CN114231906A - 一种船用燃气轮机高压涡轮叶片的热障涂层及其制备方法 - Google Patents
一种船用燃气轮机高压涡轮叶片的热障涂层及其制备方法 Download PDFInfo
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Abstract
本发明提供一种船用燃气轮机高压涡轮叶片的热障涂层及其制备方法，采用电子束物理气相沉积技术通过蒸发金属锭和陶瓷锭沉积在金属表面形成热障涂层，金属靶材为CoNiCrAlY型合金，成分为Ni：0.1％‑2％、Cr：21％‑25％、Al：10％‑13％、Y：0.4％‑1％、Hf：0.05％‑0.2％、Zr：0.05％‑0.4％、Si：0.05％‑0.5％、Co‑余量；陶瓷靶材为ZrO2/(6％～8％)Y2O3，成分为ZrO2：93±1.0％，Y2O3：7±1.0％。本发明所制备的涂层不仅起到良好的隔热作用，也提高了基体合金抗氧化腐蚀能力，成为提高燃气轮机效率并延长涡轮叶片使用寿命的重要手段之一。
Description
技术领域
本发明属于热障涂层制备技术领域，特别是涉及一种采用电子束物理气相沉积方法通过蒸发金属锭及陶瓷锭形成蒸气沉积在船用燃气轮机涡轮动叶表面形成氧化锆热障涂层的制备方法，属于国际专利分类表中的C23C4/10(2006.01)I技术领域。
背景技术
涡轮叶片作为船用燃气轮机的关键部件之一，工作环境极为恶劣，受到了高温、燃气腐蚀、离心力、弯曲应力、热应力、振动和热疲劳等因素的综合影响。船用燃气轮机因在海洋性环境条件下工作，涡轮叶片除要求很好的综合机械性能以外，其表面防护涂层也应具备优异的抗氧化和抗高温腐蚀性能。
随着燃气轮机功率的不断提升，涡轮进口温度的提高对涡轮叶片冷却结构及涂层提出了更高的要求。在涡轮叶片表面制备热障涂层，不仅起到良好的隔热作用，也提高了基体合金抗氧化和抗热腐蚀能力，成为提高燃气轮机效率并延长涡轮叶片使用寿命的重要手段之一。
目前的热障涂层基本上是由金属粘结层与陶瓷面层所构成的双涂层结构，在现有技术中等离子喷涂方法制备的涂层与基体结合力相对较低，在冷热循环的作用下极易剥落，所以传统等离子喷涂热障涂层很少在燃机涡轮转子叶片等热端部件进一步推广应用。
近年来也有采用电子束物理气相沉积(EB-PVD)技术制备涂层，原理为利用高能量密度的电子束轰击沉积材料使之气化蒸发，材料蒸气以原子或分子的形式沉积到基体上形成涂层。该方法制备的涂层与等离子喷涂法相比具有明显优势：柱状晶结构的涂层具有更高的应变容限；致密的涂层使得抗氧化和抗热腐蚀性能更好；以化学结合为主的涂层界面使结合力显著增大；更光洁的表面有利于提高叶片的空气动力学性能；可在复杂构件上沉积。
因此，研究开发出合适的电子束物理气相沉积工艺制备氧化锆热障涂层是近年来涡轮叶片基体上沉积热障涂层研究的热点之一。公开号为CN 105369202的发明专利申请曾给出了《一种重型燃机涡轮叶片热障涂层的制备方法》，即利用EB-PVD技术在重型燃机涡轮叶片上制备CoCrAlY粘结层，并对所述CoCrAlY粘结层进行真空扩散处理；对CoCrAlY粘结层的表面，使用通用喷丸设备，应用玻璃丸进行喷丸处理；对带有CoCrAlY粘结层的重型燃机涡轮叶片进行消除应力处理；利用EB-PVD技术在带有CoCrAlY粘结层的重型燃机涡轮叶片上制备YSZ面层。该技术方案给出了氧化锆热障涂层的制备方法，虽具有操作简单，工艺流程少，制备成本低，有利于工业化生产等优点，但是该方法并不适用于所有EB-PVD制备的热障涂层，也未对预处理及沉积制备方法进行详尽描述，因此不具有很强的参考价值。
发明内容
本发明目的在于解决现有技术存在的上述技术问题，通过研究改进提供了一种用于船用燃气轮机涡轮动叶表面氧化锆热障涂层及其制备方法。该方法为采用电子束物理气相沉积技术，通过蒸发金属锭和陶瓷锭形成蒸气沉积在金属表面形成热障涂层。粘结层采用CoNiCrAlY型系列合金，以实现陶瓷层与基体热膨胀应力的适配，同时保护基体在高温下免受氧化和热腐蚀；陶瓷层采用氧化钇部分稳定的氧化锆(ZrO2/(6～8％)Y2O3)。该方法制备的涂层致密，与基体结合力良好，具有良好的抗热循环能力及抗高温腐蚀的能力。
本发明给出的技术方案是：
一种用于船用燃气轮机涡轮动叶的氧化锆热障涂层，采用电子束物理气相沉积技术通过蒸发金属锭和陶瓷锭沉积在金属表面形成热障涂层，
金属靶材为CoNiCrAlY型合金，成分为Ni：0.1％-2％、Cr：21％-25％、Al：10％-13％、Y：0.4％-1％、Hf：0.05％-0.2％、Zr：0.05％-0.4％、Si：0.05％-0.5％、Co-余量；
陶瓷靶材为ZrO2/(6％～8％)Y2O3，成分为ZrO2：93±1.0％，Y2O3：7±1.0％。
上述技术方案提及的氧化钇部分稳定的氧化锆(ZrO2/(6～8％)Y2O3)是指：氧化钇在涂层材料中起到稳定剂的作用，并且由于添加稳定剂种类不同，因此，一般在写涂层名称的同时也将稳定剂名称写出，由于本发明添加的是氧化钇，因此称为氧化钇部分稳定的氧化锆涂层，括号中(ZrO2/(6～8％)Y2O3)是指涂层的化学成分及含量，意思为添加含(6～8％)氧化钇的氧化锆。
本发明给出船用燃气轮机涡轮动叶的氧化锆热障涂层制备方法，包括如下步骤：
(1)蒸发料锭的准备：金属靶材为CoNiCrAlY型合金，陶瓷靶材为ZrO2/(6％～8％)Y2O3，两种料锭直径均为68.4-68.9mm，长度均为200-300mm，金属锭在真空感应炉中熔炼不少于两次，浇注成靶锭后机械加工制成靶材,陶瓷锭由两组分混合均匀后按规定尺寸机械压制而成；
(2)表面预处理：对叶片表面进行吹砂，粗糙度达到Ra1.0-2.0μm，对叶片进行振动光饰，吹干后安装在叶片支撑架上，将叶片支撑送入真空室；
(3)将粘结层用金属靶材、面层用陶瓷靶材分别放置在坩埚中；
(4)将真空室抽真空至所需真空度10-3Pa；
(5)设定旋转基板架所需旋转的速度10～20rpm，用电子束将基板加热至800～900℃，电子束电流0.10～0.40A，对工件进行预热；
(6)预蒸发粘结层金属锭，并调节电子束流1.4～1.8A，料棒上升速率0.8～1.0mm/min，控制蒸发量；
(7)拉开挡板，进行蒸发沉积粘结层：
沉积金属粘结层，沉积室真空度应小于10-3Pa，电子束流1.70～1.80A，料锭消耗速率0.40～0.80mm/min，控制蒸发量；沉积完成后，卸载工件；
根据涂层厚度对粘结层厚度的要求，当蒸发到粘结层总厚度的2/3时，调节电子束电流，由原来的1.8A逐渐变化至0.8A，变化速率：0.2～0.3A/min；
(8)粘结层沉积结束，对粘结层进行扩散热处理：温度1050±10℃，时间2.0～2.25h；
(9)扩散热处理结束，对粘结层进行喷丸强化，喷丸强度0.06～0.10A，随后进行扩散退火：温度1050±10℃，时间2.0～2.25h；
(10)蒸发沉积陶瓷层，电子束电流为1.5～1.6A，电子束电压为18.0～21.0kV，料锭消耗速率0.40～0.80mm/min；
(11)陶瓷层沉积结束后，对陶瓷层进行扩散热处理：温度1050±10℃，时间2.0～2.25h；
(12)继续保持真空状态，待基板自然冷却至50℃以下后，开启真空室，取出热障涂层材料，制备结束。
为更好地实现本发明的目的，所述步骤(5)中对基板进行预热，预热时间至少为60min，其目的在于排放基板上所吸附的气体，同时利用基板的热量烘烤真空室壁，以使吸附的气体在正式蒸发之前排放出来，保证蒸发过程中具有较高的真空度，提高涂层与基体的结合强度。
为更好地实现本发明的目的，所述步骤(7)中过渡层的铝含量呈梯度上升，铝含量可控。
与现有技术相比，本发明的有益效果是：
1、涂层表面光滑无需再加工，工艺参数易于控制，涂层可修复；
2、粘结层中的镍、钴、铬、铝、钇成分可控；
3、粘结层与陶瓷层之间形成扩散，实现了金属粘结层与陶瓷层之间结构和成分的连续过渡；
4、粘结层具有良好的塑性与抗长时间高温氧化腐蚀的能力；
5、热障涂层服役寿命大幅度提高；
6、本发明所制备的涂层不仅起到良好的隔热作用，也提高了基体合金抗氧化腐蚀能力，成为提高燃气轮机效率并延长涡轮叶片使用寿命的重要手段之一。其原理是：利用高能量密度的电子束轰击沉积材料使之气化蒸发，材料蒸气以原子或分子的形式沉积到基体上形成涂层；
7、本发明方法制备的涂层与等离子喷涂法相比具有明显优势：柱状晶结构的涂层具有更高的应变容限，致密的涂层使得抗氧化和抗热腐蚀性能更好，以化学结合为主的涂层界面使结合力显著增大，更光洁的表面有利于提高叶片的空气动力学性能，可在复杂构件上沉积。
说明书附图
图1为船用燃气轮机高压涡轮动叶EB-PVD热障涂层典型组织结构。
具体实施方式
实施例1
船用燃气轮机涡轮叶片的基体为K444合金，粘结层材料为Cr：22.6％、Al：12.9％、Ni：0.14％、Y：1.064％、Hf：0.145％、Zr：0.055％、Si：0.141％、Co-余量，陶瓷层材料为氧化钇部分稳定的氧化锆(ZrO2/(6～8％)Y2O3)：ZrO2为93±1.0％，Y2O3为7±1.0％。
制备船用燃气轮机涡轮叶片的热障涂层的方法有下列步骤：
(1)来件检查：检查零件表面状态及外观情况，表面不应有有磕伤、碰伤、划伤等。
(2)蒸发料锭的准备：金属靶材为CoCrAlY，料锭直径68.4-68.9mm，长度200-300mm，陶瓷靶材为(ZrO2/(6～8％)Y2O3)，料锭直径68.4-68.9mm，长度200-300mm，采用真空感应炉在1600℃下反复熔炼合金料棒3次，熔炼功率40KW，工作频率4KHz，背底真空度为0.3Pa；
(3)表面预处理：对叶片表面进行吹砂，粗糙度达到Ra1.0-2.0μm，对叶片进行振动光饰，吹干后安装在叶片支撑架上，将叶片支撑送入真空室；
(4)将粘结层用金属靶材、面层用陶瓷靶材分别放置在坩埚中；
(5)将真空室抽真空至所需真空度10-3Pa；
(6)工件的加热，设定旋转基板架所需旋转的速度10～20rpm，用电子束将基板加热至800～900℃，电子束电流0.10～0.40A，对工件进行预热；
(7)预蒸发粘结层金属锭，并调节电子束流1.4～1.8A，料棒上升速率0.8～1.0mm/min，控制蒸发量；
(8)拉开挡板，进行蒸发沉积粘结层
沉积金属粘结层，沉积室真空度应小于10-3Pa，电子束流1.70～1.80A，料锭消耗速率0.40～0.80mm/min，控制蒸发量；沉积完成后，卸载工件。
根据涂层厚度对粘结层厚度的要求，当蒸发到粘结层总厚度的2/3时，调节电子束电流，由原来的1.8A逐渐变化至0.8A，变化速率：0.2～0.3A/min；
(9)粘结层沉积结束，对粘结层进行扩散热处理：温度1050±10℃，时间2.0～2.25h；
(10)扩散热处理结束，对粘结层进行喷丸强化，喷丸强度0.06～0.10A，随后进行扩散退火：温度1050±10℃，时间2.0～2.25h；
(11)蒸发沉积陶瓷层，电子束电流为1.5～1.6A，电子束电压为18.0～21.0kV，料锭消耗速率0.40～0.80mm/min，；
(12)陶瓷层沉积结束后，对陶瓷层进行扩散热处理：温度1050±10℃，时间2.0～2.25h；
(13)继续保持真空状态，待基板自然冷却至50℃以下后，开启真空室，取出热障涂层材料，制备结束。
Claims (4)
1.一种船用燃气轮机高压涡轮叶片的热障涂层，采用电子束物理气相沉积技术通过蒸发金属锭和陶瓷锭沉积在金属表面形成热障涂层，其特征是：
金属靶材为CoNiCrAlY型合金，成分为Ni：0.1％-2％、Cr：21％-25％、Al：10％-13％、Y：0.4％-1％、Hf：0.05％-0.2％、Zr：0.05％-0.4％、Si：0.05％-0.5％、Co-余量；
陶瓷靶材为ZrO2/(6％～8％)Y2O3，成分为ZrO2：93±1.0％，Y2O3：7±1.0％。
2.一种船用燃气轮机高压涡轮叶片的热障涂层的制备方法，其特征是，包括如下步骤：
(1)蒸发料锭的准备：金属靶材为CoNiCrAlY型合金，陶瓷靶材为ZrO2/(6％～8％)Y2O3，两种料锭直径均为68.4-68.9mm，长度均为200-300mm，金属锭在真空感应炉中熔炼不少于两次，浇注成靶锭后机械加工制成靶材，陶瓷锭由两组分混合均匀后按规定尺寸机械压制而成；
(2)表面预处理：对叶片表面进行吹砂，粗糙度达到Ra1.0-2.0μm，对叶片进行振动光饰，吹干后安装在叶片支撑架上，将叶片支撑送入真空室；
(3)将粘结层用金属靶材、面层用陶瓷靶材分别放置在坩埚中；
(4)将真空室抽真空至所需真空度10-3Pa；
(5)设定旋转基板架所需旋转的速度10～20rpm，用电子束将基板加热至800～900℃，电子束电流0.10～0.40A，对工件进行预热；
(6)预蒸发粘结层金属锭，并调节电子束流1.4～1.8A，料棒上升速率0.8～1.0mm/min，控制蒸发量；
(7)拉开挡板，进行蒸发沉积粘结层：
沉积金属粘结层，沉积室真空度应小于10-3Pa，电子束流1.70～1.80A，料锭消耗速率0.40～0.80mm/min，控制蒸发量；沉积完成后，卸载工件；
根据涂层厚度对粘结层厚度的要求，当蒸发到粘结层总厚度的2/3时，调节电子束电流，由原来的1.8A逐渐变化至0.8A，变化速率：0.2～0.3A/min；
(8)粘结层沉积结束，对粘结层进行扩散热处理：温度1050±10℃，时间2.0～2.25h；
(9)扩散热处理结束，对粘结层进行喷丸强化，喷丸强度0.06～0.10A，随后进行扩散退火：温度1050±10℃，时间2.0～2.25h；
(10)蒸发沉积陶瓷层，电子束电流为1.5～1.6A，电子束电压为18.0～21.0kV，料锭消耗速率0.40～0.80mm/min；
(11)陶瓷层沉积结束后，对陶瓷层进行扩散热处理：温度1050±10℃，时间2.0～2.25h；
(12)继续保持真空状态，待基板自然冷却至50℃以下后，开启真空室，取出热障涂层材料，制备结束。
3.根据权利要求2所述的一种船用燃气轮机高压涡轮叶片的热障涂层的制备方法，其特征是，所述金属靶材为CoNiCrAlY型合金，成分为Ni：0.1％-2％、Cr：21％-25％、Al：10％-13％、Y：0.4％-1％、Hf：0.05％-0.2％、Zr：0.05％-0.4％、Si：0.05％-0.5％、Co-余量；陶瓷靶材为ZrO2/(6％～8％)Y2O3，成分为ZrO2：93±1.0％，Y2O3：7±1.0％。
4.根据权利要求3所述的一种船用燃气轮机高压涡轮叶片的热障涂层的制备方法，其特征是，所述步骤(5)中对基板进行预热，预热时间至少为60min。
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