CN109986074A - Fe3Al/Cr7C3粉末及其制备方法和相应涂层 - Google Patents
Fe3Al/Cr7C3粉末及其制备方法和相应涂层 Download PDFInfo
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
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- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
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- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
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- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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Abstract
本发明公开了一种Fe3Al/Cr7C3粉末及其制备方法和相应涂层,属于中高温耐磨特种涂层材料技术领域。采用惰气保护的真空雾化工艺制备原位自生Cr7C3为强化相的的金属/陶瓷复合粉末,实现金属间化合物粘结相Fe3Al和陶瓷增强相Cr7C3的原位生成,陶瓷相弥散分布,陶瓷硬质相与粘结相界面成分自然过渡,结合紧凑;以该粉末为原料,通过热喷涂等工艺方法制备的相结构基本不变的金属间化合物基金属陶瓷涂层,具有陶瓷硬质相体积分数可控、分散性好的结构特征。本发明述及的涂层具有高温硬度高、耐磨性好、适用范围广、成本低的优点。
Description
技术领域
本发明属于中高温耐磨特种涂层材料技术领域,涉及一种以Fe3Al金属间化合物为粘结相、碳化物Cr7C3原位自生的金属陶瓷粉末及其制备方法和相应涂层。
背景技术
金属陶瓷耐磨涂层是金属部件耐磨防护所采用的主要措施之一。目前工业部件耐磨涂层材料主要以碳化铬或碳化钨硬质相强化的金属陶瓷为主,此类材料作为高温传动摩擦部件防护涂层在连续高温边界润滑条件下与特定摩擦副对磨时,往往无法满足严苛复杂工况下的使用要求,需在现有材料体系基础上,克服缺陷,发挥新材料复合特性,提高碳化物强化相的耐磨优势,提高综合性能。
Fe-Al合金具有反常屈服行为,从室温至500℃左右其屈服强度降低很慢。Fe3Al金属间化合物由于优异的抗氧化性能、良好的机械性能以及低廉的成本,成为高温结构材料中的一类。将Fe3Al应用于耐中高温磨损具有很大潜力,特别是在200℃-600℃范围内的气蚀和滑动磨损条件下,这源于Fe3Al金属间化合物具有加工硬化和在一定温度范围内屈服强度随着温度升高而基本保持不变的特性,这是Ni基(如Ni、NiCr)和钴基(如Co、CoCr)等最常用金属陶瓷耐磨涂层材料粘结相所不具备的工业高温应用所梦寐以求的性能。已有部分研究采用常规复合粉末制备方法(如胶粘团聚)制备出Ni3Al-Cr3C2粉末,但存在成分不均匀、成本高的缺点。
发明内容
本发明的目的之一是提供一种以Fe3Al金属间化合物为粘结相、碳化物Cr7C3原位自生的金属陶瓷粉末。所述的粉末材料的特征是在Fe3Al型金属间化合物基相中原位自生Cr7C3碳化物,采用真空雾化工艺实现Cr7C3碳化物在所制备Fe3Al型金属间化合物粉末中的原位自生。
本发明的目的是通过以下技术方案实现的:
Fe3Al/Cr7C3粉末,其特征在于,该粉末以Fe3Al金属间化合物为粘结相,碳化物Cr7C3原位自生;粉末中元素组成为:Al:10-14wt%;Cr:15-33wt%;C:0.5-3wt%;B:0.1-0.3wt%;Fe:余量。
进一步地,该粉末是以铁、铬、高碳铬铁、铝、硼铁作为原料,通过气体雾化工艺制备,所述Fe3Al是在气体雾化过程中直接形成的金属间化合物相、有部分Cr元素固溶,Fe3Al与碳化物Cr7C3呈冶金型结合。所述Fe3Al是在气体雾化过程中直接形成的金属间化合物相、有部分Cr元素固溶,从而形成(Fe,Cr)3(Al,Cr)复杂成分,Fe3Al在粉末内部作为粘结相,与碳化物强化相呈冶金型结合,组织致密无孔隙,并均匀地包裹着碳化物相,有利于碳化物降低失碳或防止被氧化。
进一步地,所述Cr7C3是在气体雾化过程中直接原位自生成的碳化物强化相,碳化物呈条纹状弥散分布粘结相之中,与基相之间的界面干净、无污染、结合强度高,不存在润湿性问题,并且分布均匀。
本发明的另一目的是提供所述Fe3Al/Cr7C3粉末的制备方法,包括以下步骤:
步骤A:按粉末元素组成:Al:10-14wt%;Cr:15-33wt%;C:0.5-3wt;B:0.1-0.3wt%;Fe:余量计算铁、铬、高碳铬铁、铝和硼铁原料的投料量,将原料放入坩埚中;
步骤B:密闭气雾化设备,抽真空,将原料在坩埚中加热熔化,熔化过程中用Ar气体保护;
步骤C:引导坩埚中的液体金属从坩埚的底部导流管流出,进入雾化室,雾化气体Ar气经雾化喷嘴冲击熔融合金液流,将液流雾化成弥散细小的液态颗粒,液态颗粒冷却凝固后得到Fe3Al/Cr7C3原始粉末;
步骤D:对Fe3Al/Cr7C3原始粉末进行破碎和筛分,从而制得Fe3Al/Cr7C3粉末。
优选地,步骤A熔炼时间90-120min,真空度25-40Pa,熔池温度由“铂铑30-铂铑6”热电偶测量,保持在1873K~2073K。
优选地,步骤C雾化条件为:雾化温度1960-1965K,喷嘴直径3-10mm,雾化气体为高纯Ar,气体压力为3.3-3.5MPa。
本发明的另一目的是提供一种Fe3Al/Cr7C3粉末形成的涂层,由该粉末为原料,采用热喷涂、激光熔覆、堆焊或冷喷涂技术形成涂层,其特征在于,涂层中原位自生Cr7C3陶瓷相以纳米或接近纳米尺度,呈条纹状分布,将Fe3Al/Cr7C3粉末中的碳化物分布形态较好地延续承至涂层中,改变了传统硬质相的分布状态。
该复合型Fe3Al/Cr7C3粉末可以通过包括但不限于热喷涂、激光熔覆、堆焊、冷喷涂等涂层制备工艺,制备复合型Fe3Al/Cr7C3涂层,所形成的涂层在200~600℃温度范围内具有优秀的耐磨损性,特别适合用于300℃~500℃范围内的气蚀和滑动磨损条件下摩擦磨损防护,且制备材料成本低。
进一步地,采用HVOF喷涂制备涂层。由于在HVOF喷涂过程中,Fe3Al/Cr7C3粉末中的碳化物分布形态沿袭至涂层中以及陶瓷相和金属相之间形成类冶金结合,涂层具有优异的摩擦磨损防护性能。
由上述本发明提供的技术方案可以看出,本发明提供的复合型Fe3Al/Cr7C3粉末采用气雾化工艺直接制备,所得粉末具有雾化粉末通常呈现的球形的形状,表面较光滑,结构致密,原位自生的暗色条纹状的碳化物强化相弥散地分布在基相之中,并与基相呈冶金型结合,组织致密无孔隙。与传统团聚方法制备的NiCr/Cr3C2、Ni3Al/Cr3C2、Fe3Al/Cr3C2等金属陶瓷复合粉末相比,金属相与陶瓷相间的结合力明显提高,基体相均匀地包裹着碳化物相,有利于碳化物降低失碳或被氧化的风险。从而通过HVOF方法所制备出的复合型Fe3Al/Cr7C3涂层中,组织均匀致密,灰黑色条纹状初生陶瓷相均匀分布于细小的灰白色共晶基体上。雾化涂层比团聚复合涂层具有更好的减轻对磨材料磨损量的作用,这主要源于专利中的涂层中的Cr7C3陶瓷相是在粉末熔炼—雾化制备过程中直接原位生成的,陶瓷相和金属相之间形成类冶金结合,原位自生的陶瓷强化相呈条纹状和针状,并在HVOF喷涂过程中沿袭至涂层中,这种细长的弥散高硬相形成对基体的“纤维”复合作用,从而陶瓷相不易脱落形成第三粒,降低了磨粒磨损的可能性,磨损过程中有利于降低对对磨材料的磨损作用。而常规方法的复合型金属/陶瓷涂层由于外添加的陶瓷相多为具有多边棱角的陶瓷颗粒,沉积到涂层中形成对基体的“颗粒”复合作用,在后续磨损过程中,相对结合更差的“颗粒”复合使不规则多棱角的陶瓷颗粒往往容易脱落在摩擦表面形成第三粒,造成涂层和对磨材料的过度磨损。
本发明所提供的复合型Fe3Al粉末采用雾化工艺实现Cr7C3型碳化物在所制备Fe3Al型金属间化合物粉末中的原位自生,其特征是在Fe3Al金属间化合物基相中原位自生Cr7C3,通过热喷涂等涂层制备工艺,粉末中的原位自生Cr7C3较好的延续承至涂层中。由于沿袭至涂层中以及陶瓷相和金属相之间形成类冶金结合,所制备涂层在高温下拥有更好耐磨性,与传统的WC-Co和Cr3C2-NiCr涂层相比,涂层在200~600℃温度范围内具有更加优秀的耐磨损性,且制备成本更低,特别适合用于300℃~500℃范围内的气蚀和滑动磨损条件下摩擦磨损防护。可以用于航空航天热端耐磨件、重载柴油发动机气缸、曲轴等防护。
附图说明
图1是本发明提供的Fe3Al/Cr7C3粉末及涂层SEM照片,其中(a)为粉末低倍表面形貌;(b)为粉末高倍截面形貌;(c)为涂层截面形貌。
具体实施方式
下面对本发明中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明的保护范围。
下面对本发明所提供的复合型Fe3Al/Cr7C3粉末及其制备方法进行详细描述。本发明实施例中未作详细描述的内容属于本领域专业技术人员公知的现有技术。
一种复合型Fe3Al/Cr7C3粉末,该粉末是由铁、铬、高碳铬铁、铝、硼铁块体材料作为原料,通过气体雾化工艺制备,粉末成分为:Al:10~14wt%;Cr:15~33wt%;C:0.5~3wt%;B:0.1-0.3wt%;Fe:余量。
具体地,本发明所提供的复合型Fe3Al/Cr7C3粉末的制备方法可以包括以下步骤:
步骤A、将原料在坩埚中加热熔化,熔池温度由“铂铑30-铂铑6”热电偶测量,真空度25-40Pa,熔炼时间90-120min,熔炼温度保持在1873K~2073K。熔化过程中用Ar气体保护。
步骤B、引导气雾化塔坩埚中的液体金属从坩埚的底部导流管流出,进入雾化室,采用高压高速的雾化气体Ar气经雾化喷嘴冲击熔融合金液流,将液流雾化成弥散细小的液态颗粒,雾化温度1960-1965K,喷嘴直径3-10mm,气体压力为3.3-3.5MPa,待这些液态小颗粒冷却凝固后,得到Fe3Al/Cr7C3粉末。
其具体特点如下:
①本发明在雾化前需经过精确的成分设计与计算,在原位自生碳化物的真空雾化制粉工艺中,成分设计是至关重要的。成分设计中,为避免单相Fe3Al金属间化合物韧性差,向合金中添加0.1~0.3wt.%B来有效避免这种内在脆性,增加韧性。为了得到理想的材料,碳化物的设计投料比(at.%)既包含了生成Cr7C3的需要,又考虑到部分Cr将固溶,形成(Fe,Cr)3(Al,Cr)复杂组织的补偿Cr含量;同时,为了抑制包晶反应析出易堵雾化喷嘴的FeAl,设计中还对Al化学计量比做了限定。
②本发明中选择气雾化方法制得的类合金型Cr7C3弥散强化Fe-Al复合粉末球形度高,氧含量低,陶瓷增强相在基体中原位自生,且与基体合金之间的界面干净、无污染、结合强度高,不存在润湿性问题,并且分布均匀,减少夹杂。
③本发明中采用低成本的Fe为最主要的成分,与目前同类型防护涂层中大量使用的Ni基、Co基材料相比,耐磨性不明显降低,而成本大幅下降。
进一步地,以上述本发明所提供的复合型Fe3Al/Cr7C3粉末为原料,采用包括但不限于热喷涂、冷喷涂、激光熔覆、堆焊等涂层制备技术可以在金属部件表面制备出Fe3Al/Cr7C3涂层。与现有其它同用途的粉末相比,本发明所提供的粉末及其所制备出的涂层至少具有以下优点:
(1)所得粉末呈球形的形状,表面光滑,结构致密,原位自生的暗色条纹状的碳化物弥散强化相弥散分布在基相之中,并与基相呈冶金型结合,组织致密无孔隙。
(2)与传统团聚方法制备的NiCr/Cr3C2、Fe3Al/Cr3C2等金属陶瓷复合粉末相比,金属相与陶瓷相间的结合力明显提高,基体相均匀地包裹着碳化物相,有利于碳化物降低失碳或被氧化的风险。
(3)与传统团聚方法制备的NiCr/Cr3C2、Ni3Al/Cr3C2、Co/WC等金属陶瓷复合粉末相比,高温耐磨性更优,且粉末原料成本大幅降低。
(4)所形成的复合型Fe3Al/Cr7C3涂层改变了硬质相的分布状态,提高了涂层的高温强度和高温耐磨性,提高了涂层的自润滑寿命,在改善200℃~600℃范围内的气蚀和滑动磨损条件下的材料防护具有很好的应用价值。
为了更加清晰地展现出本发明所提供的技术方案及所产生的技术效果,下面以具体实施例对本发明实施例所提供的复合型Fe3Al/Cr7C3粉末、涂层及其制备方法与应用进行详细描述。
实施例1
一种复合型Fe3Al/Cr7C3粉末及涂层,其制备方法可包括以下步骤:
步骤A、按投料比为:Al:13.60wt%;Cr:18.33wt%;C:1.35;B:0.2wt%;Fe:余量,计算铁、铬、高碳铬铁、铝、硼铁块等原料的投料量,将原料放入坩埚。
步骤B、密闭气雾化设备,抽真空,熔化过程中用Ar气体保护,控制真空度30Pa。将原料在坩埚中加热熔化,热电偶实时测量熔池温度,熔炼温度保持在1900K~2060K,熔炼时间90min。
步骤C、引导气雾化塔坩埚中的液体金属从坩埚的底部导流管流出,进入雾化室,采用高压高速的雾化气体Ar气经雾化喷嘴冲击熔融合金液流,将液流雾化成弥散细小的液态颗粒,雾化温度1963K,喷嘴直径6mm,气体压力为3.5MPa,待这些液态小颗粒冷却凝固后,得到Fe3Al/Cr7C3原始粉末。
步骤D、对烧结块进行破碎和筛分,从而即可制得复合型Fe3Al/Cr7C3粉末。
综上可见,本发明实施例改变了硬质相的分布状态,降低了涂层材料成本,提高了涂层的高温强度和高温耐磨性,提高了涂层的自润滑寿命,在改善200℃-600℃范围内的气蚀和滑动磨损条件下的材料防护具有很好的应用价值。
所制备的粉末及涂层的电镜形貌见图1,粉末球形度高,陶瓷增强相在基体中原位自生,且分布均匀;粉末与采用该粉末喷涂制备而成的涂层的成分见表1,可见通过喷涂,粉末成分较好地遗传到涂层当中。
表1 Fe3Al/Cr7C3粉末与涂层的成分(wt.%)
如上工艺所制备的粉末的基本性能见表2。
表2 Fe3Al/Cr7C3粉末的性能
采用以上粉末为原料制备的涂层的基础性能见表3。
表3 Fe3Al/Cr7C3涂层的基础性能
在室温分别比较了实施例中制备的涂层与商用RuT350铸铁(基体材料)在室温和400℃下,同销盘磨损条件(对磨材料灰铸铁,载荷20N、行程3mm、频率30Hz、温度室温/400℃、试验时间8分钟)下的磨损量值,见表4。
表4 Fe3Al/Cr7C3涂层和对磨灰铸铁磨损量
可见,相比于RuT350铸铁基体,Fe3Al/Cr7C3涂层中由于添加原位自生(Cr,Fe)7C3,对于对材料的抗磨损性能有很大的改善。这种趋势在室温和400℃温度下是一致的。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。
Claims (8)
1.Fe3Al/Cr7C3粉末,其特征在于,该粉末以Fe3Al金属间化合物为粘结相,碳化物Cr7C3原位自生;粉末中元素组成为:Al:10-14wt%;Cr:15-33wt%;C:0.5-3wt%;B:0.1-0.3wt%;Fe:余量。
2.根据权利要求1所述的Fe3Al/Cr7C3粉末,其特征在于,该粉末是以铁、铬、高碳铬铁、铝、硼铁作为原料,通过气体雾化工艺制备,所述Fe3Al是在气体雾化过程中直接形成的金属间化合物相、有部分Cr元素固溶,Fe3Al与碳化物Cr7C3呈冶金型结合。
3.根据权利要求2所述的Fe3Al/Cr7C3粉末,其特征在于,所述Cr7C3是在气体雾化过程中直接原位自生成的碳化物强化相,碳化物呈条纹状弥散分布在粘结相之中。
4.根据权利要求1-3任一权利要求所述的Fe3Al/Cr7C3粉末的制备方法,其特征在于,包括以下步骤:
步骤A:按粉末元素组成:Al:10-14wt%;Cr:15-33wt%;C:0.5-3wt;B:0.1-0.3wt%;Fe:余量计算铁、铬、高碳铬铁、铝和硼铁原料的投料量,将原料放入坩埚中;
步骤B:密闭气雾化设备,抽真空,将原料在坩埚中加热熔化,熔化过程中用Ar气体保护;
步骤C:引导坩埚中的液体金属从坩埚的底部导流管流出,进入雾化室,雾化气体Ar气经雾化喷嘴冲击熔融合金液流,将液流雾化成弥散细小的液态颗粒,液态颗粒冷却凝固后得到Fe3Al/Cr7C3原始粉末;
步骤D:对Fe3Al/Cr7C3原始粉末进行破碎和筛分,从而制得Fe3Al/Cr7C3粉末。
5.根据权利要求4所述的制备方法,其特征在于,步骤A控制真空度25-40Pa,熔炼温度保持在1873K~2073K,熔炼时间90-120min。
6.根据权利要求4所述的制备方法,其特征在于,步骤C雾化温度1960-1965K,喷嘴直径3-10mm,气体压力为3.3-3.5MPa。
7.根据权利要求1-3任一权利要求所述的Fe3Al/Cr7C3粉末形成的涂层,由该粉末为原料,采用热喷涂、激光熔覆、堆焊或冷喷涂技术形成涂层,其特征在于,涂层中原位自生Cr7C3陶瓷相以纳米或接近纳米尺度,呈条纹状分布。
8.根据权利要求7中所述的涂层,其特征在于,采用HVOF喷涂制备涂层。
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