CN108396278B - 长寿命MCrAlY涂层、制备方法和在热端部件的应用 - Google Patents
长寿命MCrAlY涂层、制备方法和在热端部件的应用 Download PDFInfo
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Abstract
本发明公开了一种长寿命MCrAlY涂层、制备方法和在热端部件的应用,属于表面工程技术领域。涂层中Y与M主要以金属间化合物M5Y的形式存在,涂层制备方法包括以下步骤:(1)配料;(2)熔炼‑雾化制粉;(3)热喷涂制备MCrAl涂层;(4)配制渗剂:按照渗剂成分要求将渗剂原料按比例配制渗剂,配好的渗剂进行球磨混合;(5)稀土多元扩散渗:将渗剂和喷涂MCrAl涂层的部件放入真空炉中,进行高温稀土多元共渗,制备MCrAlY涂层。涂层具有结合强度高、耐高温氧化及抗热震性能优良、使用寿命长等特点,可广泛用于航空、舰船、电力、冶金等领域发动机高温热端部件的防护。
Description
技术领域
本发明属于表面工程技术领域,涉及一种长寿命MCrAlY涂层及其制备方法,以及该长寿命MCrAlY涂层在高温热端部件的应用。特别涉及一种采用扩散渗Y技术制备长寿命MCrAlY涂层的技术,该技术制备得到的含有M5Y的MCrAlY防护涂层,以及利用该MCrAlY防护涂层提高高温热端部件使用寿命。
背景技术
航空、舰船、电力等重(大)型装备涡轮发动机的叶片、燃烧室、火焰筒等关键热端部件的高温氧化和腐蚀破坏是影响整机寿命、可靠性和运行安全性的主要因素,在热端部件表面制备MCrA1Y(M:Ni,Co或Fe)高温防护涂层,是解决这一问题最有效的方法之一。MCrAlY涂层服役过程中,活性元素Y比Al或Cr与O生成焓更低,在高温环境下Y被优先氧化生成Y2O3,富集于氧化膜/合金界面处,通过细化Al2O3晶粒和“钉扎”作用,能将氧化膜与涂层基体紧紧“锚住”,增强了合金与氧化膜的粘附性,通过“晶界正效应”,降低了Al,Cr元素的扩散速率,显著增强了涂层高温抗氧化性能。但Y在服役温度过高或时间过长条件下,生成的Y2O3会进一步反应生成AlYO3(YAP)和Al5Y3O12(YAG)等Y-Al-O复杂氧化物,上述氧化物会引起沿晶界的“短路扩散”,导致涂层中剩余合金的大量氧化及外层氧化膜的快速增长(1200℃时Y-Al-O体积占比超过40%),热应力失配导致涂层/基体和涂层/氧化层界面处产生裂纹,降低涂层抗热震性能,加速涂层失效。
金属间化合物是金属的原子按一定比例化合,形成与原来两者的晶格均不同的合金组成物,能形成新的有序超点阵结构,具有优于高温合金的耐热性、比强度、比寿命等优点,高温下具有良好的稳定性及出色的抗氧化性能,MCrA1Y中的Y以高稳定金属间化合物M5Y形式存在,可通过M5Y实现Y在涂层中的稳定“供给”,避免Y的快速氧化,具有比Y更出色的高温稳定性和抗氧化性能,显著降低Y-Al-O复杂氧化物对涂层性能的影响,改善涂层热稳定性能,延长高温下涂层的使用寿命。获得M5Y是提高MCrAlY涂层高温热稳定性的关键。
MCrA1Y合金粉末主要采用感应熔炼-惰气雾化的方法制备,传统粉末制备方法是在熔炼过程中添加Y元素,但由于稀土元素Y的高反应活性,1000℃下Y在O分压为10-5mbar情况下即发生显著的氧化,即在MCrAlY真空制粉过程中Y已经被氧化生成了氧化物,并通过“遗传效应”保留到涂层中,因此采用在合金化过程中添加元素Y的传统方法,涂层中的Y主要以氧化物形式存在,因此无法获得含有M5Y的MCrAlY涂层。
发明内容
为了解决现有技术中,涂层中Y以氧化物形式存在,显著降低涂层高温耐氧化及抗热震性能,导致涂层使用寿命和可靠性不足问题,本发明提供了一种提高长寿命MCrAlY(M:Ni、Co或Fe)涂层及其制备方法,具体包括一种采用稀土多元扩散渗Y的技术,以及使用该技术制备MCrAlY防护涂层的方法。采用该技术制备的涂层具有涂层性能稳定、结合强度高、耐高温氧化及抗热震性能优良、使用寿命长等特点。
本发明的发明人经过大量研究工作发现,Y以高稳定Anderson结构的金属间化合物M5Y形式存在,是制备优异MCrAlY防护涂层、提高燃气轮机高温热端部件使用寿命的前提和基础。
本发明的发明人通过感应熔炼-惰气雾化的制粉技术,获得了化学成分均匀、稳定性和一致性好的喷涂用MCrAl合金粉末,采用热喷涂技术制备了MCrAl合金涂层,再采用稀土多元扩散渗Y的技术获得了含有金属间化合物M5Y的MCrAlY涂层,涂层具有结合强度高、耐高温氧化及抗热震性能优良、使用寿命长等特点,可广泛用于航空、舰船、电力、冶金等领域发动机高温热端部件的防护。
本发明所提供的一种长寿命MCrAlY涂层,M是Ni、Co或Fe中的一种或几种,涂层中Y与M主要以金属间化合物M5Y的形式存在。
进一步地,所述长寿命MCrAlY涂层厚度0.05-0.2mm,氧含量≤1wt%,结合强度50-80MPa,孔隙率0.2-10%,1200℃下500h恒温氧化测试涂层达到完全抗氧化级别。
本发明所提供的一种长寿命MCrAlY涂层的制备方法,通过不含Y的MCrAl合金粉末制备MCrAl合金涂层,Y采用扩散渗工艺引入MCrAl合金涂层,包括以下步骤:
(1)配料:按照MCrAl合金粉末成分要求准备M、Cr、Al金属单质或合金等原材料;
(2)熔炼-雾化制粉:采用感应熔炼-惰气雾化方法制备MCrAl合金粉末;
(3)热喷涂制备MCrAl涂层:将步骤(2)得到的粉末产品采用热喷涂工艺在部件表面制备MCrAl涂层;
(4)配制渗剂:按照渗剂成分要求,将含Y原料和其他渗剂原料按比例配制渗剂,配好的渗剂进行球磨混合;
(5)高温扩散渗:将渗剂和喷涂MCrAl涂层的部件放入真空炉中,进行高温扩散渗,制备MCrAlY涂层。
扩散渗工艺是一种原位的化学气相沉积技术,是指将基体合金埋入含被渗元素的粉末、催化剂和填充剂组成的渗剂内,在高温下含被渗元素的粉末与活化剂在一定温度下反应产生被渗元素的活性原子,活性原子首先吸附在基体合金表面自由能较高的区域,然后陆续被基体合金吸收形成金属间化合物。采用扩散渗可实现原子态的[Y]直接与MCrAl基体元素生成M5Y,扩散渗法所制备的渗层组织均匀致密、厚度可控,且能够用于结构复杂的零部件表面渗层的制备。同时,由于渗层的形成基于被渗元素的活性原子与基体合金之间的反应扩散,因此渗层与基体合金之间的结合界面为微冶金界面,结合强度高,不易发生开裂或剥落。
进一步地,Y采用稀土元素(Re)进行催渗,步骤(4)中所述其他渗剂原料含有催渗稀土元素,步骤(5)的高温扩散渗为稀土多元共渗。Re可显著加快活性原子[Y]的产生、在渗层中的扩散及与M反应的速度,提高渗速和渗层厚度;采用稀土催渗元素Re,活性原子[Y]与M反应速率常数K值提高40~200%,可获得厚度≥0.08mm的渗层。
催渗原理为通过大尺寸稀土原子渗入引起基体合金晶格严重畸变,增加空位,形成被渗原子[Y]扩散的流畅渠道,提高渗速和渗层厚度。
进一步地,步骤(4)中渗剂原料由被渗元素或其氧化物、催渗元素或其氧化物、催化剂、填充剂组成,具体为:被渗元素,0.5~10wt%的Y粉或Y2O3粉;催渗元素,0.5~10wt%的Ce或CeO2粉、Zr或ZrO2粉、Hf或HfO2粉中的一种或几种;催化剂,5~30wt%的NaF、NH4F、NH4Cl和NaBr的一种或几种;余量为填充剂Al2O3粉末。渗剂所用粉末纯度均为分析纯(99%以上),粒度为200目以下。
进一步地,步骤(5)中所述稀土多元共渗反应在高温真空炉中进行,共渗温度为800~1300℃,保温时间为0.5-20h。
本发明还提供长寿命MCrAlY涂层在热端部件的应用,所述MCrAlY涂层在热端部件表面作为防护涂层,提高热端部件高温抗氧化和耐热冲击性能。
进一步地,所述热端部件为发动机叶片、燃烧室或火焰筒。
进一步地,所述发动机为航空发动机或者燃气轮机。
本发明具有以下显著优点:采用稀土多元扩散渗Y的技术获得了含有金属间化合物M5Y(能谱分析中M:Y约为5:1,摩尔比)的MCrAlY涂层,解决现有技术在MCrAl合金熔炼过程添加Y导致涂层中Y以氧化物形式存在,显著降低涂层高温耐氧化及抗热震性能,涂层使用寿命和可靠性不足问题。涂层具有结合强度高、耐高温氧化及抗热震性能优良、使用寿命长等特点,可广泛用于航空、舰船、电力、冶金等领域发动机高温热端部件的防护。本发明所提供的MCrAlY合金涂层,用于航空发动机叶片防护,涂层使用寿命提升至600h以上,比传统MCrAlY涂层提高2倍以上;采用该涂层用于舰船燃气轮机叶片防护,涂层使用寿命超过18000h,比传统MCrAlY涂层提高1.5倍以上。
附图说明
图1为本发明的一种长寿命MCrAlY涂层的制备方法工艺流程图。
图2为多元稀土扩散渗Y示意图。
图3为采用扫描-透射电镜分析实施例2渗层中Co5Y的分布。
具体实施方式
下面结合附图对本发明做进一步说明。本发明的一种长寿命MCrAlY涂层的制备方法工艺流程如图1所示,具体说明如下。
实施例1
金属元素按照如下成分配料:Al,8wt%;Cr,20wt%;Ni:余量。将上述材料共计50kg放入真空雾化设备中,利用中频感应加热,当温度加热至1600℃时,保温20分钟,待合金液充分合金化后利用氩气雾化,雾化工艺参数为:雾化压力为1.8MPa,雾化器角度为60°,获得NiCrAl合金粉末。
采用低压等离子喷涂NiCrAl合金粉末,在表面预处理后的燃气轮机热端部件表面制备防护涂层。取粒度为-38μm≥90%的合金粉末,喷涂工艺参数为:弧电流600A;弧电压65V;氩气流量65L/min,压力55Torr;氢气流量6L/min;送粉速度62g/min;喷涂距离220mm。涂层厚度0.12mm,氧含量0.6wt%,结合强度55MPa,孔隙率0.4%;
多元稀土扩散渗Y过程如图2所示。多元稀土扩散用渗剂的配制如下:采用5%的Y2O3粉,5%的CeO2粉,10%的NaF;余量为填充剂Al2O3粉末,具体步骤为:
(1)渗剂配置:按预定的质量比例配置渗剂,然后在行星式球磨机中球磨8h以均匀和细化渗剂粉末;
(2)装样:将试样埋入装有渗剂的刚玉坩埚中,试样覆盖10-15mm厚的渗剂并压实;
(3)密封:将渗罐加盖后,使用硅胶进行密封,随后将渗罐放入电阻炉内加热至100℃,保温4h以使粘结剂干燥;
(4)装炉:将密封好的渗罐装入电阻炉升温,升温速率约为20℃/min,稀土多元共渗反应在高温真空炉中进行,共渗温度为1150℃,保温时间为3h;
(5)取样:渗罐随空气冷却至室温后取出试样,用酒精超声波清洗,然后吹干备用。
NiCrAlY渗层厚度为0.12mm,Y以Ni5Y金属间化合物形式存在,结合强度65MPa,孔隙率0.02%,渗层1200℃*500h达到完全抗氧化级别。采用该涂层用于航空发动机叶片防护,涂层使用寿命680h;采用该涂层用于舰船燃气轮机叶片防护,涂层使用寿命超过21000h。
实施例2
金属元素按照如下成分配料:Al,6wt%;Cr,30wt%;Co:余量。将上述材料共计50kg放入真空雾化设备中,利用中频感应加热,当温度加热至1700℃时,保温12分钟,待合金液充分合金化后利用氩气雾化,雾化工艺参数为:雾化压力为1.8MPa,雾化器角度为60°,获得CoCrAl合金粉末。
采用低压等离子喷涂CoCrAl合金粉末,在表面预处理后的燃气轮机热端部件表面制备防护涂层。取粒度为-38μm≥90%的合金粉末,喷涂工艺参数为:弧电流600A;弧电压65V;氩气流量65L/min,压力55Torr;氢气流量6L/min;送粉速度62g/min;喷涂距离220mm。涂层厚度0.08mm,氧含量0.06wt%,结合强度60MPa,孔隙率0.4%;
多元稀土扩散渗Y过程如图2所示。多元稀土扩散用渗剂的配制如下:被渗元素,采用5%的Y2O3粉;催化剂,3%的CeO2粉;催化剂,5%的NaF和5%的NH4F;余量为填充剂Al2O3粉末,具体步骤为:
(1)渗剂配置:按预定的质量比例配置渗剂,然后在行星式球磨机中球磨6h以均匀和细化渗剂粉末;
(2)装样:将试样埋入装有渗剂的刚玉坩埚中,试样覆盖10-15mm厚的渗剂并压实;
(3)密封:将渗罐加盖后,使用硅胶进行密封,随后将渗罐放入电阻炉内加热至100℃,保温4h以使粘结剂干燥;
(4)装炉:将密封好的渗罐装入电阻炉升温,升温速率约为20℃/min,稀土多元共渗反应在高温真空炉中进行,共渗温度为1050℃,保温时间为5h;
(5)取样:渗罐随空气冷却至室温后取出试样,用酒精超声波清洗,吹干备用。
CoCrAl渗层厚度为0.08mm,采用扫描-透射电镜分析渗层中Co5Y的分布如图3所示。图3中所标记位置的EDS分析结果如下表所示。
从上表可以看出,Y主要以Co5Y金属间化合物形式存在(能谱分析中Co:Y约为5:1,摩尔比),结合强度65MPa,孔隙率0.03%,渗层1200℃*500h达到完全抗氧化级别。采用该涂层用于航空发动机叶片防护,涂层使用寿命620h;采用该涂层用于舰船燃气轮机叶片防护,涂层使用寿命超过20000h。
以上所述为本发明的较佳实施例而已,但本发明不应该局限于该实施例和附图所公开的内容。所以凡是不脱离本发明所公开的精神下完成的等效或修改,都落入本发明保护的范围。
Claims (9)
1.长寿命MCrAlY涂层,M是Ni、Co或Fe中的一种或几种,其特征在于,涂层中Y与M主要以金属间化合物M5Y的形式存在;涂层厚度0.05-0.2mm,氧含量≤1wt%,结合强度50-80MPa,孔隙率0.2-10%,1200℃下500h恒温氧化测试涂层达到完全抗氧化级别。
2.权利要求1所述的长寿命MCrAlY涂层的制备方法,其特征在于,通过不含Y的MCrAl合金粉末制备MCrAl合金涂层,Y采用扩散渗工艺引入MCrAl合金涂层,包括以下步骤:
(1)配料:按照MCrAl合金粉末成分要求准备M、Cr、Al金属单质或合金原材料;
(2)熔炼-雾化制粉:采用感应熔炼-惰气雾化方法制备MCrAl合金粉末;
(3)热喷涂制备MCrAl涂层:将步骤(2)得到的粉末产品采用热喷涂工艺在部件表面制备MCrAl涂层;
(4)配制渗剂:按照渗剂成分要求,将含Y原料和其他渗剂原料按比例配制渗剂,配好的渗剂进行球磨混合;
(5)高温扩散渗:将渗剂和喷涂MCrAl涂层的部件放入真空炉中,进行高温扩散渗,制备MCrAlY涂层。
3.根据权利要求2所述的制备方法,其特征在于,步骤(4)中所述其他渗剂原料含有催渗稀土元素,步骤(5)的高温扩散渗为稀土多元共渗。
4.根据权利要求2所述的制备方法,其特征在于,步骤(4)中渗剂原料由被渗元素或其氧化物、催渗元素或其氧化物、催化剂、填充剂组成,具体为:被渗元素,0.5~10wt%的Y粉或Y2O3粉;催渗元素,0.5~10wt%的Ce或CeO2粉、Zr或ZrO2粉、Hf或HfO2粉中的一种或几种;催化剂,5~30wt%的NaF、NH4F、NH4Cl和NaBr的一种或几种;余量为填充剂Al2O3粉末。
5.根据权利要求2所述的制备方法,其特征在于,步骤(4)中渗剂所用粉末纯度均为分析纯,粒度为200目以下。
6.根据权利要求3所述的制备方法,其特征在于,步骤(5)中所述稀土多元共渗反应在高温真空炉中进行,共渗温度为800~1300℃,保温时间为0.5-20h。
7.权利要求1所述的长寿命MCrAlY涂层在热端部件的应用,其特征在于,所述MCrAlY涂层在热端部件表面作为防护涂层,提高热端部件高温抗氧化和耐热冲击性能。
8.根据权利要求7所述的应用,其特征在于,所述热端部件为发动机叶片、燃烧室或火焰筒。
9.根据权利要求8所述的应用,其特征在于,所述发动机为航空发动机或者燃气轮机。
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