CN113930705B - 一种长寿命热障涂层材料及其制备工艺、以及一种热障涂层系统及其制备工艺 - Google Patents

一种长寿命热障涂层材料及其制备工艺、以及一种热障涂层系统及其制备工艺 Download PDF

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CN113930705B
CN113930705B CN202111085557.6A CN202111085557A CN113930705B CN 113930705 B CN113930705 B CN 113930705B CN 202111085557 A CN202111085557 A CN 202111085557A CN 113930705 B CN113930705 B CN 113930705B
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王卫泽
方焕杰
杨挺
黄继波
叶东东
张显程
轩福贞
涂善东
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East China University of Science and Technology
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Abstract

本发明公开了一种长寿命热障涂层材料及其制备工艺、以及一种热障涂层系统及其制备工艺。所述长寿命热障涂层材料为二元稀土共掺杂氧化锆，其化学组成为xYb2O3‑yY2O3‑ZrO2，其中x+y≤6mol.％,x≥3mol.％，所述长寿命热障涂层材料呈现单一四方相氧化锆。根据本发明提供的二元稀土共掺杂氧化锆热障涂层材料有着出色的高温相稳定性和高热膨胀系数，由此材料制备得到的热障涂层系统具有较长热震和热循环寿命，相比传统YSZ热障涂层材料分别提高了10％和20％以上，根据本发明提供的长寿命热障涂层材料以及热障涂层系统可应用于燃气轮机或航空发动机高温金属热端部件的防护。

Description

一种长寿命热障涂层材料及其制备工艺、以及一种热障涂层 系统及其制备工艺
技术领域
本发明属于热障涂层材料领域，更具体的涉及一种长寿命热障涂层材料及其制备工艺、以及一种热障涂层系统及其制备工艺。
背景技术
航空燃气涡轮发动机是人类实现飞行梦想的源动力，被誉为“工业皇冠上的一颗明珠”。随着航天航空工业的迅速发展，高推重比和流量比成为了航空发动机的发展趋势。推重比和流量比越高，工作温度也越高，从而可提高发动机的效率和性能。当推重比为10时，涡轮进口温度为1600℃～1700℃；当推重比为15时，涡轮进口温度可达到1800℃～1900℃，而未来发动机推重比达到20时，涡轮进口温度将远远超过2000℃。为了提高燃气涡轮叶片和发动机的抗高温性能，早在20世纪50年代美国NASA-Lewis研究中心就提出了“热障涂层”这一概念，并于70年代在燃气涡轮发动机上试验成功。
热障涂层(TBCs)是一种多层结构系统，它沉积在耐高温金属或超合金的表面，热障涂层对于基底材料起到隔热作用，降低基底温度，使得用其制成的器件(如发动机涡轮叶片)能在高温下运行，并且可以提高器件(发动机等)热效率达到60％以上。通过将耐高温、低导热、抗腐蚀的陶瓷材料以涂层的形式与基体合金相复合，进而实现降低金属热端部件的表面温度以及提高基体合金的抗高温氧化腐蚀性能。如图1所示，典型的热障涂层通常包含三层结构，陶瓷隔热层、金属粘结层和金属基底。
目前热障涂层系统最常用的陶瓷材料为6-8wt％氧化钇部分稳定氧化锆(6-8YSZ)。该材料有着热导率低、热膨胀系数高以及断裂韧性高等特点。然而，随着操作温度的不断升高，YSZ涂层容易发生过早的剥落失效，其主要原因有以下几个方面：1)热应力。在高温服役环境下，由于陶瓷层与基体之间存在热膨胀差异，在热循环过程中会诱发巨大热应力，从而导致涂层的失效。2)高温烧结作用。涂层内部约含有15～25％的孔隙，这些孔隙的存在，能够有效缓解热应力。然而，长时间的高温作用下，陶瓷涂层不可避免发生烧结作用，孔隙率急剧下降，涂层应变容限也随之降低。过低的应变容限会导致热障涂层系统在加热或冷却过程中，涂层内承受较大的裂纹扩展驱动力，大大降低涂层的耐久性。3)相变。YSZ在高温下(大于1200℃)容易发生四方相向单斜相的转变，同时伴随着体积膨胀，加速涂层内部裂纹的扩展，影响涂层的可靠性。因此，迫切需要寻找一种新型热障涂层材料来代替传统YSZ材料。
美国专利6231991B1提出了一种烧绿石结构的热障涂层材料A2B2O7。文中着重指出La2Zr2O7，它具有较低的热导率和出色的相稳定性，有希望成为新一代的热障涂层材料。公开号CN101898889B的中国专利公开了一种具有磁铅石结构的六铝酸盐化合物，该材料高温相稳定性优越，室温至2000℃之间不发生相变，有望应用于更高温度。这些新型热障涂层材料不可避免地会与传统YSZ材料进行比较，结果表明，上述新型热障涂层材料制备的涂层寿命远低于传统YSZ涂层。例如，传统YSZ涂层在1300℃热循环实验中寿命超过了441次，而Gd2Zr2O7涂层仅48次就发生了失效。喷涂态YSZ涂层通常为四方相氧化锆，其独特的铁弹性畴转变增韧效应赋予YSZ涂层出色的弯曲强度、高裂纹扩展能、高断裂韧性和高耐受热冲击性能。
综上所述，YSZ材料体系仍是目前世界上最具潜力的热障涂层材料，通过对传统YSZ材料改性处理提高材料的相稳定性和热膨胀系数有利于进一步提高涂层耐久性和可靠性。
发明内容
本发明的目的是提供一种长寿命热障涂层材料及其制备工艺、以及一种热障涂层系统及其制备工艺，从而解决现有技术中的热障涂层材料无法同时满足耐高温、低导热、抗腐蚀、耐久性好、可靠性高的问题。
根据本发明的第一方面，提供一种长寿命热障涂层材料，所述长寿命热障涂层材料为二元稀土共掺杂氧化锆，所述二元稀土共掺杂氧化锆的化学组成为xYb2O3-yY2O3-ZrO2,其中x+y≤6mol.％,x≥3mol.％，所述长寿命热障涂层材料呈现单一四方相氧化锆，即t-ZrO2。
根据本发明的第二方面，提供一种上述长寿命热障涂层材料的制备工艺，包括以下步骤：A1：按一定的摩尔比分别称量Yb2O3、Y2O3、ZrOCl2·8H2O，并将其分别溶于稀盐酸和去离子水中，混合制成混合溶液，然后加入聚乙二醇进行分散，磁力搅拌1～2小时得到澄清透明的溶液，得到前驱溶液；A2：将步骤A1所得前驱溶液逐滴加入到氨水溶液中，并保持pH＝10.0～11.0，以充分形成沉淀，在原液中陈化24～28小时后，所得沉淀物用去离子水洗涤3次，再用无水乙醇洗涤2次；A3：将步骤A2所得沉淀物在1100～1300℃空气气氛中煅烧6～8小时后，冷却至室温，即可获得一种二元稀土共掺杂氧化锆的长寿命热障涂层材料。
优选地，步骤A1中，所述Yb2O3、Y2O3、ZrOCl2·8H2O的纯度为99.99％以上。
优选地，步骤A3中，将步骤A2所得沉淀物在1100～1200℃空气气氛中煅烧6～7小时。
根据本发明的第三方面，提供一种热障涂层系统的制备工艺，包括以下步骤：B1：提供一种根据权利要求1所述的长寿命热障涂层材料；B2：将所述长寿命热障涂层材料进行喷雾造粒，干燥处理，制成粒径为15～60μm的高流动性粉末作为陶瓷层粉末；B3：提供一种镍基合金基体，在所述镍基合金基体上喷涂NiCrAlY粉末形成金属粘结层；B4：采用喷涂工艺将步骤B2制备的陶瓷层粉末喷涂到步骤B3制备的金属粘结层上，形成陶瓷层，即得。
优选地，步骤B3中，所述金属粘结层制备过程中的参数为：首先利用喷枪预热基体至380～420℃，然后进行喷涂，喷涂电压为55～65V，喷涂电流为400～600A，主气压力为0.4～0.5MPa，氢气压力为0.2～0.3Mpa，喷枪移动速度为450～550mm/s，喷涂距离为50～150mm，送粉转速为1.0～1.5r/min。
优选地，所述金属粘结层的厚度控制在130～180μm。
优选地，步骤B4中，陶瓷层制备过程的参数为：首先利用喷枪将基体预热至480～520℃，然后进行喷涂，喷涂电压为55～65V，喷涂电流为500～700A，主气压力为0.4～0.5MPa，氢气压力为0.2～0.3MPa，喷枪移动速度为100～200mm/s，喷涂距离为60～100mm，送粉转速为1.3～1.7r/min。
优选地，所述陶瓷层的厚度控制为300～400μm。
优选地，步骤B4中的喷涂工艺包括：等离子喷涂、电子束物理气相沉积或其他喷涂技术。
根据本发明的第四方面，提供一种根据上述制备工艺制备得到的热障涂层系统，所述热障涂层系统包括：基底层；形成于所述基底层表面的金属粘结层；以及通过所述金属粘结层连接的陶瓷层；其中，所述基底层的成分为高温镍基合金IN738，所述金属粘结层的成分为NiCrAlY，所述陶瓷层为化学组成为xYb2O3-yY2O3-ZrO2的二元稀土共掺杂氧化锆，其中x+y≤6mol.％,x≥3mol.％，呈现单一四方相氧化锆。
正如背景技术部分所述，目前商用YSZ热障涂层在使用过程中存在容易失效、耐久性不高、可靠性差的问题，因此，本发明通过稀土掺杂改性方式提供一种二元稀土共掺杂氧化锆长寿命热障涂层材料以解决上述问题，该材料的化学组成为xYb2O3-yY2O3-ZrO2,其中x+y≤6mol.％,x≥3mol.％，并且该热障涂层材料还应呈现单一四方相氧化锆，即t-ZrO2。由于铁弹性畴转变增韧效应能够提高涂层的断裂韧性，因此上述二元稀土共掺杂氧化锆热障涂层材料较高的断裂韧性有利于提高涂层寿命，从而提高部件整体的可靠性和耐久性。
本发明不仅限定了两种稀土的掺杂含量，避免了掺杂含量过高或者过低时出现立方相或者单斜相的现象，同时还限定了煅烧温度，避免了温度过低时稀土未能完成掺杂进去氧化锆晶格中，导致单斜相的现象。因此，根据本发明提供的二元稀土共掺杂氧化锆长寿命热障涂层材料的制备工艺，结合所采用的稀土掺杂比例，能够有效地将新型二元稀土共掺杂氧化锆长寿命热障涂层材料的相成分控制在单一四方相。
最后，本发明还提供了一种通过上述二元稀土共掺杂氧化锆长寿命热障涂层材料制备的热障涂层系统及其制备工艺。该热障涂层系统包括基底层、金属粘结层以及通过金属粘结层连接在基底层上的陶瓷层。喷涂涂层测试表明，根据本发明制备的热障涂层系统结合紧密，系统完整。
综上所述，本发明相对现有技术具有以下有益效果：
1)本发明通过在氧化锆材料中掺杂加入两种半径和质量不同的稀土元素，在保证断裂韧性的基础上，提高材料的相稳定性和热膨胀系数，提供了一种长寿命热障涂层材料，该材料由两种稳定剂Yb2O3和Y2O3以及主剂ZrO2组成，化学组成为xYb2O3-yY2O3-ZrO2，并呈现单一四方相ZrO2，即t-ZrO2，因此该二元稀土共掺杂氧化锆热障涂层材料有着出色的高温相稳定性和高热膨胀系数。
2)本发明还提供了一种该二元稀土掺杂氧化锆长寿命热障涂层材料的制备工艺，该制备工艺操作简单精准，成本较低，可靠性较强。
3)本发明还提供了一种通过上述二元稀土共掺杂氧化锆热障涂层材料所制成的热障涂层系统及其制备工艺，热障涂层系统具有较长热震和热循环寿命，相比传统YSZ热障涂层材料分别提高了10％和20％以上，该热障涂层系统可应用于燃气轮机或航空发动机高温金属热端部件的防护。
附图说明
图1是一种典型的热障涂层的结构示意图；
图2是实施例制备的二元稀土共掺杂氧化锆长寿命热障涂层的截面组织结构；
图3是实施例制备的二元稀土共掺杂氧化锆粉末和热障涂层的X射线衍射图；
图4是实施例制备的二元稀土共掺杂氧化锆和传统YSZ材料在室温到1000℃的热膨胀系数变化；
图5是实施例制备的二元稀土共掺杂氧化锆涂层经过1500℃保温300h后的X射线衍射图，其中，a是衍射角度为10-80°的X射线衍射结果，b是对27-33°衍射角进行慢扫后的X射线衍射结果；
图6示出了传统YSZ涂层与新型二元稀土共掺杂氧化锆热障涂层的抗热震性能对比；
图7是热循环实验的装置示意图；
图8示出了传统YSZ涂层与新型二元稀土共掺杂氧化锆热障涂层的抗热循环性能对比。
具体实施方式
以下结合具体实施例，对本发明做进一步说明。应理解，以下实施例仅用于说明本发明而非用于限制本发明的范围。
实施例1喷涂粉末制备
在本实施例中，选用化学组成为4mol.％Yb2O3-0.5mol.％Y2O3-ZrO2的二元稀土共掺杂氧化锆为优选对象。以纯度为99.99％的Yb2O3、Y2O3和ZrOCl2·8H2O为原料，按摩尔比Yb2O3：Y2O3：ZrOCl2·8H2O＝4：0.5：95.5称量，将Yb2O3和Y2O3溶于稀盐酸中，ZrOCl2·8H2O溶于去离子水中，将所配溶液混合后，加入聚乙二醇进行分散，磁力搅拌1小时得到澄清透明的溶液。将前驱溶液逐滴加入到稀释后的氨水溶液中，并保持pH＝10.5，以充分形成沉淀。在原液中陈化24小时后，所得沉淀物用去离子水洗涤3次，再用无水乙醇洗涤2次，以去除离子杂质。将沉淀在1100℃空气气氛中煅烧7小时后，冷却至室温，获得所需材料粉体。
实施例2热障涂层系统制备
热障涂层样品采用常规大气等离子喷涂方法制备。利用前述化学共沉淀法得到二元稀土共掺杂氧化锆粉体，经过喷雾造粒、干燥处理制成粒径15～60微米的高流动性粉末作为陶瓷层粉末。基体和粘结层材料分别采用高温镍基合金IN738和国产NiCrAlY。利用喷枪预热基体至400℃后，喷涂NiCrAlY粉末制备金属粘结层。喷涂电压和电流分别为60V和500A，主气压力为0.47MPa，氢气压力为0.25MPa。喷枪移动速度设定为500mm/s，喷涂距离为100mm，送粉转速控制在1.2r/min，粘结层的厚度控制在150μm左右。对于陶瓷层，同样在不送粉的情况下利用喷枪将基体预热至500℃。此时，电压为60V，电流为600A，主气压力为0.45MPa，氢气压力为0.25MPa。将喷枪移动速度设定为150mm/s，喷涂距离为80mm，送粉率为1.5r/min。陶瓷层厚度控制在350μm左右。
根据该方法制备得到的热障涂层系统结构如图2所示。涂层表现出典型大气等离子喷涂工艺的微观结构特征且多层之间结合紧密，无明显裂纹产生。
X射线衍射结果表明，步骤一制备的粉末和喷涂态涂层均呈现单一的四方相(图3)。
为了便于比较，本实施例还采用相同工艺制备了传统YSZ涂层，其化学组成为4.5mol.％Y2O3-ZrO2。经过测量，传统YSZ涂层与二元稀土共掺杂氧化锆长寿命热障涂层的热膨胀系数随温度变化如图4所示。结果显示，本实施例制备的二元稀土掺杂氧化锆材料的热膨胀系数为11.25×10-6℃(1000℃)，比传统YSZ材料(10.36×10-6/℃，1000℃)高约10％。
如图5中的a和b所示，本实施例制备的二元稀土共掺杂氧化锆材料经1500℃保温300小时后的X射线衍射图谱未发现单斜相衍射峰出现，即没有发生相变，表明材料在高温条件下具有良好的相稳定性，适用于高温长时间服役热障涂层。
实施例3热震实验
使用实施例2中所制备的二元稀土共掺杂氧化锆长寿命热障涂层与常用YSZ热障涂层进行对比热震试验。将试样放入1050℃马弗炉中，保温10min后迅速取出试样放入25℃去离子水中水淬并擦干，即为一次热震。涂层失效定义为超过20％的涂层发生剥落时所经历的热震次数。每种涂层都采用3个试样来确定其热震寿命。两种涂层的热震寿命结果的比较如图6所示。在相同喷涂工艺下，新型二元稀土共掺杂氧化锆热障涂层表现出更好的热震性能。相比于传统YSZ涂层，新型二元稀土共掺杂氧化锆涂层的热震寿命提高10％以上。
实施例4热循环实验
使用步骤2中所制备的二元稀土共掺杂氧化锆长寿命热障涂层与常用YSZ热障涂层进行对比热循环实验。利用丙烷火焰加热方式对热障涂层进行热循环考核，装置示意图见图7。利用手持式红外测温枪进行测温，热循环实验时涂层表面温度达到1350℃，基体温度为950℃。每次热循环经历5分钟加热和5分钟冷却。涂层失效定义为超过20％的涂层发生剥落时所经历的热循环次数。两种涂层的热循环寿命结果的比较如图8所示。结果表明，相比于传统YSZ涂层，新型二元稀土共掺杂氧化锆热障涂层表现出更好的热循环性能，寿命提高20％以上。
以上结果证明，相比于传统YSZ材料，本发明提供的一种二元稀土共掺杂氧化锆热障涂层材料具有较长的寿命，且制备成本低、制备方法简单，易于实现工业化生产运用。
以上所述的，仅为本发明的较佳实施例，并非用以限定本发明的范围，本发明的上述实施例还可以做出各种变化。凡是依据本发明申请的权利要求书及说明书内容所作的简单、等效变化与修饰，皆落入本发明专利的权利要求保护范围。本发明未详尽描述的均为常规技术内容。

Claims (5)

1.一种热障涂层系统的制备工艺，其特征在于，包括以下步骤：
B1：提供一种长寿命热障涂层材料；
B2：将所述长寿命热障涂层材料进行喷雾造粒，干燥处理，制成粒径为15~60μm的高流动性粉末作为陶瓷层粉末；
B3：提供一种镍基合金基体，在所述镍基合金基体上喷涂NiCrAlY粉末形成金属粘结层；所述金属粘结层制备过程中的参数为：首先利用喷枪预热基体至380~420℃，然后进行喷涂，喷涂电压为55~65V，喷涂电流为400~600A，主气压力为0.4~0.5MPa，氢气压力为0.2~0.3Mpa，喷枪移动速度为450~550 mm/s，喷涂距离为50~150 mm，送粉转速为1.0~1.5 r/min；
B4：采用喷涂工艺将步骤B2制备的陶瓷层粉末喷涂到步骤B3制备的金属粘结层上，形成陶瓷层，即得，所述陶瓷层为化学组成为xYb2O3-yY2O3-ZrO2的二元稀土共掺杂氧化锆，其中x+y≤6 mol.%, x≥3 mol.%，呈现单一四方相氧化锆；所述陶瓷层制备过程的参数为：首先利用喷枪将基体预热至480~520℃，然后进行喷涂，喷涂电压为55~65V，喷涂电流为500~700 A，主气压力为0.4~0.5 MPa，氢气压力为0.2~0.3MPa，喷枪移动速度为100~200 mm/s，喷涂距离为60~100 mm，送粉转速为1.3~1.7 r/min；
其中，所述长寿命热障涂层材料为二元稀土共掺杂氧化锆，其化学组成为xYb2O3-yY2O3-ZrO2, 其中x+y≤6 mol.%，x≥3 mol.%，所述长寿命热障涂层材料呈现单一四方相氧化锆，所述长寿命热障涂层材料的制备工艺包括以下步骤：
A1：按一定的摩尔比分别称量Yb2O3、Y2O3、ZrOCl2·8H2O，然后将Yb2O3和Y2O3溶于稀盐酸中，ZrOCl2·8H2O溶于去离子水中，混合制成混合溶液，然后加入聚乙二醇进行分散，磁力搅拌1~2小时得到澄清透明的溶液，得到前驱溶液；
A2：将步骤A1所得前驱溶液逐滴加入到氨水溶液中，并保持pH=10.0~11.0，以充分形成沉淀，在原液中陈化24~28小时后，获得沉淀物，然后依次用去离子水洗涤3次，再用无水乙醇洗涤2次；
A3：将步骤A2所得沉淀物在1100~1300℃空气气氛中煅烧6~8小时后，冷却至室温，即可获得一种二元稀土共掺杂氧化锆的长寿命热障涂层材料。
2.根据权利要求1所述的制备工艺，其特征在于，步骤A1中，所述Yb2O3、Y2O3、ZrOCl2·8H2O的纯度为99.99%以上。
3.根据权利要求1所述的制备工艺，其特征在于，步骤A3中，将步骤A2所得沉淀物在1100~1200℃空气气氛中煅烧6~7小时。
4.根据权利要求1所述的制备工艺，其特征在于，所述金属粘结层的厚度控制在130~180 μm。
5. 根据权利要求1所述的制备工艺，其特征在于，所述陶瓷层的厚度控制为300~400 μm。
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