CN107267877B - 一种洁净燃料发动机粉末冶金高速钢阀座及其制备工艺 - Google Patents
一种洁净燃料发动机粉末冶金高速钢阀座及其制备工艺 Download PDFInfo
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- 229910000997 High-speed steel Inorganic materials 0.000 title claims abstract description 20
- 239000000446 fuel Substances 0.000 title claims abstract description 16
- 238000004663 powder metallurgy Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 230000008595 infiltration Effects 0.000 claims abstract description 21
- 238000001764 infiltration Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000004615 ingredient Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 229910017116 Fe—Mo Inorganic materials 0.000 claims description 6
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- 239000002994 raw material Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
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- 229910000831 Steel Inorganic materials 0.000 description 2
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
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- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000008450 motivation Effects 0.000 description 1
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- 210000004872 soft tissue Anatomy 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 238000005728 strengthening Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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Abstract
本发明公开了一种洁净燃料发动机粉末冶金高速钢阀座及其制备工艺,以W6Mo5Cr4V2高速钢粉末为基体材料,添加有Cu、Co‑Cr‑Mo和Fe‑Mo硬质颗粒;成分质量百分比为W6Mo5Cr4V2为45%~57%;Co‑Cr‑Mo为13%~17%;Fe‑Mo为4%~7%;Cu为17%~22%;固体润滑剂和易切削成分为2%~3%。本发明采用熔渗烧结和热处理技术降低提升粉末冶金高速钢阀座密度、硬度和耐磨性等,一方面能得到稳定的合金回火马氏体和细小弥散二次合金碳化物。另一方面,基体和硬质颗粒结合更加牢固,摩擦磨损时不容易从基体上剥落。通过熔渗烧结和热处理工艺提升了材料密度、硬度和耐磨性等性能。
Description
技术领域
本发明涉及金属材料技术领域,尤其涉及一种洁净燃料发动机粉末冶金高速钢阀座及其制备工艺。
背景技术
气门阀阀座是发动机上的重要部件,与气门配合控制燃气和废气的进出,其性能的好坏直接影响发动机的功率和经济性。原燃油阀座长期工作在高温、高冲击载荷、热腐蚀气氛等环境下,工况十分恶劣。进入21世纪以来,发动机采用CNG、LPG等洁净燃料成为我国新能源战略重点扶持方向,但发动机使用CNG、LPG等洁净燃料后,燃料润滑成分减少,气门与阀座直接接触;燃烧时间延长,燃烧温度升高,阀座红硬性下降;富含有H2S气体等杂质,S含量较高,容易发生硫化腐蚀。因此,原燃油阀座磨损严重,不能满足洁净燃料发动机使用要求。
W6Mo5Cr4V2高速钢具有硬度高、耐磨性好、耐腐蚀性强,而且在550~600℃仍可保持高硬度和高耐磨性,是常用的耐磨材料。但W6Mo5Cr4V2高速钢硬度高,切削加工困难,而且有些情况下材料并不需要太高硬度,如气门阀座、气门导管和衬套等。
目前,现有粉末冶金高速钢阀座制备大多采用铁基或铁基合金材料为基体粉末,并添加一定量的Co、Cr、Mo、Ni、C、Si等元素,烧结后形成碳化物弥散镶嵌在基体中,起到提高粉末冶金高速钢阀座硬度和耐磨性作用。中国专利(公开号CN102994917A,公开日2013.03.27)公开了一种乙醇燃料发动机气门座圈及其制备方法,其材料为C:1.1-1.6%;Cr:6.0-8.0%;Mo:6.0-8.0%;Co:10.0-13.0%;N:i2.0-4.0%;Mn:0.9-1.7%;S:0.7-1.5%;其它不可避免的杂质1.0%以下,余量为Fe。添加合金粒子Cr、Mo、Co,辅以MnS作润滑剂。制备特征为:烧结温度为1090~1110℃,烧结时间为14~16min。在热水蒸气中处理40~60min,其中,温度为540~560℃,表面生成厚度为3-4μm的Fe3O4氧化膜,以提高粉末冶金高速钢阀座耐磨和耐腐蚀性。中国专利(公开号CN102996196A,公开日2013.03.27)公开了一种发动机气门座圈及其制造方法,主要组分的铁(Fe);约0.6~1.2wt%的碳(C);约1.0~3.0wt%的镍(Ni);约8.0~11.0wt%的钴(Co)、约3.0~6.0wt%的铬(Cr);约4.0~7.0wt%的钼(Mo);约0.5~2.5wt%的钨(W);约1.0~3.0wt%的锰(Mn);约0.2~1.0wt%的钙(Ca);和其他不可避免的杂质。冲压该金属粉末混合物以形成密度为约6.85g/cm3或更高的致密结构;以及在约1130~1180℃的氮氛下烧结所述致密结构,省略浸渗或热处理。
上述方法存在有如下不足:
①粉末冶金高速钢阀座基体材料中添加的合金元素主要以固溶和碳化物形式存在才能有效提高材料性能,而上述专利采用的高碳、高合金材料没有合理配比碳化物的形成所需要的一定比例的C和合金元素,即使通过经验公式进行配比,烧结时也难以控制,并且与基体结合较差;
②采用铁基或铁基合金材料为基体,添加大量合金元素而不进行或热处理温度低,很难得到高合金组织和细小弥散碳化物,在气缸内气体燃烧时(约600℃左右)不能保持高硬度,耐磨性大大降低,同时,不进行或热处理温度低,得到珠光体等较软组织,而硬质颗粒硬度较高,这种硬度差别会造成基体和硬质颗粒剥落。
③采用W6Mo5Cr4V2高速钢材料,热处理后硬度≥63HRC,切削加工困难,塑韧性差,不适合批量生产。
发明内容
为了解决洁净燃料发动机粉末冶金阀座磨损情况严重的问题,本发明目的在于提供一种洁净燃料发动机粉末冶金高速钢阀座及其制备工艺。
本发明采取的技术方案是:
本发明的粉末冶金高速钢阀座材料以W6Mo5Cr4V2高速钢粉末为基体材料,添加有Co-Cr-Mo和Fe-Mo硬质颗粒、Cu;成分质量百分比为W6Mo5Cr4V2为45%~57%;Co-Cr-Mo为13%~17%;Fe-Mo为4%~7%;Cu为17%~22%;固体润滑剂和易切削成分为2%~3%,其中元素质量百分比含量组成如下:C:0.7~1.4%、Cr:3.5~12.5%、Mo:7.6~16%、Co:3.1~12%、Cu:18~22%、Mn:1~2.5%、S:0.5~1.5%、V:1~4%、W:2.4~7.3%、杂质3%以下,Fe:余量。
所述的杂质包括Ca、F、Si等。
所述的固体润滑剂是CaF2。
所述的易切削成分是MnS。
所述的粉末冶金高速钢阀座材料中基体材料添加Cu,Cu有5%左右为混合在压坯中即与其它粉末混合压制,剩余Cu粉为单独压制成与材料同尺寸的块状,放置在材料上,通过熔渗烧结(1180℃~1220℃),熔化成液态,渗入材料压坯孔隙中。
本发明的粉末冶金高速钢阀座的制备工艺的具体步骤如下:
(1)将原材料按比例进行称量;
(2)将配好的粉末原料进行混料;
(3)用液压机压制成压坯;
(4)在真空烧结炉中进行烧结,同时进行渗铜处理,熔渗烧结完成后随炉冷却;
(5)在真空淬火炉中进行淬火处理,然后多次回火。
(6)机械加工成成品。
步骤(4),真空熔渗烧结温度在1130℃~1200℃,烧结时间40min~100min,真空度1.0×10-3Pa左右。
步骤(5),淬火温度在1140℃~1260℃,真空度1.0×10-3Pa左右。回火温度520℃~580℃,回火2~4次,每次1h。
提高耐磨性原理:采用W6Mo5Cr4V2高速钢粉末为基体材料制备粉末冶金高速钢阀座,能得到较多和较稳定的合金碳化物,并且材料来源简单。通过渗铜处理填充粉末冶金高速钢阀座孔隙,提高粉末冶金高速钢阀座密度、导热性、力学性和改善耐腐蚀性。添加一定比例Co-Cr-Mo和Fe-Mo硬质颗粒进行强化,减少粉末冶金高速钢阀座材料和对磨件直接接触,提高耐磨性能。添加一定量CaF2、MoS2等高温固体润滑剂和硬脂酸锌等成型剂,提高粉末冶金高速钢阀座自润滑性能和成型性。通过合适的淬火+高温回火工艺,得到饱和合金回火马氏体和细小弥散二次合金碳化物,基体与硬质颗粒硬度差别缩小,在550~600℃仍可保持高硬度和高耐磨性,能充分发挥材料高红硬性、导热性、耐腐蚀等性能,提高洁净燃料发动机粉末冶金高速钢阀座耐磨性。
本发明的积极效果如下:
①本发明采用W6Mo5Cr4V2高速钢粉末为基体材料制备洁净燃料发动机粉末冶金高速钢阀座。粉末冶金高速钢问世已50多年,成分配比合理,性能稳定,能得到较多和较稳定的合金碳化物,材料来源简单;
②采用渗铜处理,填充材料孔隙,提高阀座密度、导热性;渗铜具有固溶强化、液相烧结和一定活化烧结作用,促进材料合金化;通过渗铜降低W6Mo5Cr4V2高速钢材料烧结温度和硬度,增强阀座切削性。
③通过合适的淬火+高温回火工艺,使热处理后材料中填充的铜挥发和流失少,保持粉末冶金高速钢阀座形貌正常,得到稳定的饱和合金回火马氏体和细小弥散二次合金碳化物,减小基体和硬质颗粒硬度差别,使基体和硬质颗粒结合更加牢固,充分发挥材料密度、硬度和耐磨性等性能。
附图说明
图1一种粉洁净燃料发动机粉末冶金高速钢阀座制备工艺曲线图。
具体实施方式
下面的实施例是对本发明的进一步详细描述。
(1)将原材料按比例进行称量。W6Mo5Cr4V2高速钢粉末颗粒≤150目,Co-Cr-Mo和Fe-Mo硬质颗粒≤250目。
(2)将配好的粉末原料在混料机置入双锥高效混合机中混合2h。
(3)用液压机压制成压坯。材料主体坯料密度控制6.7g/cm3左右;渗铜粉压制成环状,密度控制在6.5~6.8g/cm3。
实施例1
(1)在真空烧结炉中进行直接熔渗烧结,于600℃和800℃保温15min,1165℃保温40~100min,升温速度为10℃/min,熔渗烧结完成后随炉冷却。
(2)在真空淬火炉中加热到1140℃,保温30~50min,升温速度为10℃/min,在温油(50℃左右)中淬火,然后加热到300℃保温10min,520℃保温60min,回火处理3次。
(3)机械加工成成品
实施例2
(1)在真空烧结炉中进行直接熔渗烧结,于600℃和800℃保温15min,1165℃保温40~100min,升温速度为10℃/min,熔渗烧结完成后随炉冷却。
(2)在真空淬火炉中加热到1180℃,保温30~50min,升温速度为10℃/min,在温油(50℃左右)中淬火,然后加热到300℃保温10min,580℃保温60min,回火处理3次。
(3)机械加工成成品
实施例3
(1)在真空烧结炉中进行直接熔渗烧结,于600℃和800℃保温15min,1165℃保温40~100min,升温速度为10℃/min,熔渗烧结完成后随炉冷却。
(2)在真空淬火炉中加热到1220℃,保温30~50min,升温速度为10℃/min,在温油(50℃左右)中淬火,然后加热到300℃保温10min,520℃保温60min,回火处理3次。
(3)机械加工成成品
耐磨性试验。试验条件:磨损试验在M-2000型摩擦磨损试验机上进行,采用盘-销磨损,树脂氧化铝材料作磨料,载荷为120N,摩擦速度为200r/min,磨损时间为30min。
利用本发明技术方案制备的粉末冶金高速钢阀座具体指标为:
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (2)
1.一种制备粉洁净燃料发动机粉末冶金高速钢阀座的工艺,其特征在于:
所述的粉末冶金高速钢阀座材料以W6Mo5Cr4V2高速钢粉末为基体材料,添加有Cu、Co-Cr-Mo和Fe-Mo硬质颗粒;所述的粉末冶金高速钢阀座材料的成分质量百分比为:W6Mo5Cr4V2为45%~57%;Co-Cr-Mo为13%~17%;Fe-Mo为4%~7%;Cu为17%~22%,固体润滑剂和易切削成分为2%~3%,以上质量百分比总和是100%;所述的粉末冶金高速钢阀座材料的元素质量百分比含量组成如下:C:0.7~1.4%、Cr:3.5~12.5%、Mo:7.6~16%、Co:3.1~12%、Cu:18~22%、Mn:1~2.5%、S:0.5~1.5%、V:1~4%、W:2.4~7.3%、杂质3%以下,Fe:余量;
所述的杂质包括Ca、F、Si;
所述的固体润滑剂是CaF2;所述的易切削成分是MnS;所述的粉末冶金高速钢阀座材料中基体材料添加Cu,Cu有5%为混合在压坯中即与其它粉末混合压制,剩余Cu粉为单独压制成与材料同尺寸的块状,放置在材料上,通过熔渗烧结,熔化成液态,渗入材料压坯孔隙中;
所述工艺的具体步骤如下:
(1)将原材料按比例进行称量;
(2)将配好的粉末原料进行混料;
(3)用液压机压制成压坯;
(4)在真空烧结炉中进行烧结,同时进行渗铜处理,熔渗烧结完成后随炉冷却;
(5)在真空淬火炉中进行淬火处理,然后回火;
(6)机械加工成成品;
步骤(4),真空熔渗烧结温度在1130℃~1200℃,烧结时间40min~100min,真空度1.0×10-3Pa;步骤(5),淬火温度在1140℃~1260℃,真空度1.0×10-3Pa;回火温度520℃~580℃,回火2~4次,每次1h。
2.如权利要求1所述的制备粉洁净燃料发动机粉末冶金高速钢阀座的工艺,其特征在于:具体步骤是:将筛分好的粉末按质量分数配好,置入双锥高效混合机中混合2h,将混好的粉末放入模具中压制成圆环型坯料,压坯尺寸为Φ42mm×Φ28mm×9.4mm,密度控制在6.7g/cm3,压制好的生坯,生坯包含材料主体压坯和放置在上面的Cu-Fe-Mn,Cu占90%以上,压制的铜环,在WZC-30型真空烧结炉中进行熔渗烧结,随后进行热处理,熔渗烧结和热处理升温速度为10℃/min。
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