CN110423976A - 高温抗剥落Y-Al2O3/MCrAlY复合涂层及其制备方法 - Google Patents
高温抗剥落Y-Al2O3/MCrAlY复合涂层及其制备方法 Download PDFInfo
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Abstract
高温抗剥落Y‑Al2O3/MCrAlY复合涂层及其制备方法，属于表面工程技术领域。Y‑Al2O3/MCrAlY复合涂层，M是Ni、Co或Fe中的一种或几种，涂层具有多层结构，且Al2O3膜中不含有Y2O3及Y‑Al‑O氧化物。该涂层由Y‑Al2O3层和MCrAlY层组成，Y‑Al2O3层位于MCrAlY层上表面。Y‑Al2O3层中，Y原子占据Al2O3晶格中Al原子位置，涂层结构仍为Al2O3晶型；Y‑Al2O3层不含有Y2O3及Y‑Al‑O氧化物。本发明提供的Y‑Al2O3/MCrAlY复合涂层具有结合强度高、耐高温氧化、使用寿命长等特点，可用于防护航空、舰船、电力、冶金等领域高温热端部件。
Description
技术领域
本发明属于表面工程技术领域，涉及一种抗氧化膜剥落的Y-Al2O3/MCrAlY复合涂层及其制备方法，以及该Y-Al2O3/MCrAlY复合涂层在发动机高温热端部件的应用。
背景技术
MCrAlY(M指Co、Ni、Fe或其合金)涂层是一种广泛适用于航空发动机包括燃气轮机、涡轮叶片等耐高温氧化和耐高温腐蚀的材料的保护层。工件在高温条件下，MCrAlY涂层上表面会形成一层以Al2O3为主的热生长氧化物层(TGO)，连续致密的Al2O3膜层阻隔了高温氧化及腐蚀介质对基体的侵蚀，为热端部件提供良好的高温防护性能。Al2O3膜粘附力和临界脱落厚度是影响MCrAlY涂层使用寿命的关键因素。
添加活性元素Y(也可以是Hf、Ta、La、Gr等)可有效提高MCrAlY涂层的抗高温氧化性能。但传统的MCrAlY涂层在高温下使用，涂层中的活性元素Y极易被氧化形成Y2O3，Y2O3的形成会加速MCrAlY涂层中氧原子的内扩散(如700℃时，O在Al2O3中的扩散速率为1×10- 17cm2/s，而O在Y2O3中的扩散速率为2.2×10-11cm2/s，远远高于在Al2O3膜中的扩散速率)，不仅提高涂层的内氧化速率，而且生成的Y2O3会与Al2O3进一步形成大颗粒Y-Al-O(如YAl5O12、YAlO3等，Y-Al-O等多为尖晶石或钙钛矿型，结构疏松多孔)氧化物，使得Al2O3膜层的组分不仅含有Y2O3，而且含有Y-Al-O氧化物，上述多种复杂氧化物在冷热循环过程中会促进Al2O3膜空洞形成以及裂纹的萌生，降低Al2O3膜层的粘附性能，通常Al2O3膜厚度约为10μm时即出现剥离(临界厚度)，导致氧化层过早脱落，加速MCrAlY涂层失效。因此，抑制Y的氧化及Y-Al-O氧化物的生成，是提高Al2O3膜层的粘附性能和延长涂层使用寿命的关键。
发明内容
为了解决现有技术中，Y易氧化生成Y2O3及Y-Al-O氧化物显著降低Al2O3/MCrAlY界面的粘附性和Al2O3膜临界厚度，导致涂层使用寿命和可靠性不足问题，本发明提供了一种高温抗剥落Y-Al2O3/MCrAlY复合涂层及其制备方法。采用该方法制备的涂层，Al2O3/MCrAlY界面结合好，具有出色的耐高温氧化性能及服役寿命长等特点。
本发明提供的高温抗剥落Y-Al2O3/MCrAlY复合涂层，M是Ni、Co或Fe中的一种或几种，其特征在于，涂层具有多层结构，且Al2O3膜中不含有Y2O3及Y-Al-O氧化物。本发明所提供的新型Y-Al2O3/MCrAlY复合涂层，可有效抑制Y2O3及尖晶石结构的Y-Al-O的形成，提高Al2O3膜层与基体的粘附性，增加氧化膜剥落临界厚度，延长涂层使用寿命。
进一步地，本发明提供的高温抗剥落Y-Al2O3/MCrAlY复合涂层，涂层厚度0.05-0.2mm，氧含量≤0.05％，结合强度50-80MPa，孔隙率0.02-1％，1000℃、12000h后涂层瞬时氧化速率≤2×10-11g2·cm-4·s-1，Al2O3膜保护层连续致密，无翘起或剥落，厚度≥15μm；1100℃、3000h后涂层瞬时氧化速率≤1.6×10-11g2·cm-4·s-1，Al2O3膜保护层连续致密，无翘起或剥落，厚度≥12μm。
进一步地，本发明提供的高温抗剥落Y-Al2O3/MCrAlY复合涂层，该涂层由Y-Al2O3层和MCrAlY层组成，Y-Al2O3层位于MCrAlY层的上表面。Y-Al2O3层中，Y原子占据Al2O3晶格中Al原子的位置，因此涂层结构仍为Al2O3晶型。Y-Al2O3层不含有Y2O3及Y-Al-O氧化物。
本发明所提供的新型Y-Al2O3/MCrAlY复合涂层具有以下优点：
(1)Y以原子态的形式存在于Al2O3膜层中，因为Y-Al2O3层仍保持Al2O3晶体结构，高温性质稳定，可有效抑制Y的氧化以及Y2O3和Y-Al-O氧化物的形成，显著改善Al2O3/MCrAlY界面的粘附性，并提高氧化膜临界脱落厚度。
(2)新型Y-Al2O3/MCrAlY是一种多层结构的复合涂层，采用包埋渗的技术制备，因此活性元素[Y]的含量由外至内逐渐降低，浓度梯度连续可控，涂层上表面中高浓度的[Y]稳定存在于Y-Al2O3膜层中，涂层内部Y元素含量较低，延缓生成Y2O3及Y-Al-O氧化物的生成，显著降低O的扩散速率，使得涂层内部也不易被氧化，从而提高涂层使用寿命。
(3)MCrAlY复合涂层使用过程中的活性元素Y不断会被消耗，但是由于[Y]的浓度梯度，Y-Al2O3层会不断地为涂层提供原子态的[Y]，使得涂层中的有效[Y]稳定供给的时间更长，进一步提高了涂层使用寿命。
本发明的发明人经过大量研究工作发现，原子态的[Y]存在于Al2O3保护膜中，可有效抑制Y的氧化及Y-Al-O氧化物的生成，是提高Al2O3膜层的粘附性能和延长燃气轮机高温热端部件使用寿命的前提和基础。
本发明还提供高温抗剥落Y-Al2O3/MCrAlY复合涂层的制备方法，包括以下步骤：
(1)按照化学成分要求制备MCrAlY合金粉末或靶材；
(2)将步骤(1)得到的MCrAlY合金粉末或靶材采用常规方法制备MCrAlY涂层；
(3)配制渗剂：按照被渗元素、催化剂、填充剂要求的比例配制渗剂，配好的渗剂进行球磨混合；
(4)包埋渗：将渗剂和带有MCrAlY涂层的部件放入真空炉中，进行包埋渗反应，获得高温抗剥落Y-Al2O3/MCrAlY复合涂层。
包埋渗法是把涂层零件放在高温渗炉中，在真空或在有部分惰性气体保护的情况下进行热处理，通过蒸汽迁移和反应扩散形成所需组分和结构的涂层。包埋渗基本原理为在一定的温度下被渗物质与活化剂反应产生气相的金属卤化物，卤化物在活度梯度力的驱动下向基体表面扩散，在基体表面发生分解或置换等相界面反应生成待渗元素的活性原子；反应生成的活性原子首先吸附在基体金属表面自由能高的各点上，然后陆续被基体金属吸收，形成金属间化合物层或表面固溶体层；被渗原子在高温下向内部基体扩散，渗层增厚。包埋渗可实现原子态的[Y]直接进入MCrAlY表层的Al2O3膜中，包埋渗法所制备的渗层组织致密、厚度及被渗原子浓度可控，且能够用于结构复杂的零部件表面渗层的制备。
进一步地，步骤(3)中渗剂由三部分组成：被渗元素Y重量百分比为0.05-2％，或Y2O3重量百分比为0.125-5％；活化剂，为NaF、NH4Cl或NH4F中的一种或几种，重量百分比为5-15％；其余为填充剂，为Al2O3、SiO2、SiC中的一种或几种。
进一步地，步骤(4)中所述包埋渗反应在高温真空炉中进行，共渗温度为600～1200℃，保温时间为0.1-2h，真空度低于6.67×10-2Pa或用氩气保护。
本发明还提供高温抗剥落Y-Al2O3/MCrAlY复合涂层在热端部件的应用，所述Y-Al2O3/MCrAlY复合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性能和使用寿命。
进一步地，所述热端部件为发动机叶片、涡轮外环、燃烧室或火焰筒。进一步地，所述发动机为航空发动机或者船用燃气轮机。
本发明具有以下优点：采用包埋渗Y的技术获得了含有Y-Al2O3/MCrAlY复合涂层，解决现有技术中保护性Al2O3膜中Y以Y2O3及Y-Al-O氧化物形式存在，从而显著降低氧化膜粘附性和临界脱落厚度，导致涂层使用寿命和可靠性不足问题。本发明提供的Y-Al2O3/MCrAlY复合涂层具有结合强度高、耐高温氧化使用寿命长等特点，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。本发明所提供的高温抗剥落Y-Al2O3/MCrAlY复合涂层，用于航空发动机涡轮外环的防护，1100℃、3000h后MCrAlY涂层中Al2O3膜连续致密，厚度≥12μm且未出现脱落，比传统涂层寿命提高3倍以上。采用该涂层用于舰船燃气轮机叶片防护，1100℃、3000h后涂层中Al2O3层连续致密，厚度≥15μm且未出现脱落，比传统涂层寿命提高2倍以上。
附图说明
图1为Y-Al2O3/MCrAlY复合涂层制备流程图。
图2为包埋渗Y制备Y-Al2O3/MCrAlY复合涂层示意图。
图3为Al2O3和Y-Al2O3晶体结构示意图。
图4为实施例1中Y-Al2O3涂层中[Y]元素含量与涂层厚度的关系图。
具体实施方式
下面结合附图对本发明做进一步说明。具体说明如下。
实施例1
金属元素按照如下成分配料：Al，12wt％；Cr，22wt％；Y，0.5wt％；Ni：余量。将上述材料共计10kg放入真空熔炼-惰气雾化设备中，待合金液温度≥1500℃，采用氩气雾化，压力为2.2MPa，筛分后获得NiCrAlY合金粉末。
采用大气等离子喷涂工艺制备NiCrAlY涂层，喷涂工艺参数为：弧电流650A；弧电压60V；送粉速度55g/min；喷涂距离200mm。涂层厚度0.10mm，氧含量0.5wt％，孔隙率0.3％。
包埋渗用渗剂的配制如下：采用5％的Y2O3粉，10％的NaF；余量为填充剂Al2O3粉末，渗剂颗粒大小均为53-100μm，渗剂用球磨机机械混合至均匀，热处理具体步骤为：
(1)装炉：将渗剂和试样放入高温渗炉中；
(2)抽真空：密封炉管，打开抽真空气阀开始抽真空，直到气压被抽到0.01MPa以下；
(3)换气：关闭真空泵，打开另一端气阀和氩气流量控制器进行充气，直至管内气压达到一个大气压左右时停止充气，关闭左端气阀，再次抽真空，重复3次。
(4)尾气处理管安装：按照(3)中的充气方法向管内充氩气，直到管内气压略大于1个标准大气压时，依次关闭左端进气阀和真空泵。
(5)升温：开启电源，升温速率约为10℃/min，升至1200℃。
(6)保温：加热到设定温度，保温2.5h。
(7)取样：试样随炉冷却至室温后取出。
Y-Al2O3/MCrAlY复合涂层厚度为0.13mm，其中Y-Al2O3层约为5-10μm，Al2O3膜中无明显Y2O3及Y-Al-O氧化物。涂层结合强度65MPa，孔隙率0.03％，复合涂层1100℃×200h后，Al2O3膜与MCrAlY涂层结合紧密，厚度约为4μm，约为传统涂层的40％，瞬时氧化速率约为5×10-12g2·cm-4·s-1，约为传统涂层的50％，且[Y]原子浓度从外之内呈现连续梯度变化，[Y]浓度与涂层厚度的关系如图4所示。采用该涂层用于航空发动机叶片防护，涂层使用超过600h后；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15000h。
实施例2
金属元素按照如下成分配料：Al，5wt％；Cr，22wt％；Y，0.6wt％；Co：余量。将上述材料放入真空熔炼炉中制备合金靶材，加工后靶材尺寸为Ф100×40mm，O≤0.002％，C≤0.002％，H≤0.0001％.
采用电子束物理气相沉积工艺(EB-PVD)制备CoCrAlY涂层，真空室内真空度低于5×10-2Pa，用电子束加热基体温度至为900℃，电弧放电电压为30V，放电电流为300A，当涂层厚度达到约50μm后停止沉积，关闭设备，取出沉积完毕基体材料。
包埋渗用渗剂的配制如下：采用3％的Y2O3粉，8％的NH4F；余量为填充剂Al2O3粉末，渗剂颗粒大小均为26-75μm，渗剂用球磨机机械混合至均匀，热处理具体步骤为：
(1)装炉：将渗剂和试样放入高温渗炉中；
(2)抽真空：密封炉管，打开抽真空气阀开始抽真空，直到气压被抽到0.01MPa以下；
(3)洗炉：关闭真空泵，打开另一端气阀和氩气流量控制器进行充气，直至管内气压达到一个大气压左右时停止充气，关闭左端气阀，再次抽真空，重复3次。
(4)升温：开启电源，升温速率约为15℃/min，升至1050℃。
(5)保温：加热到设定温度，保温0.2h。
(6)取样：试样随炉冷却至室温后取出。
Y-Al2O3/MCrAlY复合涂层厚度为53μm，其中Y-Al2O3层约为3-5μm，Al2O3膜中无明显Y2O3及Y-Al-O氧化物。复合涂层1100℃×100h瞬时氧化速率约为3.5×10-12g2·cm-4·s-1，为传统涂层的35％。采用该涂层用于航空发动机叶片防护，涂层使用寿命超过900h；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22000h。
Claims (12)
1.高温抗剥落Y-Al2O3/MCrAlY复合涂层，M是Ni、Co或Fe中的一种或几种，其特征在于，涂层具有多层结构，且Al2O3膜中不含有Y2O3及Y-Al-O氧化物。
2.根据权利要求1所述的高温抗剥落Y-Al2O3/MCrAlY复合涂层，其特征在于，涂层厚度0.05-0.2mm，氧含量≤0.05％，结合强度50-80MPa，孔隙率0.02-1％，1000℃、12000h后涂层瞬时氧化速率≤2×10-11g2·cm-4·s-1，Al2O3膜保护层连续致密，无翘起或剥落，厚度≥15μm；1100℃、3000h后涂层瞬时氧化速率≤1.6×10-11g2·cm-4·s-1，Al2O3膜保护层连续致密，无翘起或剥落，厚度≥12μm。
3.根据权利要求1所述的高温抗剥落Y-Al2O3/MCrAlY复合涂层，其特征在于，该涂层由Y-Al2O3层和MCrAlY层组成，Y-Al2O3层位于MCrAlY层的上表面。
4.根据权利要求3所述的高温抗剥落Y-Al2O3/MCrAlY复合涂层，其特征在于，Y-Al2O3层中，Y原子占据Al2O3晶格中Al原子位置，涂层结构仍为Al2O3晶型。
5.根据权利要求3所述的高温抗剥落Y-Al2O3/MCrAlY复合涂层，其特征在于，Y-Al2O3层不含有Y2O3及Y-Al-O氧化物。
6.权利要求1-5任一权利要求所述的高温抗剥落Y-Al2O3/MCrAlY复合涂层的制备方法，其特征在于，包括以下步骤：
(1)按照化学成分要求制备MCrAlY合金粉末或靶材；
(2)将步骤(1)得到的MCrAlY合金粉末或靶材采用常规方法制备MCrAlY涂层；
(3)配制渗剂：按照被渗元素、催化剂、填充剂要求的比例配制渗剂，配好的渗剂进行球磨混合；
(4)包埋渗：将渗剂和带有MCrAlY涂层的部件放入真空炉中，进行包埋渗反应，获得高温抗剥落Y-Al2O3/MCrAlY复合涂层。
7.根据权利要求6所述的制备方法，其特征在于，步骤(3)中渗剂由三部分组成：被渗元素Y重量百分比为0.05-2％，或Y2O3重量百分比为0.125-5％；活化剂，选自NaF、NH4Cl或NH4F中的一种或几种，重量百分比为5-15％；其余为填充剂，选自Al2O3、SiO2、SiC中的一种或几种。
8.根据权利要求6所述的制备方法，其特征在于，步骤(3)中渗剂所用粉末纯度均为分析纯，粒度为10-104μm。
9.根据权利要求6所述的制备方法，其特征在于，步骤(4)中所述包埋渗反应在高温真空渗炉中进行，温度为600～1300℃，保温时间为0.1-5h，真空度低于6.67×10-2Pa或用氩气保护。
10.权利要求1-5任一权利要求所述的高温抗剥落Y-Al2O3/MCrAlY复合涂层在热端部件的应用，其特征在于，所述Y-Al2O3/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性能和使用寿命。
11.根据权利要求10所述的应用，其特征在于，所述热端部件为发动机叶片、涡轮外环、燃烧室或火焰筒。
12.根据权利要求11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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Application publication date: 20191108 |