CN115584425A - 一种高硬度高耐磨的高熵合金涂层及其制备方法 - Google Patents
一种高硬度高耐磨的高熵合金涂层及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种高硬度高耐磨的高熵合金涂层及其制备方法,其特征在于:合金分子式为:AlCoCrMoVx,x为0‑1。所制备的AlCoCrMoVx高熵合金涂层具有硬度高、耐磨性好的特点,在电化学腐蚀过程中会生成一层黑色的氧化膜,随着电压增加,其氧化膜不会被击穿,说明其在动态电压条件下性能优异。
Description
技术领域
本发明涉及合金技术领域,具体涉及一种高硬度高耐磨的高熵合金涂层及其制备方法。
背景技术
可以通过调控合金元素的成分,使得高熵合金兼具耐磨性和耐蚀性,有希望作为替代材料。高熵合金又称为多组元合金,其主金属元素至少为五种并且以等原子比或近等原子比组成。它的出现为开拓新材料提供了新思路。高熵合金具有众多优于传统Fe、Ti、Ni基合金的性质,如组织结构上呈现简单的固溶体结构以及优异的高温组织稳定性,性能上表现出高强度和硬度、优良的耐蚀及耐磨性等,在高速切削用刀具、各类工模具、涡轮机叶片等领域具有广阔的应用前景。
CoCrMo合金具有优异的疲劳强度以及耐腐蚀性能,Co为自钝化元素, Mo为可钝化元素,Cr具有很高的耐腐蚀性。但是CoCrMo基合金的摩擦磨损性能比较差。
激光熔覆是一种表面改性技术,通过预置法在基材表面预置一层高熵合金,利用高能密度激光束使之与基材熔凝。由于激光熔覆的冷却速度比较快,使得过冷度比较大,导致晶粒得形核速率要比生长速率要大,从而可以得到细小的晶粒。通常情况下,材料的结构决定性能。因此,选择激光熔覆作为制备方法以获得细小晶粒而提高机械性能以及硬度。
发明内容
针对现有技术中所存在的不足,本发明的目的在于提供一种高硬度高耐磨的高熵合金涂层,本发明还提供了其制备方法,以CoCrMo为基体,通过添加Al元素和钒元素,提高硬度和耐磨性。
为实现上述第一目的,本发明采用了如下的技术方案:一种高硬度高耐磨的高熵合金涂层,其特征在于:合金分子式为:AlCoCrMoVx,x为0-1。
优选:所述x为0.6或0.8。
本发明的第二目的是这样实现的:一种高硬度高耐磨的高熵合金涂层的制备方法,其特征在于,按照如下步骤制备:
1)准确称取Al、Co、Cr、Mo、V粉末;
2)将称取好的粉末放入球磨罐中球磨,为防止粉末粘结,加入适量酒精,
3)使得粉末混合均匀,然后烘干、过筛、干燥保存;
4)对基材表面进行打磨以除去表面氧化皮,直到露出光亮面;
5)采用预置粉末法,将球磨后的合金粉末预置于基材打磨面,在基材表面预涂合金粉末,利用宽带激光熔覆设备进行涂层制备。
上述方案中:Co、Cr、Mo、V粉末,粉末粒度为45-105μm,纯度均≥ 99.9%。
上述方案中:球磨时,球料比为5:1,球磨转数350rpm/min,球磨时间 t=1.5h。
上述方案中:使用激光器型号为RC-LMS-6000-R光纤激光器,激光熔覆参数:激光功率P=3500W,扫描速率v=5mm/s,矩形光斑尺寸20×2mm2,气流密度为15L/min。
本发明通过添加Al元素对钝化膜进行修复以及保护,在空气中形成的 Al2O3氧化膜也可以提高其耐磨性能。V元素的熔点比较高,为难熔金属,钒大多应用于钢铁,通过细化钢的组织和晶粒,从而可以提高钢的强度、韧性以及耐磨性。但是钒在高熵合金中的应用研究还比较少,所以本专利通过研究钒在高熵合金中的应用,熔覆在904L不锈钢上得到一层强度高、耐磨性优异且具有一定耐腐蚀性能的涂层。所制备的AlCoCrMoVx高熵合金涂层具有硬度高、耐磨性好的特点,在电化学腐蚀过程中会生成一层黑色的氧化膜,随着电压增加,其氧化膜不会被击穿,说明其在动态电压条件下性能优异。
附图说明
图1为AlCoCrMoVx(x=0,0.2,0.4,0.6,0.8,1.0)激光熔覆涂层的 XRD图,右图为XRD主峰的偏移。
图2为AlCoCrMoVx激光熔覆涂层显微硬度图。
图3为AlCoCrMoVx激光熔覆涂层平均硬度图。
图4为AlCoCrMoVx微观形貌图。
图5为AlCoCrMoV0.4激光熔覆涂层选区衍射图像。
图6为AlCoCrMoVx激光熔覆涂层摩擦磨损曲线图。
图7为AlCoCrMoVx激光熔覆涂层磨痕激光共聚焦图像。
图8为AlCoCrMoVx激光熔覆涂层在0.5mol/L H2SO4溶液中的电化学曲线图。
图9为AlCoCrMoVx激光熔覆涂层在0.5mol/L H2SO4溶液中的阻抗图。
具体实施方式
下面通过具体实施方式对本发明作进一步详细的说明:
实施例1
成分设计:以AlCoCrMo高熵合金为基体,通过添加不同的V,获得 AlCoCrMoVx高熵合金熔覆涂层。具体化学成分见表一;
表一AlCoCrMoVx高熵合金化学成分
(1)粉末选择:AlCoCrMoV高熵合金粉末中的Al Co Cr Mo V均购于长沙天久金属材料有限公司,粉末粒度为45-105μm,纯度均≥99.9%。将粉末按照表一进行配制,采用精度为0.001g的AL204型电子天平进行称量。
(2)粉末球磨:将配置好的粉末置于不锈钢球磨罐中进行球磨,为防止粉末粘结,加入适量酒精。球磨参数:球料比为5:1,球磨转数为350rpm/min,球磨时间1.5h。球磨后的粉末经过80目不锈钢分样筛过筛后,将样品干燥进行保存。
(3)基材选择:选用尺寸长宽高为50mm×30mm×10mm的904L不锈钢作为基材。利用砂轮机去除基材表面的氧化皮,并用酒精清洗表面油污,吹风机吹干备用。
(4)激光熔覆涂层制备:采用预置粉末法,利用模具在基材表面预置一层1.5mm厚的粉末。采用宽带熔覆激光制备涂层,并且在熔覆过程中通氩气进行保护,激光熔覆参数为:激光功率P=3500W,扫描速率 v=5mm/s,矩形光斑尺寸20×2mm2,气流密度为15L/min。
图1为AlCoCrMoVxXRD图像,由于大尺寸的Mo融入到尺寸相差不大的FeCoCr中使得晶格发生畸变而生成σ相。随着V元素的增加,晶格畸变程度逐渐减小转化为bcc结构,V元素可以促进AlCoCrMoVx中固溶相的形成。
图2AlCoCrMoVx显微硬度图。由于AlCoCrMoV0.2微观结构存在微小的孔隙,从而硬度最低。随着V含量的增加,硬度逐渐增大。由于存在σ相而使得硬度比较低,但是随着V的增加,σ相逐渐消失,硬度逐渐增加。
图3AlCoCrMoVx平均显微硬度图。加入AlCoCrMo加入后,使得基材硬度提高,随着V含量的增加,其平均硬度先降低后增加。而在AlCoCrMoV0.2平均硬度最低,为832.5HV0.1。随后随着V的增加,平均硬度逐渐增加。
图4AlCoCrMoVx微观形貌图;(a)AlCoCrMoV0;(b)AlCoCrMoV0.2; (c)AlCoCrMoV0.4;(d)AlCoCrMoV0.6;(e)AlCoCrMoV0.8;(f)AlCoCrMoV1.0。从显微组织中可以看到针状组织、花瓣组织以及黑色的第二相的存在。但是随着V含量的增加,针状组织以及花瓣状组织逐渐消失,合金成分中存在的 Al元素和空气中的N2反应从而偏聚在黑色第二相,黑色的第二相始终存在。
图5AlCoCrMoV0.4HEA涂层的亮场TEM图像。(a)第二相粒子的TEM 图像;(b)第二相粒子的SAED图像,从衍射斑点可以看出是六方结构;(c)第二相粒子的FFT图;(d)针状结构的TEM图像;(e)针状结构的SAED图像,可以从衍射斑点说明是四方结构;(f)针状结构的FFT图;(g)花瓣状结构的 TEM图像;(h)花瓣状结构的SAED图像,可以从衍射斑点证实为bcc结构; (i)花瓣状结构的FFT图。图6为AlCoCrMoVx激光熔覆涂层在50N载荷运行20min作用下的摩擦磨损曲线图以及平均摩擦系数.随着V含量的增加,平均摩擦系数先增加后减少。而V含量为0.6的时候是一个转折点,从XRD图中我们可以看出,涂层基体在0.6的时候发生了改变,从两个bcc转变成单一 bcc结构。
图7AlCoCrMoVx激光熔覆涂层磨痕激光共聚焦图像。从图中可以直观看出AlCoCrMoV0.8的磨损程度最小,磨损宽度以及深度都是最低的。其中磨损比较严重的是基材,虽然有些涂层磨损性能比较差,但是涂层的磨损性能相比于基材都更加优异。
图8AlCoCrMoVx激光熔覆涂层在0.5mol/L H2SO4溶液中的电化学曲线图。电化学曲线图可以说明材料在动态条件下的腐蚀情况。AlCoCrMoV0位于图的最右端,说明其耐腐蚀性能比较差。通过tafel外推法可以发现 AlCoCrMoV0.8的耐腐蚀性能较为优异。
图9AlCoCrMoVx激光熔覆涂层在0.5mol/L H2SO4溶液中的阻抗图。阻抗图一般为半圆状,圆的半径越大就说明涂层在静态下的耐腐蚀性能就越好。随着V的增加,阻抗逐渐增大,而AlCoCrMoV0.8的阻抗图半径最大,说明其的耐腐蚀性能最好。
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (6)
1.一种高硬度高耐磨的高熵合金涂层,其特征在于:合金分子式为:AlCoCrMoVx,x为0-1。
2.根据权利要求1所述高硬度高耐磨的高熵合金涂层,其特征在于:所述x为0.6或0.8。
3.一种权利要求1-2任一项所述的高硬度高耐磨的高熵合金涂层的制备方法,其特征在于,按照如下步骤制备:
1)准确称取Al、Co、Cr、Mo、V粉末;
2)将称取好的粉末放入球磨罐中球磨,为防止粉末粘结,加入适量酒精,使得粉末混合均匀,然后烘干、过筛、干燥保存;
3)对基材表面进行打磨以除去表面氧化皮,直到露出光亮面;
4)采用预置粉末法,将球磨后的合金粉末预置于基材打磨面,在基材表面预涂合金粉末,利用宽带激光熔覆设备进行涂层制备。
4.根据权利要求3所述高硬度高耐磨的高熵合金涂层的制备方法,其特征在于:Co、Cr、Mo、V粉末,粉末粒度为45-105μm,纯度均≥99.9%。
5.根据权利要求3所述高硬度高耐磨的高熵合金涂层的制备方法,其特征在于:球磨时,球料比为5:1,球磨转数350rpm/min,球磨时间t=1.5h。
6.根据权利要求5所述高硬度高耐磨的高熵合金涂层的制备方法,其特征在于:使用激光器型号为RC-LMS-6000-R光纤激光器,激光熔覆参数:激光功率P=3500W,扫描速率v=5mm/s,矩形光斑尺寸20×2mm2,气流密度为15L/min。
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