CN114606457A - 一种高熵合金氧化物涂层及其制备方法 - Google Patents
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Abstract
本发明公开了一种高熵合金氧化物及其制备方法,合金元素为Cu、Mn、Co、Fe和Ni,所述高熵合金氧化物涂层分为三层,从外向内依次为(Mn,Cu)3O4尖晶石层、Fe氧化物层和NiCo氧化物层;所述高熵合金氧化物的制备方法为:机械球磨混合纯金属粉末,等离子喷涂CuMnCoFeNi高熵合金涂层,涂层厚度控制15‑30µm,高温高氧压热生长形成复合导电氧化物涂层。本发明制备的高熵合金氧化物涂层有利于抑制铁素体不锈钢基体中Cr元素的外扩散,提高金属连接体的高温抗氧化性能;通过在铁素体不锈钢表面施加高浓度CuMnCo元素的高熵合金氧化物涂层,使涂层复合连接体具有高电子传导率和低离子传导率,提高燃料电池金属连接体的高温应用性能。
Description
技术领域
本发明属于燃料电池阴极侧金属连接体高温防护涂层技术领域,具体涉及一种高熵合金氧化物涂层材料及其制备方法。
背景技术
随着对固体氧化物燃料电池的深入探究和不断的改进,在降低电解质厚度而不损害其扩散屏障的有效性情况下,与较高温度(1000℃)所需的导电陶瓷连接材料相比,金属连接材料有着导热与导电性高、成本低、易加工等优点。金属连接体可以分为Cr,Ni,Fe基合金,Fe基合金相对于前两种合金有着更高的延展性、好的可加工性、热膨胀系数匹配以及成本低等优点,唯一不足的就是在高温环境下抗氧化能力不足,这就使得该合金在中温(600℃-800℃)氧化时所产生的Cr的氧化物或氢氧化物外扩散而导致“阴极中毒”现象,综合比较,铁素体不锈钢因其良好的导电导热性、热膨胀系数与其他组件匹配、价格低廉等优点,成为目前最具潜力的连接体材料。
与传统的高温防护不同,低离子传导率和高电子导电率是高温耐蚀导电涂层必有的特性,除此之外,还要求热膨胀系数与电池内部组件要相匹配以及自身有着良好的化学相容性,因此可以用于铁素体不锈钢连接体的高温耐蚀导电涂层并不多。目前研究的较多的金属连接体表面防护涂层大致可以分为以下四大类:MAlCrYO涂层;活性元素氧化物(REO)涂层;稀土钙钛矿型涂层;尖晶石涂层。MAlCrYO涂层(M代指钴、锰、钛金属),该涂层能提高金属连接体的高温抗氧化性,且能有效地抑制Fe合金中Cr元素的外扩散,但涂层制备的工艺较为复杂且成本较高,不利于投入大面积运用。与之相比,部分不含Cr的尖晶石涂层如Cu-Mn、Mn-Co、Co-Fe等尖晶石涂层其综合性能优异而备受研究者们的关注,如:(Mn,Co)3O4,(Cu,Mn)3O4等尖晶石具有高的电导率和与电池内部组件相接近的热膨胀系数,且能降低不锈钢基体表面富Cr氧化物的生长。
高熵合金的定义是合金中的每一种主要元素都具有高的原子百分比,但元素的最高含量不能超过35%,从整体来看,高熵合金的特色是由组成其元素的共同作用显示出来的。高熵合金中由多种元素引起的迟滞扩散效应和严重的晶格畸变效应的特点使得它们具有优异的结构稳定性和力学性能。
目前高熵合金的应用领域有:高硬度且耐磨耐温耐腐蚀的工具、化学工厂、船舰的耐蚀高强度材料;涡轮叶片、焊接材料、热交换器及高温炉的耐热材料等。高熵合金之所以在应用领域有着极其广泛的前景,正是由于它本身所体现出来的高硬度、耐磨性、耐蚀性等性能特点。高熵合金中晶体的每个空位也与混合焓和混合熵有关,在混合焓和混合熵之间的竞争使得合金中产生了一定的平衡空位浓度,在扩散过程中,全溶质基体中的空位实际上被不同的元素原子所包围和争夺,空位或原子都由波动扩散路径迁移,扩散速度较慢,活化能较高,因此,在高熵合金中扩散相变较慢。这个特性有利于抑制铁素体不锈钢基体中Cr元素的外扩散,提高燃料电池金属连接体的高温性能。
因此,基于提高金属连接器抗氧化性能和防止Cr挥发的双重目的,本发明在铁素体不锈钢表面施加特殊的高熵合金氧化物涂层,使涂层与金属基复合连接体具有高电子传导率和低离子传导率,具有与相邻的燃料电池部件相近的热膨胀系数和化学相容性。
发明内容
本发明为了提高固体氧化物燃料电池金属连接材料的高温抗氧化性以及防止高温下铬化物CrO3或CrO2(OH)2挥发所引发的阴极中毒现象,提供一种高熵合金氧化物涂层及其制备方法。
本发明的技术方案如下:
一种高熵合金氧化物涂层,其合金元素为Cu、Mn、Co、Fe和Ni,所述高熵合金氧化物涂层分为三层,从外向内依次为(Mn,Cu)3O4尖晶石层、Fe氧化物层和NiCo氧化物层。
进一步地,所述高熵合金氧化物涂层采用五种纯金属粉末制备而成,所述金属粉末分别为Cu粉、Mn粉、Co粉、Fe粉和Ni粉。
进一步地,所述Cu粉、Mn粉和Co粉的原子百分比分别为 (20~25) at.%、(20~25)at.%和 (20~25) at.%。
进一步地,所述Fe粉和Ni粉的原子百分比分别为 (10~20) at.%和(10~20) at.%。
进一步地,所述高熵合金氧化物涂层可应用于固体氧化物燃料电池连接体材料。
本发明提供了上述高熵合金氧化物涂层的制备方法,按以下步骤进行:
① 称取Cu、Mn、Co、Fe和Ni纯金属粉末混合,机械球磨10h,得到的超细0.01-1μm的混合粉末;
② 铁素体不锈钢基体表面预处理:预磨、丙酮清洗,干燥密封;
③ 使用等离子喷涂技术,在铁素体不锈钢基体上制备CuMnCoFeNi高熵合金涂层,所选择的参数为功率25KW,喷距100mm,送粉率20-25 g∕min,氩气流量80 L∕min,不锈钢基体预热250 ℃;
④ CuMnCoFeNi高熵合金涂层在高温高氧压环境中热生长,得到复合导电氧化物涂层。
所述步骤③中CuMnCoFeNi高熵合金涂层厚度为15-30 µm。
所述步骤④中所采用的高温高氧压环境中,温度为750℃~950℃,氧分压为104~105帕,时间为25-50 h。
本发明的技术方案能产生以下的有益效果:
(1)本发明制备形成的高熵合金氧化物涂层,在CuMnCoFeNi高熵合金中采取了高于平均浓度的CuMnCo元素,使较大浓度的Mn的氧化物可有效与Cu氧化物、Co氧化物合成复合尖晶石氧化物,同时抑制Fe、Cr元素外扩散,能使涂层与金属基复合连接体具有高电子传导率和低离子传导率,具有与相邻的燃料电池部件相近的热膨胀系数和化学相容性,提高了燃料电池金属连接体的耐高温性能。
(2)通过高温热生长形成涂层,该方法制备的复合涂层与金属不锈钢基材的粘附性较好,解决了此类复合氧化物陶瓷涂层易剥落的问题。
附图说明
图1为本发明实施例1中制备的高熵合金涂层在高温高氧压环境中热生长得到的复合导电氧化物涂层的截面形貌。
图2为本发明实施例5中制备的高熵合金涂层在高温高氧压环境中热生长得到的复合导电氧化物涂层的截面形貌。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合附图和实施例对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。
实施例1
本发明是一种高熵合金氧化物涂层的制备方法,称取Cu、Mn、Co、Fe和Ni纯金属粉末,其中Cu粉、Mn粉和Co粉的原子百分比分别为20 %、20 %和 20 %,Fe粉和Ni粉的原子百分比分别为20 %和20 %。机械球磨Cu、Mn、Co、Fe和Ni混合粉末10h,得到的超细0.01-1μm的均匀混合粉末。铁素体不锈钢430 SS基体表面预处理,经水磨砂纸打磨至800#,然后用蒸馏水和丙酮清洗吹干。使用等离子喷涂技术,在铁素体不锈钢基体上制备CuMnCoFeNi高熵合金涂层,等离子喷涂参数设置为:功率25KW,喷距100mm,送粉率20 g∕min,氩气流量80 L∕min,不锈钢基体预热250 ℃,等离子喷涂CuMnCoFeNi高熵合金涂层的厚度控制约为15 µm。进而在高温高氧压环境中热生长高熵合金氧化物涂层,设定温度750℃,氧分压104帕,氧化时间25 h,得到复合导电氧化物涂层金属连接体,所得复合氧化物涂层分为三层,外测(Mn,Cu)3O4尖晶石层、中间Fe氧化物层和内侧NiCo氧化物层。在800 ℃时测试其高温电导率低于100S/cm,可有效阻止高温下铬化物的挥发,提高燃料电池金属连接体的高温性能,使复合连接体有与相邻的燃料电池部件相近的热膨胀系数和化学相容性,其高温热膨胀系数居于11~12.5x 10-6/℃之间。
实施例2
本发明是一种高熵合金氧化物涂层的制备方法,称取Cu、Mn、Co、Fe和Ni纯金属粉末,其中Cu粉、Mn粉和Co粉的原子百分比分别为25 %、25 %和 25 %,Fe粉和Ni粉的原子百分比分别为10 %和15 %。机械球磨Cu、Mn、Co、Fe和Ni混合粉末10h,得到的超细0.01-1μm的均匀混合粉末。铁素体不锈钢430 SS基体表面预处理,经水磨砂纸打磨至600#,然后用蒸馏水和丙酮清洗吹干。使用等离子喷涂技术,在铁素体不锈钢基体上制备CuMnCoFeNi高熵合金涂层,等离子喷涂参数设置为:功率25KW,喷距100mm,送粉率25 g∕min,氩气流量80 L∕min,不锈钢基体预热至250 ℃,等离子喷涂CuMnCoFeNi高熵合金涂层的厚度控制约为30µm。进而在高温高氧压环境中热生长高熵合金氧化物涂层,设定温度950℃,氧分压104帕,氧化时间50 h,得到复合导电氧化物涂层金属连接体,所得复合氧化物涂层分为三层,外测(Mn,Cu)3O4尖晶石层、中间Fe氧化物层和内侧NiCo氧化物层。在800 ℃时测试其高温电导率低于100 S/cm,可有效阻止高温下铬化物的挥发,提高燃料电池金属连接体的高温性能,使复合连接体有与相邻的燃料电池部件相近的热膨胀系数和化学相容性,其高温热膨胀系数居于11~12.5x 10-6/℃之间。
实施例3
本发明是一种高熵合金氧化物涂层的制备方法,称取Cu、Mn、Co、Fe和Ni纯金属粉末,其中Cu粉、Mn粉和Co粉的原子百分比分别为22 %、20 %和 23 %,Fe粉和Ni粉的原子百分比分别为15 %和10 %。机械球磨Cu、Mn、Co、Fe和Ni混合粉末10h,得到的超细0.01-1μm的均匀混合粉末。铁素体不锈钢430 SS基体表面预处理,经水磨砂纸打磨至400#,然后用蒸馏水和丙酮清洗吹干。使用等离子喷涂技术,在铁素体不锈钢基体上制备CuMnCoFeNi高熵合金涂层,等离子喷涂参数设置为:功率25KW,喷距100mm,送粉率20 g∕min,氩气流量80 L∕min,不锈钢基体预热至250 ℃,等离子喷涂CuMnCoFeNi高熵合金涂层的厚度控制约为25µm。进而在高温高氧压环境中热生长高熵合金氧化物涂层,设定温度850℃,氧分压105帕,氧化时间35 h,得到复合导电氧化物涂层金属连接体,所得复合氧化物涂层分为三层,外测(Mn,Cu)3O4尖晶石层、中间Fe氧化物层和内侧NiCo氧化物层。在800 ℃时测试其高温电导率低于100 S/cm,可有效阻止高温下铬化物的挥发,提高燃料电池金属连接体的高温性能,使复合连接体有与相邻的燃料电池部件相近的热膨胀系数和化学相容性,其高温热膨胀系数居于11~12.5x 10-6/℃之间。
实施例4
本发明是一种高熵合金氧化物涂层的制备方法,称取Cu、Mn、Co、Fe和Ni纯金属粉末,其中Cu粉、Mn粉和Co粉的原子百分比分别为20 %、25 %和 25%,Fe粉和Ni粉原子百分比分别为15 %和15 %。机械球磨Cu、Mn、Co、Fe和Ni混合粉末10h,得到的超细0.01-1μm的均匀混合粉末。铁素体不锈钢430 SS基体表面预处理,经水磨砂纸打磨至800#,然后用蒸馏水和丙酮清洗吹干。使用等离子喷涂技术,在铁素体不锈钢基体上制备CuMnCoFeNi高熵合金涂层,等离子喷涂参数设置为:功率25KW,喷距100mm,送粉率25 g∕min,氩气流量80 L∕min,不锈钢基体预热至250 ℃,等离子喷涂CuMnCoFeNi高熵合金涂层的厚度控制约为26 µm。进而在高温高氧压环境中热生长高熵合金氧化物涂层,设定温度900℃,氧分压104帕,氧化时间40 h,得到复合导电氧化物涂层金属连接体,所得复合氧化物涂层分为三层,外测(Mn,Cu)3O4尖晶石层、中间Fe氧化物层和内侧NiCo氧化物层。在800 ℃时测试其高温电导率低于100S/cm,可有效阻止高温下铬化物的挥发,提高燃料电池金属连接体的高温性能,使复合连接体有与相邻的燃料电池部件相近的热膨胀系数和化学相容性,其高温热膨胀系数居于11~12.5x 10-6/℃之间。
实施例5
本发明是一种高熵合金氧化物涂层的制备方法,称取Cu、Mn、Co、Fe和Ni纯金属粉末,其中Cu粉、Mn粉和Co粉的原子百分比分别为25 %、20 %和 20 %,Fe粉和Ni粉原子百分比分别为15 %和20 %。机械球磨Cu、Mn、Co、Fe和Ni混合粉末10h,得到的超细0.01-1μm的均匀混合粉末。铁素体不锈钢430 SS基体表面预处理,经水磨砂纸打磨至200#,然后用蒸馏水和丙酮清洗吹干。使用等离子喷涂技术,在铁素体不锈钢基体上制备CuMnCoFeNi高熵合金涂层,等离子喷涂参数设置为:功率25KW,喷距100mm,送粉率22 g∕min,氩气流量80 L∕min,不锈钢基体预热至250 ℃,等离子喷涂CuMnCoFeNi高熵合金涂层的厚度控制约为21µm。进而在高温高氧压环境中热生长高熵合金氧化物涂层,设定温度800℃,氧分压104帕,氧化时间26 h,得到复合导电氧化物涂层金属连接体,所得复合氧化物涂层分为三层,外测(Mn,Cu)3O4尖晶石层、中间Fe氧化物层和内侧NiCo氧化物层。在800 ℃时测试其高温电导率低于100S/cm,可有效阻止高温下铬化物的挥发,提高燃料电池金属连接体的高温性能,使复合连接体有与相邻的燃料电池部件相近的热膨胀系数和化学相容性,其高温热膨胀系数居于11~12.5x 10-6/℃之间。
上述仅为本发明的优选实施例而已,并不对本发明起到任何限制作用。任何所属技术领域的技术人员,在不脱离本发明的技术方案的范围内,对本发明揭露的技术方案和技术内容做任何形式的等同替换或修改等变动,均属未脱离本发明的技术方案的内容,仍属于本发明的保护范围之内。
Claims (8)
1.一种高熵合金氧化物涂层,所述高熵合金氧化物涂层的合金元素为Cu、Mn、Co、Fe和Ni,其特征在于,所述高熵合金氧化物涂层分为三层,从外向内依次为(Mn,Cu)3O4尖晶石层、Fe氧化物层和NiCo氧化物层。
2.根据权利要求1所述的一种高熵合金氧化物涂层,其特征在于,所述高熵合金氧化物涂层采用五种纯金属粉末制备而成,所述金属粉末分别为Cu粉、Mn粉、Co粉、Fe粉和Ni粉。
3.根据权利要求2所述的一种高熵合金氧化物涂层,其特征在于,所述Cu粉、Mn粉和Co粉的原子百分比分别为 (20~25) at.%、(20~25) at.%和 (20~25) at.%。
4.根据权利要求2所述的一种高熵合金氧化物涂层,其特征在于,所述Fe粉和Ni粉的原子百分比分别为 (10~20) at.%和(10~20) at.%。
5.一种如权利要求1-4任一项所述的高熵合金氧化物涂层制备方法,其特征在于,包括以下步骤:
① 称取Cu、Mn、Co、Fe和Ni纯金属粉末混合,机械球磨10h,得到的超细0.01-1μm的混合粉末;
② 铁素体不锈钢基体表面预处理:预磨、丙酮清洗,干燥密封;
③ 使用等离子喷涂技术,在铁素体不锈钢基体上制备CuMnCoFeNi高熵合金涂层,所选择的参数为功率25KW,喷距100mm,送粉率20-25 g∕min,氩气流量80 L∕min,不锈钢基体预热250 ℃;
④ CuMnCoFeNi高熵合金涂层在高温高氧压环境中热生长,得到复合导电氧化物涂层。
6.根据权利要求5所述的一种高熵合金氧化物涂层制备方法,其特征在于,所述步骤③中CuMnCoFeNi高熵合金涂层厚度为15-30 µm。
7.根据权利要求5所述的一种高熵合金氧化物涂层制备方法,其特征在于,所述步骤④中所采用的高温高氧压环境中,温度为750℃~950℃,氧分压为104~105帕,时间为25-50 h。
8.权利要求1-4任一项所述的高熵合金氧化物涂层的应用,其特征在于,应用所述高熵合金氧化物涂层来制备固体氧化物燃料电池的连接体材料。
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US20200056272A1 (en) * | 2018-08-14 | 2020-02-20 | The Industry & Academic Cooperation In Chungnam National University(Iac) | Twinning/transformation induced plasticity high entropy steels and method of manufacturing the same |
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