CN105734345A - 填满了耐磨损性钴基合金的发动机阀门 - Google Patents

填满了耐磨损性钴基合金的发动机阀门 Download PDF

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CN105734345A
CN105734345A CN201610118422.8A CN201610118422A CN105734345A CN 105734345 A CN105734345 A CN 105734345A CN 201610118422 A CN201610118422 A CN 201610118422A CN 105734345 A CN105734345 A CN 105734345A
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mass
engine valve
alloy
mar proof
cobalt
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乙部胜则
西村信一
仓桥一宪
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Fukuda Metal Foil and Powder Co Ltd
Nittan Corp
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Fukuda Metal Foil and Powder Co Ltd
Nittan Valve Co Ltd
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    • B23K10/00—Welding or cutting by means of a plasma
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K10/00—Welding or cutting by means of a plasma
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K9/00—Arc welding or cutting
    • B23K9/04—Welding for other purposes than joining, e.g. built-up welding
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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
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    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • F01L3/04—Coated valve members or valve-seats
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K51/00—Other details not peculiar to particular types of valves or cut-off apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B23K2101/00—Articles made by soldering, welding or cutting
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    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2301/00—Using particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2303/00—Manufacturing of components used in valve arrangements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2303/00—Manufacturing of components used in valve arrangements
    • F01L2303/01—Tools for producing, mounting or adjusting, e.g. some part of the distribution
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2800/00—Methods of operation using a variable valve timing mechanism
    • F01L2800/18—Testing or simulation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2820/00—Details on specific features characterising valve gear arrangements
    • F01L2820/01—Absolute values

Abstract

本发明提供一种耐磨损性优越并具有抗冲击性的表面硬化用材料。耐磨损性钴基合金含有总量为20.0～30.0质量％的Mo或/和W，0.8～2.2质量％的B，5.0～18.0质量％的Cr，总量为5.0质量％以下的Fe、Ni、Mn、Cu、Si、C，并且含有1.0质量％以下的Si、0.3质量％以下的C，余量包含55.0～70.0质量％的Co以及不可避免的杂质，还提供填满了耐磨损性钴基合金的发动机阀门。

Description

填满了耐磨损性钴基合金的发动机阀门
本申请是申请人于2011年5月23日提交的国际申请号PCT/JP2011/061748，进入中国国家阶段的申请号为2011800522839、发明名称为“耐磨损性钴基合金以及用它进行填满的发动机阀门”的申请的分案申请。
技术领域
本发明涉及一种使用于PTA粉末堆焊、TIG堆焊、喷镀等各种施工工艺的表面硬化用材料，尤其涉及用于要求耐磨损性的构件的耐磨损性钴基合金和用它进行填满的发动机阀门。
背景技术
以往，在发动机阀门上使用以Stellite(注册商标)为代表的Co-Cr-W-C系材料(包括专利文献1、2)或以Tribaloy(注册商标)为代表的Co-Mo-Si系材料(包括专利文献3～7)，尤其是在要求耐磨损性的构件中使用Tribaloy。
Co-Cr-W-C系的材料，作为表面硬化用材料，虽然具有较高的韧性，但是耐磨损性不够，不能承受长期的使用。另外，Co-Mo-Si系的材料，作为表面硬化用材料虽然具有较高的耐磨损性，但是抗冲击特性不够，有产生裂纹、伴随裂纹的剥离问题。
在先技术文献
专利文献
[专利文献1]日本特开2001-123238号公报
[专利文献2]日本特表2008-522039号公报
[专利文献3]日本专利第4463763号公报
[专利文献4]日本特开平5-131289号公报
[专利文献5]日本特开平9-296241号公报
[专利文献6]日本特开平7-278780号公报
[专利文献7]日本特开平4-107235号公报
发明内容
发明所要解决的课题
把耐磨损性和抗冲击性作为目的的表面硬化，现在被广泛地使用于各种工业领域。然而，通过近几年环境意识的提高，对工业机器的使用环境要求更为严格，随之也要求表面硬化用材料具有更高的性能。尤其是对于使用于发动机阀门的填满(filling)材料，耐磨损性优越并具有抗冲击性的表面硬化用材料的开发已成为课题。
用于解决课题的手段
本发明在为了开发耐磨损性优越的表面硬化用材料而对合金成分进行研究时，设定了下列的目标值，并将满足所有此目标作为条件。
(目标值)
(1)摆锤式冲击值→5J/cm2以上
(2)硬度→52HRC以上
(3)堆焊操作性→堆焊时形成的熔池的熔液流动良好
(4)热冲击试验→直到600℃也不发生裂纹、剥离。
即，满足上述目标(1)～(4)的本发明的耐磨损性钴基合金，其特征在于，其含有总量为20.0～30.0质量％的W和/或Mo、0.8～2.2质量％的B、5.0～18.0质量％的Cr，余量包含55.0～70.0质量％的Co以及不可避免的杂质。在此，所谓不可避免的杂质，是指不是有意添加但在各原料的制造工艺等中不可避免地混入的杂质，作为这样的杂质，可以举出Mg、S、O、N、V、Zr、Sn等，这些的总量通常为0.3质量％以下，不会对本发明的作用产生影响。
另外，本发明的耐磨损性钴基合金，其特征在于，其含有总量为20.0～30.0质量％的W和/或Mo、0.8～2.2质量％的B、5.0～18.0质量％的Cr，进而含有总量为5.0质量％以下的Fe、Ni、Mn、Cu、Si、C，并且含有1.0质量％以下的Si、0.3质量％以下的C，余量包含55.0～70.0质量％的Co以及不可避免的杂质。
另外，本发明的发动机阀门，其特征在于，被填满和涂敷了具有上述组成的耐磨损性钴基合金；优选的发动机阀门，其特征在于，至少在表面与阀座的接触面上被填满或涂敷了所述耐磨损性钴基合金。
下面，对本发明的钴基合金的各成分进行限定的理由加以说明。
Mo、W在作为基体(基质)的Co固溶体中固溶，可赋予耐磨损性、抗冲击性，同时，其一部分与B形成金属间化合物，更有助于提高耐磨损性，但是，在Mo和W的总量低于20.0％质量的时候，固溶强化不充分，若超过30.0质量％，则会大量地形成金属间化合物，韧性(抗冲击性)会大幅度降低。为此，将Mo和/或W的总量定为20.0～30.0质量％的范围。
关于B，与Cr或Mo形成金属间化合物，可赋予耐磨损性，同时，可净化熔液，使填满时的熔液流动较好，由此可提高PTA、TIG堆焊或喷镀等施工操作性。但是，在含量低于0.8质量％的时候，不能形成足够量的金属间化合物，磨损性降低，除此以外，熔液的净化作用变得不充分。另外，若超过2.2质量％，则金属间化合物的量较多，韧性(抗冲击性)会大幅度降低。因此，将B的含量定为0.8～2.2质量％的范围。
Cr在Co固溶体中固溶，可赋予耐磨损性、抗冲击性、抗腐蚀性、抗氧化性。另外，Cr的一部分与B形成金属间化合物，在基质内分散，由此，更有助于提高耐磨损性。但是，在Cr的含量低于5.0质量％的时候，不能得到充分的耐磨损性、抗腐蚀性、抗氧化性，若超过18.0质量％，则在金属组织中大量地形成金属间化合物，韧性会大大降低，因此，将含量范围定为5.0～18.0质量％。
本发明的钴基合金，作为不对物性造成不良影响的添加元素，可含有总量为5.0质量％以下的Fe、Ni、Mn、Cu、Si、C，并含有1.0质量％以下的Si、0.3质量％以下的C。
发明效果
本发明的钴基合金，具有摆锤式冲击值为5J/cm2以上且硬度为52HRC以上的特性，PTA堆焊操作性好，在堆焊试验片的热冲击试验中，到600℃为止没有产生裂纹、剥离，因此，作为具有优越的耐磨损性和抗冲击性的表面硬化用材料，能够适用于广泛的用途。
附图说明
图1是填满了本发明的耐磨损性钴基合金的发动机阀门的一例的模式图。
具体实施方式
将作为基体的Co以及作为添加成分的Mo和/或W、Cr、B和根据需要添加的Fe、Si、Mn、Cu、Ni、C的每个以规定的质量％加以调整、配合而成为基块，并将此基块在熔化炉中的坩锅内加热、熔融而成为液状的合金之后，利用雾化法、熔融粉碎法制成粉末，或用规定的模具铸造成棒状或板状等，可获得本发明的钴基合金。
尤其是用雾化法制造的钴基合金粉末，通过调整成适于目的施工方法的粒度，可用于PTA堆焊、喷镀等表面改性施工，用连续浇铸法制造的堆焊焊条，能够用于气堆焊等表面改性施工。另外，通过将该粉末或棒材施工于各种材质的发动机阀门的表面，能够赋予发动机阀门以耐磨损性。
实施例
对如上述那样调整、配合的本发明的实施例合金以及比较例合金进行熔炼，并用以下所示的方法测量了摆锤式冲击值和洛氏硬度，并实施了堆焊试验和热冲击试验。
(1)摆锤式冲击试验；将具有各种合金的配合组成的100g的基块用电炉在氩气流中加热至约1600℃、熔化，在壳模(shellmold)中进行铸造，并机械加工成JISZ2242:2005中记载的试验片(没有缺口)。然后，用摆锤式冲击试验机进行了以JISZ2242:2005为基准的冲击试验，并测量了冲击值。
(2)硬度的测量；将用与上述(1)同样的方法熔炼的铸造片机械加工成10×10×20mm的形状，并作出平行面，将此平行面上部用240号的耐水砂纸进行湿法抛光，并实施了以JISZ2245:2005为基准的洛氏硬度试验。而且，用C标尺(Cscale)进行了测量。
(3)PTA堆焊试验；将具有各种合金的配合组成的100kg的基块用高频熔化炉在氩气流中加热至约1600℃、熔化，利用气体雾化法使其粉末化，并在振动筛中调整其粒度为80～350mesh。将该合金粉末，在用JISG4311:1991中规定的耐热钢(SUH3)制造的发动机阀门(伞径约为70mm，轴径约为14mm，全长约为300mm)的表面(以图1中符号2表示的部分)上进行等离子粉末堆焊，并调查了堆焊时形成的熔池的熔液流动状态。而且，熔液流动状态的评价基准，都按以下的任意一种表示，熔液流动状态为良好的合金用“非常好”或“良好”表示。
(评价基准)
非常好∶与比较例P、Q(钴基自熔合金)同等或为其以上
良好∶与比较例A(Stellite(钨铬钴合金)6)同等或为其以上
稍差∶虽然比比较例A差，但比比较例F(Tribaloy400)好
差∶与比较例F同等或为其以下。
(4)热冲击试验；将用与上述(3)同样的方法制造的发动机阀门在设成400℃的电炉中热处理1小时，然后放入到约20℃的水中进行急冷。接着，将热处理温度进一步上升50℃，进行1小时的热处理和水冷。将其反复进行直到热处理温度达到600℃，并调查了在600℃的热处理后的水冷中是否产生裂纹、剥离。
在表1中出示了本发明的实施例的结果，在表2和表3中出示了比较例的结果。
表2中所示的比较例合金(a)～(k)是本发明保护范围外的组成的合金。合金(a)的Co量超过了保护范围的上限，合金(h)的Fe和Ni的总量超过了保护范围的上限，合金(i)的Ni和Cu的总量超过了保护范围的上限；关于合金(f)，其Mo和B低于保护范围的下限；在这种情况下，它们的硬度都没有满足目标值。关于合金(b)，其Mo和W的总量超过了保护范围的上限，而且其Co低于保护范围的下限；合金(c)的Mo低于保护范围的下限，合金(d)的Cr低于保护范围的下限；合金(e)的Cr超过了保护范围的上限，合金(g)的B超过了保护范围的上限，合金(j)的Si超过了保护范围的上限，合金(k)的C超过了保护范围的上限；在这种情况下，它们都没有满足摆锤式冲击值。另外，不满足摆锤式冲击值目标的比较例(b)～(e)、(g)、(j)、(k)，在热冲击试验中确认到有裂纹的产生。
关于表3所示的比较例合金(A)～(Q)，虽然是以往的Co-Cr-W-C系合金(Stellite(注册商标))和Co-Mo-Si系合金(Tribaloy(注册商标))，或由其他的专利文献和JISH8303的自溶合金喷镀中示出的组成的合金，但都是摆锤式冲击值或者硬度的任一种不满足目标值，并且，比较例(C)～(O)的堆焊操作性差。另外，比较例(B)、(C)、(F)～(N)、(P)，在热冲击试验中确认到有裂纹的产生。
与此相对，如表1所示，作为本发明合金的实施例1～18，摆锤式冲击值和洛氏硬度、热冲击试验都满足目标值，作为表面硬化用材料具有合适的硬度和较高的耐磨损性，而且堆焊操作性优越。
[工业上的可利用性]
如上所述，本发明的钴基合金，具有作为表面硬化用材料的优越的耐磨损性和抗冲击特性，并且，满足熔液流动性，因此，通过将这样的材料做成粉末状或棒状并通过焊接或喷镀等在各种构件进行表面硬化，这样，这些构件就有望显著提高耐久性。
另外，本发明的钴基合金，并不限定于用作填满，也可通过复合添加到基于粉末冶金的烧结部件中而制成硬质粒子，能够形成耐磨损性良好的机械部件。
符号说明:
1：发动机阀门
2：表面(与阀座的接触面)。

Claims (3)

1.一种发动机阀门，其特征在于，
其被填满或涂敷了如下的耐磨损性钴基合金，所述耐磨损性钴基合金含有总量为20.0～30.0质量％的Mo和/或W、0.8～2.2质量％的B、5.0～18.0质量％的Cr，余量仅包含55.0～70.0质量％的Co以及不可避免的杂质。
2.根据权利要求1所述的发动机阀门，其特征在于，
所述耐磨损性钴基合金还含有总量为5.0质量％以下的Fe、Ni、Mn、Cu。
3.根据权利要求1或2所述的发动机阀门，其特征在于，
至少在表面与阀座的接触面上被填满或涂敷了所述耐磨损性钴基合金。
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