Cr3C2，Cr3C2/NiCr)或碳化钨(WC/Co，WC/Ni，WC/Co/Cr)。
爆炸喷涂或火焰振动喷涂是间断的喷涂方法。所谓的爆炸喷枪由排出管构成，在该排出管的端部处存在燃烧室。在该燃烧室中，所输送的乙炔氧气喷涂粉末混合物通过点火火花而爆燃。在管中形成的冲击波加速喷涂粒子。喷涂粒子在火焰前端被加热并且以高颗粒速度成定向射束涂布到预备的活塞表面上。在每次爆燃之后，用氮气对燃烧室和管进行清洁冲洗。
在等离子体喷涂中，粉末状的喷涂添加物在喷枪中或之外通过等离子体束熔融并且涂布到活塞表面上。等离子体通过光弧产生，该光弧在氩气、氦气、氮气、氢气或这些气体的混合物中聚束或燃烧。这些气体在此被分离和离子化，其达到高的流出速度并且在复合时将其热能输出给喷涂颗粒。在此，形成具有高达20000摄氏度的温度的等离子体火焰。在电极与喷嘴之间产生光弧。由于高温，因此尤其也可以加工陶瓷材料。
光弧是非转移的，即其在喷枪之内在中央设置的电极(阴极)与形成阳极的水冷的喷涂喷嘴之间燃烧。该方法在常规气氛下(APS-大气等离子体喷涂)在保护气流中即在惰性气氛例如氩气、真空和水中应用。通过特殊成型的喷嘴帽也可以产生高速等离子体。
陶瓷涂层主要借助大气等离子体喷涂(APS)施加到活塞表面上。
使用例如基于氧化铝(Al2O3)、氧化铬(Cr2O3)、氧化钛(TiO2)和氧化锆(ZrO2)的喷涂材料对活塞表面进行涂覆。
在激光喷涂方法中，粉末状的喷涂添加物经由合适的粉末喷嘴被引入激光束中。借助激光辐射，不仅使得粉末而且使得活塞表面的最小部分(微区域)都熔融，并且所输送的喷涂添加物在冶金学上与活塞表面的基体材料连接。为了保护熔浴使用保护气体。
在光弧喷涂方法中，相同或不同类型的两个丝线状喷涂添加物在光弧中被熔掉并且借助雾化气体例如压缩空气来涂布到预备的活塞表面上。光弧喷涂是高效的丝线喷涂方法，但其仅能喷涂导电的材料。
在使用氮气或氩气作为雾化气体时，在很大程度上抑制了材料的氧化。
金属材料例如通过光弧喷涂被施加到活塞表面上。可考虑的材料范围包括大部分金属和非常多的混合物，例如铝、铜(Cu/Al，Cu/Al/Fe)、镍(Ni/Al，Ni/Cr)、钼和锌(Zn/Al)。
冷气体喷涂方法类似于高速火焰喷涂。动能即颗粒速度在此被提高而降低热能。因此可能的是，产生几乎无氧化物的喷涂层。该方法以名称CGDM(ColdGasDynamicSprayMethod(冷气体动力喷涂法))而已知。
氧化保护层也可以通过金属涂覆系统即冷金属喷涂或冷喷涂系统被施加到活塞表面上。喷涂添加物材料借助加热到大约600摄氏度的具有相应的压力的气体束被加速到大于1000m/s的颗粒速度并且作为连续的喷涂束被施加到要涂覆的活塞表面上。
试验已表明：利用该方法产生的层具有极好的粘附强度并且格外致密。在目前常见的热喷涂的方法中粉末在喷涂过程中必须被加热到其熔融温度之上，而在冷气体喷涂中其仅被加热到几百摄氏度。喷涂材料的氧化和所喷涂的层的氧化物含量由此极为小。被涂覆的基底并末展现出由于热作用引起的材料改变。
在转移弧下利用粉末的等离子堆焊(PTA)。在PTA方法中，活塞表面被熔化。具有高密度的等离子体光弧用作热源并且金属粉末用作涂覆材料。在固定电极与工件之间形成光弧。在转移光弧中，在等离子体气体例如氩气、氦气或氩气氦气混合物中，在中央的钨电极(-)与水冷的阳极块之间产生等离子体。粉末借助载气被引至燃烧器，在等离子体束中被加热并且被涂覆到活塞表面上。在此，粉末在熔浴中完全熔化在基底上。
整个方法在保护气体的气氛例如氩气或氩气氢气混合物中进行。
PTA方法能够实现低混合度(5-10％)、小的热影响区、大的涂覆率(达到20kg/h)、在基底与层之间的真正的冶金粘附(因此完全致密的层)以及合金部件的柔性。
前面所使用的堆焊粉末可以分类为镍基的、钴基的和铁基的合金。
可替代地或补充地，氧化保护层通过激光堆焊构建在活塞表面即基底上。要涂覆的材料在此以粉末、丝线或条带输送给该过程。要涂覆的材料的表面在此被熔化。几乎可以涂覆任何材料，例如自流动的合金(NiCrBSi)、镍基合金譬如NiWC(镍-碳化钨)或Deloro在其组成部分有钴、铬、钼、钨和镍的情况下极为耐腐蚀、极为磨损和极为耐热。此外，合金中更大的分解铬比例提高了耐腐蚀性并且由此也提高了活塞表面的耐氧化性。在此涂覆20μm到300μm之间的层厚度。这些层通常不必被后处理。不需要进行基底预处理，例如通过磨蚀性的喷砂方法如刚玉喷砂。
利用粉末形式和丝线形式的焊接添加材料的激光堆焊也称作直接金属沉积(DMD)或激光金属沉积(LMD)。
可替代地或补充地，氧化保护层通过冷气体喷涂在基底上产生，在该过程中要喷涂的材料以粉末形式来输送。这些层非常致密并且颗粒在所述涂层中几乎不被氧化。几乎可以涂覆任何材料，譬如钛和钛合金，以及镍基合金、具有NiCrAl(镍-铬-铝)的c-BN(立方氮化硼、β-氮化硼)、NiCr(镍-铬)、NiAl(镍-铝)、CuAl(铝青铜)或MCrAlY粉末。典型的层厚度在20到300μm之间。在涂覆过程中，部件几乎不被加热。CBN仅次于金刚石是已知的第二硬的材料。与金刚石相比，CBN在温度作用下并不向钢发送碳，因此特别适合于钢制活塞的表面涂层。MCrAlY(金属铬铝钇；M＝金属例如镍(Ni)或钴(Co))类型的超级合金是高温合金，其通过选择性氧化形成铝氧化物层并且因此在活塞表面上形成氧化保护。镍钴铬铝钇(NiCoCrAlY)或钴镍铬铝钇(CoNiCrAlY)材料提供了对氧化的良好的耐受性。
此外，在另一设计方案中，通过热喷涂(等离子体工艺、HVOF工艺、光弧工艺、火焰喷涂工艺)对层特别是氧化保护层进行涂覆。在此情况下，涂层材料以粉末、丝线、悬浮液或杆来输送。涂层结构可以作为与涂层材料(单层的层)有关的单层来实施。不同涂层的使用或不同涂层材料譬如增附剂(例如NiCr、NiAl)(其同时也是热气体腐蚀保护(MCrAlY))的组合和TBC(绝热层)例如利用钇稳定的氧化锆(Y-ZrO)会导致多层的涂层结构。
绝热层(TBC)降低了热传递并且将基底隔离。沉积在活塞表面上的层系统优选由两个组分构成。连接层用作氧化阻挡并且由金属材料例如MCrAlY构成。以及由陶瓷材料例如利用钇稳定的氧化锆(YSZ)构成的盖层。
根据涂覆方法也可以施加Ni基合金或MoSi2/SnAl(钼二氧化硅/锌铝)。这些层可以根据需要(粘附性、气密性)借助电子束、WIG方法、扩散退火、感应退火、激光等来致密化并且在冶金上接合(类似电镀涂层的材料组)。具有高的Cr-、Si-和Al-含量(铬-、硅-和铝-含量)的钢形成非常致密的氧化物层，其保护材料免受进一步氧化。典型的层厚度在20到300μm的范围中。
WIG方法(钨-惰性气体焊接)是保护气体焊接方法，惰性保护气体用作保护气体。在焊接过程期间，光弧在工件与非熔掉的钨电极之间燃烧，该钨电极熔融基体材料和添加材料。
焊接方法可以以明显的设备开销实现，以便将氧化保护层施加到活塞底上，这样例如激光堆焊方法或钨。惰性气体焊接方法，用以由于低的设备开销而适于产生氧化保护层。
扩散退火用于消除或降低活塞或活塞表面中的浓度差例如晶体离析(Kristallseigerungen)或接合不均匀性。基于的原理是，高温有利于扩散。退火在1000摄氏度到1200摄氐度之间的温度下进行。通过使活塞表面均匀化提高其耐氧化性。
感应退火或感应硬化特别在确定的区域中在所需的硬化温度(部分硬化)上作用于复杂成型的工件例如活塞或活塞表面，以便接着对其淬火。
退火方法特别有助于使氧化保护层均匀化并且因此可以与在本文献中所述的其他方法组合，这样例如扩散退火或感应退火方法特别适于使氧化保护层均匀化并且因此可以单独地使用，但也可以与其他用于产生氧化保护层的方法组合使用。
同样存在喷涂之后将所述层浸渍或密封的可能性。在此，施加密封件，其随后将其没入和封闭到喷涂层中的空腔中并且因此防止间隙腐蚀或下面腐蚀。
可替代地或补充地，为了构建氧化保护层设置使用由铝或铝合金优选具有合金元素硅(例如AlSi12)、铜和/或镁的覆盖物，其通过形成铁铝化物和/或稳定的铁-铝混合氧化物(优选尖晶石类型例如铁尖晶石FeOAl2O3或FeAl2O4或镁铝尖晶石MgAl2O4)构建具有层厚度在5到200μm的耐氧化的保护层。在活塞底上涂覆铝(或铝合金)可以根据上面所描述的方法之一通过浸浴(铝浴)或通过施加含有铝的漆或悬浮液来进行。根据涂覆方法可以通过接着的有目的地短时加热活塞底(优选在大于660摄氏度(Al熔点)的温度下)实现了改善了层构建和层粘附。该加热例如可以通过激光处理、感应加热借助气体燃烧器等来进行，其中氧气的侵入或在最为简单的情况下空气氧气也辅助用于保护的稳定的混合氧化物的形成。
氧化保护层通过由特别纯的铝或铝合金构成的覆盖物来以特别有利的方式产生。这样的合金例如可以构成铁铝和/或稳定的铁铝混合氧化物(优选尖晶石类型)。在活塞底上涂覆铝或铝合金可以根据上面所描述的方法之一通过浸浴(铝浴)或通过施加含有铝的漆或悬浮液来进行。
替代的设置用于在内燃机的活塞的表面上构建氧化保护层的Alfin方法是用于将钢或铸铁与铝或铝合金进行金属连接的铸造方法。Al-Fin方法用于将铝(Al)和合金与钢或铸铁连接。要连接的活塞部件首先被清洁，在盐熔融物中被预热并且浸没在液体铝(830到880摄氏度)中。在此形成的金属间的铁铝层牢固地与基体材料连接，易于合金形成，并且在接着以铝材料作为氧化保护层铸造时进行粘附。Al-Fin方法能够实现铁和铝合金之间的特别良好的连接。
由铝或由至少一种铝合金构成的覆盖物至少在活塞的活塞底上借助前面所描述的方法、浸浴(铝浴)、通过施加含铝的漆和/或悬浮液来产生。
在基底与沉积的层之间的金属接合的产生可以通过在第二方法步骤中的附加的热冲击例如借助激光、WIG、电子束或感应地进行。
在活塞表面上产生氧化保护层时可以前置有用于准备表面的方法步骤。活塞表面的准备可以通过清洁和/或预处理进行。在清洁时，在不影响基底材料的情况下将污物从活塞表面去除。而预处理用于优化在活塞表面上产生氧化保护层的方法的效率。为了预处理，可以使用如下方法，该方法处理对应的活塞表面，使得其表面特性例如在氧化保护层的粘附性方面予以改进。材料改变的预处理也称作活化。例如为此使活塞表面粗化，以便能够使表面增大或形成的底切，以实现氧化保护层的微灌浆(Mikroverklammerung)，并且提高了机械粘附性。此外，可以提高表面能量，这也称作比粘附性的提高。
活塞表面的准备可以通过磨蚀性的机械方法如研磨、刷扫或喷砂方法进行。在该方法中，也可以清除掉活塞表面的一部分。待涂覆的活塞表面的至少被清除掉的部分可以通过根据在本文中提及的方法待产生的氧化保护层再被构建。
活塞表面的准备也可以通过化学预处理方法譬如刻蚀或浸酸来进行。
此外，活塞表面的准备也可以通过物理方法譬如燃烧、等离子体、电晕或激光预处理方法进行。
在通过清洁准备活塞表面以应用至少一种在本文中所述的产生氧化保护层的方法时，例如必须将来自之前的生产步骤(例如成型方法)的污物如冷却剂和/或润滑剂(KSS)、腐蚀保护油、助焊剂、氧化皮、石墨、金属皂、硫酸盐、矿物油、无机皂、金属氧化物、金属盐、粉尘和/或碎片去除。
根据在本文中所述的方法的氧化保护层的产生可以在内燃机的活塞毛坯、活塞的一个区域或在活塞的整个表面上进行。优选地，至少活塞底具有氧化保护层。
所有在本文中所述的用于在内燃机的活塞的表面上产生氧化保护层的方法可以单独使用或可以近似任意组合地使用来在内燃机的活塞的表面上产生氧化保护层。通过组合用于在内燃机的活塞的表面上产生氧化保护层的方法，可以在活塞的表面上沉积或构建多层系统。
通过在活塞表面构建作为多层系统的氧化保护层，可以顾及到对氧化保护层的要求。
在将活塞表面上的氧化保护层实施为多层系统时，可以使用有利的材料作为活塞的基础。
在将氧化保护层构建为多层系统时，至少两个层施加到活塞表面上。所述至少两个层可以具有在化学上和在物理上相同的特性，然而其也可以具有在化学上和/或在物理上彼此不同的特性。
用于产生氧化保护层的方法可以单独或近似任意组合地使用。在将方法组合时，可以形成多层氧化保护层。多层氧化保护层可以由相同的物质或不同的物质构成。
根据本发明设计为：在具有是燃烧室的部分的活塞底的活塞尤其内燃机的钢制活塞中，至少活塞底具有氧化保护层。
通过将氧化保护层施加到活塞底上，减小或甚至避免了对燃烧凹陷处的区域中的活塞材料的氧化作用。因此可以由其他材料制造活塞。通过其他材料选择可以降低成本。
前面述及的涂层材料和材料类别可以针对氧化保护层的要求来加以选择。由不同的涂层材料和材料类别的组合也是可能的，以便在活塞底的表面上构建合适的氧化保护层。
参照如下描述的附图更为详细地阐明了本发明。
图1示出了具有形式为氧化保护层的根据本发明的涂层的钢制活塞。
在以下的附图描述中，术语如上部、下部、左侧、右侧、前部、后部等仅以图1中所选择的示例性的视图以及装置和其他元件的位置为参照来描述。这些术语不能理解为限制性的，也即通过不同的位置和/或镜像对称布置等可以改变所述参照。
在图1中示出了由钢制成的活塞1。活塞1具有活塞底2，该活塞底是燃烧室3的部分。此外，活塞1具有耐火托环4和环形区5。杆7用轮毂6向下连接到环形区5上。活塞1在活塞底2的区域中设置有根据本发明的氧化保护层。
根据本发明的氧化保护层的使用并不限于在此示例性示出的内燃机的活塞的结构形式，更确切地说，任意活塞底都可以设置有根据本发明的氧化保护层。
附图标记表
1活塞
2活塞底
3燃烧室
4耐火托环
5环形区
6轮毂
7杆
Claims (22)
1.生产活塞(1)特别是内燃机的钢制活塞的方法，
其特征在于，
通过从气相沉积涂层材料的物理方法(PhysicalVapourDeposition-PVD(物理气相沉积))至少在活塞(1)的活塞底(2)上产生氧化保护层。
2.生产活塞(1)特别是内燃机的钢制活塞的方法，
其特征在于，
通过化学气相沉积的方法(ChemicalVapourDeposition-CVD(化学气相沉积))至少在活塞(1)的活塞底(2)上产生氧化保护层。
3.生产活塞(1)特别是内燃机的钢制活塞的方法，
其特征在于，
通过电化学金属沉积(ECD-ElectrochemicalDeposition(电化学沉积))的方法至少在活塞(1)的活塞底(2)上产生氧化保护层。
4.生产活塞(1)特别是内燃机的钢制活塞的方法，
其特征在于，
通过热喷涂方法至少在活塞(1)的活塞底(2)上产生氧化保护层。
5.生产活塞(1)特别是内燃机的钢制活塞的方法，
其特征在于，
通过激光堆焊或钨惰性气体焊接方法至少在活塞(1)的活塞底(2)上产生氧化保护层。
6.生产活塞(1)特别是内燃机的钢制活塞的方法，
其特征在于，
通过扩散退火或感应退火方法至少在活塞(1)的活塞底(2)上产生氧化保护层。
7.生产活塞(1)特别是内燃机的钢制活塞的方法，
其特征在于，
通过由铝或者至少一种铝合金构成的覆盖物在活塞(1)的区域上产生氧化保护层。
8.根据权利要求7的生产活塞(1)特别是内燃机的钢制活塞的方法，
其特征在于，
所述铝合金形成铁铝化物和/或稳定的铁铝混合氧化物，其优选为尖晶石类型。
9.根据权利要求7或8的生产活塞(1)特别是内燃机的钢制活塞的方法，
其特征在于，
至少在活塞(1)的活塞底(2)上通过根据权利要求1至6的方法，通过浸浴(铝浴)，通过施加含铝的漆和/或悬浮液来产生由铝或至少一种铝合金构成的覆盖物。
10.生产活塞(1)特别是内燃机的钢制活塞的方法，
其特征在于，
通过根据权利要求1至9的至少两种方法的组合来产生氧化保护层。
11.活塞(1)特别是内燃机的钢制活塞，至少在活塞底(2)的区域中具有氧化保护层，
其特征在于，
根据至少一种根据权利要求1至10的方法来产生氧化保护层。
12.根据权利要求11的活塞(1)，
其特征在于，
氧化保护层由氮化物或碳化物的物质类别形成。
13.根据权利要求11或12的活塞(1)，
其特征在于，
氧化保护层由镍、镍基合金、铬、铬基合金、抗氧化性的铁基合金、或钨合金和钼合金形成。
14.根据权利要求11、12或13的活塞(1)，
其特征在于，
氧化保护层由NiCrBSi涂层(镍-铬-硼-硅涂层)构成。
15.根据权利要求11、12、13或14的活塞(1)，
其特征在于，
氧化保护层由氧化物，特别是氧化铝(Al2O3)、氧化铬(Cr2O3)、氧化钛(TiO2)或氧化锆(ZrO2)构成。
16.根据权利要求11、12、13、14或15的活塞(1)，
其特征在于，
氧化保护层由镍基合金特别是NiWC(镍-碳化钨)、NiCrAl(镍-铬-铝)、NiCr(镍-铬)、NiAl(镍-铝)或成，其中的组成成分为钴、铬、钼、钨和镍。
17.根据权利要求11、12、13、14、15或16的活塞(1)，
其特征在于，
氧化保护层由CBN或MCrAlY形成。
18.根据权利要求11、12、13、14、15、16或17的活塞(1)，
其特征在于，
氧化保护层由两个层形成，由绝热层(TBC)形成，特别由MCrAlY以及陶瓷材料构成的盖层形成，特别由用钇稳定的氧化锆(YSZ)形成。
19.根据权利要求11、12、13、14、15、16、17或18的活塞(1)，
其特征在于，
氧化保护层由MoSi2/SnAl(钼氧化硅/锌铝)层构成。
20.根据权利要求11、12、13、14、15、16、17、18或19的活塞(1)，
其特征在于，
氧化保护层由铝或至少一种铝合金构成的覆盖物形成，优选具有合金元素硅(例如AlSi12)、铜和/或镁，其通过形成铁-铝化物和/或稳定的铁-铝混合氧化物(优选尖晶石类型，例如铁铝尖晶石FeOAl2O3或FeAl2O4或镁铝尖晶石MgAl2O4)构建耐氧化的保护层。
21.根据权利要求11至20任一项的活塞(1)，
其特征在于，
氧化保护层优选具有在3到300μm之间的厚度。
22.根据权利要求11至21任一项的活塞(1)，
其特征在于，
活塞(1)具有由至少两个根据权利要求11至21的氧化保护层构成的多层氧化保护层。
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| Country | Link |
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| US (1) | US20160138516A1 (zh) |
| EP (1) | EP3008317A1 (zh) |
| CN (1) | CN105431624B (zh) |
| DE (1) | DE102014211366A1 (zh) |
| MX (1) | MX2015016390A (zh) |
| WO (1) | WO2014198896A1 (zh) |
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| CN106435673A (zh) * | 2016-12-22 | 2017-02-22 | 日照金港活塞有限公司 | 一种内燃机锻钢活塞顶部隔热涂层的制备工艺 |
| CN111118435A (zh) * | 2020-02-27 | 2020-05-08 | 广东省新材料研究所 | 铝合金和提高其抗微动磨损的方法 |
| CN111850557A (zh) * | 2020-07-23 | 2020-10-30 | 潍柴动力股份有限公司 | 一种活塞制作方法及活塞 |
| CN117344260A (zh) * | 2023-12-04 | 2024-01-05 | 北矿新材科技有限公司 | 一种超高温陶瓷可磨耗封严涂层材料及其制备方法 |
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| DE102015213168A1 (de) * | 2015-07-14 | 2017-01-19 | Robert Bosch Gmbh | Verfahren zur Erzeugung einer strukturierten Oxidschicht sowie ein dadurch erzeugtes Substrat |
| DE102015213896A1 (de) * | 2015-07-23 | 2017-01-26 | Volkswagen Aktiengesellschaft | Verfahren zur Beschichtung eines metallischen Werkzeugs und Bauteil |
| JP6861217B2 (ja) * | 2016-02-12 | 2021-04-21 | エリコン サーフェイス ソリューションズ アーゲー，プフェフィコーンＯｅｒｌｉｋｏｎ Ｓｕｒｆａｃｅ Ｓｏｌｕｔｉｏｎｓ ＡＧ，Ｐｆａｆｆｉｋｏｎ | トライボロジーシステムとこれを有する内燃エンジン |
| US10273902B2 (en) * | 2016-02-22 | 2019-04-30 | Tenneco Inc. | Insulation layer on steel pistons without gallery |
| DE102016207893A1 (de) * | 2016-05-09 | 2017-11-09 | Siemens Aktiengesellschaft | Bauplattform für die additive Herstellung und Verfahren |
| US10690247B2 (en) | 2017-01-10 | 2020-06-23 | Tenneco Inc. | Galleryless short compression insulated steel piston |
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| DE102017002078A1 (de) | 2017-03-04 | 2018-09-06 | Man Truck & Bus Ag | Brennkraftmaschine und Verfahren zum Herstellen eines Kurbelgehäuses und/oder einer Zylinderlaufbuchse für eine Brennkraftmaschine |
| RU180719U1 (ru) * | 2017-05-02 | 2018-06-21 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) | Устройство для индукционно-термического оксидирования малогабаритных титановых изделий |
| US11149681B2 (en) * | 2018-01-19 | 2021-10-19 | Cummins Inc. | Piston with insulating air gap formed by additive manufacturing |
| DE102018103319A1 (de) * | 2018-02-14 | 2019-08-14 | Iwis Motorsysteme Gmbh & Co. Kg | Metallbauteil |
| US11168643B2 (en) * | 2018-02-21 | 2021-11-09 | Tenneco Inc. | Coating to reduce coking deposits on steel pistons |
| RU2689485C1 (ru) * | 2018-12-28 | 2019-05-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) | Способ формирования оксидных покрытий на изделиях из нержавеющих хромоникелевых сталей |
| DE102020100640A1 (de) | 2020-01-14 | 2021-07-15 | Stahlzentrum Freiberg e.V. | Verfahren zur Verbesserung der Korrosionsbeständigkeit von Befestigungs- und/oder Bewehrungsbauteilen aus hochlegierten Stählen und Befestigungs- und/oder Bewehrungsbauteile aus hochlegierten Stählen |
| US20230338915A1 (en) * | 2020-09-21 | 2023-10-26 | Dsm Ip Assets B.V. | Ceramic coating on metal parts to reduce deposit of metallic transition metals in hydrogenation reactions |
| RU2763130C1 (ru) * | 2021-03-16 | 2021-12-27 | Ирина Александровна Сологубова | Способ нанесения защитного покрытия на сталь |
| CN113250848B (zh) * | 2021-06-29 | 2022-08-23 | 潍柴动力股份有限公司 | 活塞及其制造方法 |
| CN113957429A (zh) * | 2021-09-09 | 2022-01-21 | 成都银河动力有限公司 | 一种活塞用铝合金制备及其强化方法 |
| DE102022108997A1 (de) | 2022-04-13 | 2023-10-19 | Ks Kolbenschmidt Gmbh | Kolbenrohling, kolben und verfahren |
| CN116988061B (zh) * | 2023-09-27 | 2023-12-19 | 太原科技大学 | 一种镍基高温合金及其表面改性方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106435673A (zh) * | 2016-12-22 | 2017-02-22 | 日照金港活塞有限公司 | 一种内燃机锻钢活塞顶部隔热涂层的制备工艺 |
| CN111118435A (zh) * | 2020-02-27 | 2020-05-08 | 广东省新材料研究所 | 铝合金和提高其抗微动磨损的方法 |
| CN111118435B (zh) * | 2020-02-27 | 2021-10-01 | 广东省科学院新材料研究所 | 铝合金和提高其抗微动磨损的方法 |
| CN111850557A (zh) * | 2020-07-23 | 2020-10-30 | 潍柴动力股份有限公司 | 一种活塞制作方法及活塞 |
| CN117344260A (zh) * | 2023-12-04 | 2024-01-05 | 北矿新材科技有限公司 | 一种超高温陶瓷可磨耗封严涂层材料及其制备方法 |
| CN117344260B (zh) * | 2023-12-04 | 2024-03-22 | 北矿新材科技有限公司 | 一种超高温陶瓷可磨耗封严涂层材料及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102014211366A1 (de) | 2014-12-18 |
| US20160138516A1 (en) | 2016-05-19 |
| MX2015016390A (es) | 2016-04-11 |
| WO2014198896A1 (de) | 2014-12-18 |
| CN105431624B (zh) | 2022-03-18 |
| EP3008317A1 (de) | 2016-04-20 |
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