CN110343988A - 抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料、涂层及制备方法 - Google Patents
抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料、涂层及制备方法 Download PDFInfo
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Abstract
抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料、涂层及制备方法，属于表面工程技术领域。抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料，M是Ni、Co、Fe中的一种或几种，Re是活性稀土元素Y、Zr、Ti、Ru、Hf中的一种或几种，所述MCrAlRe/RexOy涂层材料含有MCrAlRe和稀土氧化物RexOy，重量百分比为：RexOy粉末，0.01‑6％；MCrAlRe粉末，余量。Re向氧化铝层中的扩散速率显著降低，有效避免活性元素过度掺杂，极大提高了涂层使用寿命，在航空发动机或燃气轮机的风扇、压气机叶片、涡轮叶片以及轧辊部件的高温氧化及热腐蚀防护领域具有良好应用前景。
Description
技术领域
本发明属于表面工程技术领域，涉及一种抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料、涂层及制备方法。
背景技术
航空、航天领域的发动机叶片和热端部件所处环境非常复杂和恶劣，为了提高其寿命，对热端部件多采用MCrAlY(M＝Ni，Co，Fe)涂层进行高温防护。MCrAlY涂层在高温服役的条件下可以生出一层连续致密的Al2O3保护膜，致密的Al2O3膜可以防止氧气扩散到粘结层中，从而保护底层基体合金免受高温氧化和腐蚀，Al2O3的厚度超过10μm则膜层极易脱落，涂层失效。因此Al2O3膜的厚度及O在其中的扩散速率是决定涂层寿命的关键因素。
MCrAlY涂层中添加活性稀土元素(Re)，如Y、Zr、Ti、Ru、Hf等可以提高涂层的性能和使用寿命，机理主要为生成的氧化物RexOy通过晶界钉扎提高Al2O3膜的粘附性和抗剥落性能，改变氧化膜的生长机制，降低涂层的氧化速率等。但是，传统的MCrAlY涂层制备中，活性元素多数在制备MCrAlY粉末时以金属单质形式加入，在涂层高温及长时使用过程中，高反应活性的Re元素会以较高的速率向表层Al2O3膜快速扩散，而Al2O3膜中Re的含量一旦超过0.2％，则出现活性元素的“过度掺杂”，即活性元素含量越高，O在Al2O3膜中的扩散系数越高，涂层氧化增重越快，Al2O3膜易剥落，降低涂层寿命(如1000℃、500h后，Y含量为0.5％的MCrAlY涂层形成的Al2O3膜厚度为5μm，O在氧化铝膜中的扩散系数约为3×10-20cm-3s-1,Y含量为0.75％涂层的氧化膜厚度≥10μm，氧化膜起伏较大，出现褶皱及裂纹,O在氧化铝膜中的扩散系数约为6.7×10-20cm-3s-1)。过度掺杂机理为：较高含量的Y扩散到MCrAlY表面形成的保护性Al2O3膜层中，形成较多大块的Y-Al-O氧化物，Y-Al-O型氧化物结构疏松多孔且内部缺陷较多，这些氧化物会为氧的向内扩散提供通道，O在氧化铝膜中的扩散系数提高，加速了涂层中有效铝的消耗，从而导致Al2O3膜层厚度的增加，冷热循环产生应力，加速涂层的剥落，降低涂层的使用寿命。因此，降低高反应活性的金属添加量并抑制其向氧化铝膜的扩散速率，是提高传统MCrAlY涂层使用寿命的关键。
人们渴望得到能够制活性元素过度掺杂的MCrAlY涂层材料及相应涂层，从而提高传统MCrAlY涂层使用寿命。
发明内容
为了解决传统MCrAlY涂层中活性元素过度掺杂而造成涂层使用寿命不足问题，本发明提供了一种抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料的方法，以及利用该方法制备MCrAlRe/RexOy涂层的技术。该涂层在Re含量≥2％时仍具有优异的抗氧化性能，1000℃，O在氧化铝膜中的扩散系数低于6×10-20cm-3s-1，比传统涂层低3倍以上。该涂层可用于航空发动机、燃气轮机等风扇、压气机叶片、涡轮叶片，冶金行业的轧辊等部件的高温抗氧化及热腐蚀部位的防护。
发明人经过长期研究发现，在[Re]添加总量保持不变的情况下，以氧化物RexOy的形式部分或全部替代金属单质，可降低高反应活性金属Re单质的添加量，进而显著降低Re向氧化铝层中的扩散速率，有效避免出现过度掺杂。一方面，由于Re以RexOy的形式加入，可减少以金属单质形式加入的Re的量，因此涂层中高反应活性和扩散速率的Re浓度降低，显著减少向Al2O3膜扩散的活性元素的量，避免Re以活性金属形式存在而造成的Y-Al-O快速氧化问题。另一方面，弥散分布的氧化物颗粒RexOy对MCrAlY涂层中Re元素的扩散起到有效的阻碍作用。RexOy属于金属氧化物，具有高熔点及高热稳定性，自由能较低，其在涂层及Al2O3膜中的扩散速率比金属单质Re低3-5个数量级，同时，起到弥散强化作用的RexOy在涂层中显著抑制活性元素Re向Al2O3膜层的扩散传输，延缓过度掺杂出现的时间及显著降低活性元素过度掺杂的风险，提高涂层使用寿命。
本发明提供一种抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料，M是Ni、Co、Fe中的一种或几种，Re是活性稀土元素Y、Zr、Ti、Ru、Hf中的一种或几种，所述MCrAlRe/RexOy涂层材料含有MCrAlRe和稀土氧化物RexOy，其组成及重量百分比为：(1)RexOy粉末，0.01-6％；(2)MCrAlRe粉末，余量。
进一步地，所述RexOy粉末粒度为5-30μm。
进一步地，所述MCrAlRe/RexOy涂层中[Re]含量为MCrAlRe粉末中Re单质添加量[Re]1和RexOy中Re含量[Re]2之和，Re元素重量百分含量[Re]为0.02-5％。更进一步地，0.01％≤[Re]1≤0.5％，0.01％≤[Re]2≤4.5％。
进一步地，所述MCrAlRe粉末中，Cr的含量15～40％，Al的含量5～15％，Re的含量0.02-5％，余量为M，粉末粒度为10-38μm。
进一步地，所述MCrAlRe粉末采用雾化法制备。
进一步地，所述MCrAlRe/RexOy涂层材料采用机械混合法制备。
本发明提供一种抑制活性元素过度掺杂的MCrAlRe/RexOy涂层，所述涂层在1000℃、500h后，涂层中O在Al2O3的扩散速率≤2.5×10-20cm-3s-1，约为传统涂层的30％；涂层中Al2O3的厚度≤5μm，比传统涂层低2倍；显著延长了涂层的使用寿命。
本发明提供一种抑制活性元素过度掺杂的MCrAlRe/RexOy涂层的制备方法，该方法包括下述步骤：采用机械方法将原料充分混合均匀后，用热喷涂方法进行涂层的制备。热喷涂可以采用超音速火焰热喷涂或大气等离子热喷涂。超音速火焰热喷涂工艺为：氧气流量为10-30L/min，煤油为700-950L/h，喷涂距离200-400mm，送粉量50-150g/min；大气等离子热喷涂工艺参数为：功率20-50kw，喷涂距离110-250mm，送粉率20-60g/min，主气流量35-70L/min。
本发明提供的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层的用途，所述涂层用于航空发动机或燃气轮机的风扇、压气机叶片、涡轮叶片，以及冶金行业轧辊部件的高温氧化及热腐蚀防护。
本发明通过简单易行的方法，在[Re]添加总量保持不变的前提下，显著降低了Re向氧化铝层中的扩散速率，有效避免传统MCrAlY涂层容易出现过度掺杂的弊端，极大提高了涂层使用寿命，在航空发动机或燃气轮机的风扇、压气机叶片、涡轮叶片以及冶金轧辊部件的高温氧化及热腐蚀防护领域具有良好应用前景。
附图说明
图1是本发明提供的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层的制备方法流程图。
具体实施方式
以下结合附图对本发明做进一步说明。
本发明提供的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层涂层制备方法如图1所示。将MCrAlRe粉、RexOy粉末按照一定比例称量后混合，然后采用热喷涂技术制备涂层，检验合格得到产品。
MCrAlRe采用公知的方法(如惰气雾化或机械合金化)制备，RexOy粉末为市售产品，MCrAlRe/RexOy粉末采用公知的方法(例如机械混合法、球磨法等)制备。
MCrAlRe/RexOy涂层采用热喷涂的方法制备，如大气等离子喷涂，超音速火焰喷涂，低压等离子喷涂等。
在MCrAlRe和RexOy粉末装入球磨机中，充分混合均匀后，用热喷涂的方法进行涂层制备，超音速火焰喷涂工艺为：氧气流量为10-30L/min(升/分钟)，煤油为700-950L/h(升/小时)，喷涂距离200-400mm，送粉量50-150g/min；大气等离子喷涂工艺参数为：功率20-50kw，喷涂距离110-250mm，送粉率20-60g/min，主气流量35-70L/min。
涂层在1000℃的马弗炉进行恒温氧化，500h后进行扫描电镜观察，进行Al2O3膜形貌及厚度的检测。
表1 提供了超音速喷涂2种前述涂层的组份在1000℃、500h后的Al2O3膜厚度与传统涂层的对比。
Claims (11)
1.抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料，M是Ni、Co、Fe中的一种或几种，Re是活性稀土元素Y、Zr、Ti、Ru、Hf中的一种或几种，其特征在于：所述MCrAlRe/RexOy涂层材料含有MCrAlRe和稀土氧化物RexOy，其组成及重量百分比为：(1)RexOy粉末，0.01-6％；(2)MCrAlRe粉末，余量。
2.根据权利要求1所述的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料,其特征在于，所述RexOy粉末粒度为5-30μm。
3.根据权利要求1所述的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料,其特征在于，所述MCrAlRe/RexOy涂层中[Re]含量为MCrAlRe粉末中Re单质添加量[Re]1和RexOy中Re含量[Re]2之和，Re元素重量百分含量[Re]为0.02-5％。
4.根据权利要求3所述的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料,其特征在于，0.01％≤[Re]1≤0.5％，0.01％≤[Re]2≤4.5％。
5.根据权利要求1所述的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料，其特征在于，所述MCrAlRe粉末中，Cr的含量15～40％，Al的含量5～15％，Re的含量0.02-5％，余量为M，粉末粒度为10-38μm。
6.根据权利要求1所述的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料，其特征在于，所述MCrAlRe粉末采用雾化法制备。
7.根据权利要求1所述的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层材料，其特征在于，所述MCrAlRe/RexOy涂层材料采用机械混合法制备。
8.抑制活性元素过度掺杂的MCrAlRe/RexOy涂层，其特征在于，所述涂层在1000℃、500h后，涂层中O在Al2O3的扩散速率≤2.5×10-20cm-3s-1，涂层中Al2O3的厚度≤5μm。
9.抑制活性元素过度掺杂的MCrAlRe/RexOy涂层的制备方法，其特征在于，该方法包括下述步骤：采用机械方法将原料充分混合均匀后，用热喷涂方法进行涂层的制备。
10.根据权利要求8所述的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层的制备方法，其特征在于，超音速火焰热喷涂工艺为：氧气流量为10-30L/min，煤油为700-950L/h，喷涂距离200-400mm，送粉量50-150g/min；大气等离子热喷涂工艺参数为：功率20-50kw，喷涂距离110-250mm，送粉率20-60g/min，主气流量35-70L/min。
11.根据权利要求8所述的抑制活性元素过度掺杂的MCrAlRe/RexOy涂层的用途，其特征在于，所述涂层用于航空发动机或燃气轮机的风扇、压气机叶片、涡轮叶片以及冶金行业轧辊部件的高温氧化及热腐蚀防护。
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