CN112830787B - 一种非晶硅氧碳复合陶瓷热障涂层的制备方法 - Google Patents
一种非晶硅氧碳复合陶瓷热障涂层的制备方法 Download PDFInfo
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Abstract
本发明涉及一种非晶硅氧碳陶瓷复合热障涂层的制备方法。将含氢聚硅氧烷和四甲基四乙烯基环四硅氧烷,搅拌得到PSO前驱体;将氧化硅、氧化铝、氧化硼、铝和镍作为固体填料,加入溶剂混合,然后进行球磨,得到的固体填料和溶剂的混合物作为球磨浆料;将球磨浆料加入PSO前驱体中得到PSO前驱体浆料;采用提拉浸渍法,将PSO前驱体浆料在基体表面包覆一层PSO浆料;将得到的包覆了PSO浆料的基体放入烘箱中交联,在基体表面形成PSO复合涂层;放入管式炉,在惰性气氛中热解,得到硅氧碳复合涂层。陶瓷复合涂层具有较低的热导率0.314W/(m·K),且涂层与基体之间的结合强度大于10MPa,满足目前热障涂层的要求。
Description
技术领域
本发明涉及航空发动机及重型燃气轮机涡轮叶片领域,特别涉及一种非晶硅氧碳陶瓷复合热障涂层的制备方法。
背景技术
为了提高航空发动机和重型燃气轮机的性能,人们对涡轮叶片的最高服役温度和服役时间提出了新的要求,然而最先进的单晶叶片材料最高承受温度也不超过1326℃,极大地限制了发动机热效率的提高。在涡轮叶片表面涂覆一层低热导率的热障涂层可以较大程度降低叶片表面的温度,从而使得涡轮叶片在较高环境温度下能正常工作。热障涂层材料一般为无机陶瓷材料,因在高温极端环境下工作,一般具有以下特点:低的热导率、高的热膨胀系数、与基体材料之间有较高的结合强度,高温下不发生相变和一定的机械强度。常用的热障涂层是氧化锆基系列材料,纯氧化锆由于存在温度型相变,伴随较大体积变化,容易导致裂纹的形成和发展,甚至造成涂层的开裂和剥落,因此通常向氧化锆中添加稳定剂来抑制相变,目前性能最好的是氧化钇掺杂稳定的氧化锆(YSZ)。但是YSZ的高温相稳定性较差,仅能在1300℃下使用,同时,烧结速率随温度升高而加快,气孔率减小,热导率升高。为了探索更高温度下可正常工作的热障涂层材料,焦绿石、萤石和其他化合物体系的热障涂层材料陆续被开发,但是因为都存在一定的问题,不能大规模推广应用。
大气等离子喷涂和电子束物理气相沉积是制备热障涂层材料的主要工艺,但是各自存在一定的缺点,大气等离子喷涂制备的热障涂层结合强度较差,服役过程中容易发生开裂;电子束物理气相沉积制备的热障涂层热导率较高,高温下严重降低其隔热性能。两种工艺都需要极高的温度环境,对设备有着较大的要求。因此,开发一种热障涂层的简单制备工艺有着一定市场需求,能扩大热障涂层的使用领域。
前驱体陶瓷是利用聚合物前驱体在高温下热解会发生有机-无机转变机理而得到的无机非晶陶瓷。前驱体陶瓷具有很多优异的特性,优良的机械性能、高的相稳定性和高的抗氧化性,其中最重要的优点是聚合物前驱体的可设计性,允许人们通过改变前驱体的成分来控制和调整前驱体陶瓷的成分和结构,从而使得人们能根据自己的需要制备合适的前驱体陶瓷。聚合物前驱体转化硅氧碳陶瓷是由聚硅氧烷前驱体热解得到的,可以看作二氧化硅中的硅氧四面体中的部分氧被碳取代,因此硅氧碳陶瓷比传统二氧化硅的性能有了较大提升,弹性模量、硬度、玻璃转变温度和结晶温度都有了一定的提高(J.Am.Ceram.Soc.2018,101,4817)。
近些年来,硅氧碳陶瓷因其优异的抗氧化性和抗腐蚀性开始被用于涂层领域的探索,多用于基体表面的抗氧化(J.Eur.Ceram.Soc.2017,37,4559)和抗腐蚀涂层(J.Eur.Ceram.Soc.2014,34,3597)。这种方法具有前驱体浆料的可设计性、涂覆工艺的简单性、复杂形状基体表面涂层的易制备性和可低温烧结等特点,越来越引起人们的注意。但是,硅氧碳陶瓷在热障涂层领域中的应用还未见报道,至今仍处于空白。同时硅氧碳陶瓷具有较低的热导率和较好的高温稳定性,在热障涂层领域具有一定的应用潜力。
发明内容
本发明的目的是提供一种利用聚合物前驱体转化法制备硅氧碳复合热障涂层。所得的硅氧碳复合陶瓷热障涂层具有多级孔结构,能够有效降低涂层的热导率,并且涂层与基体具有一定的结合强度,可适应极端条件下的工作环境。
本发明利用硅氧碳陶瓷优异的热力学性能公开了一种硅氧碳陶瓷复合热障涂层。通过硅氧碳陶瓷与不同填料的复合,以发挥两者的优异性能,并利用两者的协同作用解决了硅氧碳陶瓷作为涂层时存在的脆性、易开裂、结合差、厚度小等问题,具有低热导、高结合、耐腐蚀等优点,是一种理想的热障涂层材料。本发明进一步拓展了硅氧碳陶瓷材料在涂层领域(尤其是热障涂层领域)的应用空间,不仅能在常规环境下使用,同时在极端环境下也能具有优异的性能,满足航空航天等领域对高性能热端部件的需求。
本发明的硅氧碳复合陶瓷热障涂层利用含氢聚硅氧烷(PHMS)和四甲基四乙烯基环四硅氧烷(D4Vi)作为聚硅氧烷(PSO)前驱体,通过在前驱体中加入惰性陶瓷粉抑制聚合物热解过程中的收缩,通过加入金属粉提升复合涂层的热膨胀系数,通过加入玻璃粉实现涂层中裂纹等缺陷的自愈合。通过提拉浸渍方法在镍合金基体上涂覆前驱体复合涂层,经交联和热解后得到硅氧碳复合热障涂层。
一种非晶硅氧碳复合陶瓷热障涂层的制备方法为;包括以下步骤:
1)PSO前驱体浆料的配制:称取含氢聚硅氧烷和四甲基四乙烯基环四硅氧烷,搅拌均匀得到PSO前驱体;称取氧化硅、氧化铝、氧化硼、铝和镍作为固体填料,加入溶剂混合均匀,然后进行球磨,将球磨结束后得到的固体填料和溶剂的混合物作为球磨浆料;将球磨浆料加入PSO前驱体中得到PSO前驱体浆料;
2)硅氧碳复合涂层的制备:采用提拉浸渍法,将步骤1)得到的PSO前驱体浆料提拉1~3次,每次浸渍5~10s,在基体表面包覆一层均匀的PSO浆料;
3)PSO前驱体的交联和热解:将步骤2)得到的包覆了PSO浆料的基体放入烘箱中交联,在基体表面形成均匀的PSO复合涂层;再放入管式炉,在惰性气氛中进行热解,得到硅氧碳复合涂层。
优选的,步骤1)中的固体填料中的氧化硅、氧化铝、氧化硼、铝和镍的质量比为1:(1-2):(1-2):1:1。
优选的,步骤1)中的含氢聚硅氧烷与四甲基四乙烯基环四硅氧烷的质量比为1:(1-2)。
优选的,步骤1)中PSO前驱体与固体填料的质量比为1:(2-4)。
优选的,步骤1)中的球磨溶剂可以为正己烷、环己烷或乙醇。
优选的,步骤1)中的球磨浆料的固含量(球磨浆料中固体填料的质量分数)为40~50%。
优选的,步骤2)中的提拉速度为1000~5000μm/s。
优选的,步骤2)中的基体为高温K3镍合金。
优选的,步骤3)中的交联温度60~100℃,交联时间1~2h。
优选的,步骤3)中的热解温度1000~1200℃,保温时间2h。
优选的,步骤3)中的升温速率3~5℃/min。
本发明使用上述工艺通过聚合物前驱体转化法制备得到硅氧碳复合陶瓷热障涂层。
本发明的有益成果
本发明利用硅氧碳陶瓷优异的热力学性能和成型优势,提供了一种新型硅氧碳复合陶瓷热障涂层,具有低的热导率,0.314W/(m·K),与基体有高的结合强度,10MPa,高的高温稳定性和抗氧化性等突出性能。
本发明的新型硅氧碳复合陶瓷涂层在金属或合金基体前驱体陶瓷涂层中具有最大的厚度,100μm左右,均匀致密的表面形貌,充分克服了前驱体陶瓷易收缩、缺陷多的缺点。
附图说明
图1是实施例1所制备的硅氧碳复合陶瓷涂层的表面SEM图。
图2是实施例1所制备的硅氧碳复合陶瓷涂层的断面SEM图。
具体实施方式
下面结合具体的实施例对本发明做进一步详细说明,所述是对本发明的解释而不是限定。
实施例1
1)PSO前驱体浆料配置:称取质量为1.25g的含氢聚硅氧烷和1.25g四甲基四乙烯基环四硅氧烷,磁力搅拌1h,得到PSO前驱体。称取质量分别为1.25g、1.25g、2.5g、1.25g和1.25g的二氧化硅、氧化铝、氧化硼、铝和镍作为固体填料加入100ml球磨罐中,加入11.25g正己烷使得固含量为40%,使用行星式球磨机400r/min球磨1h,得到固体填料与溶剂组成的球磨浆料;将球磨完的浆料转移至PSO前驱体中,机械搅拌1h,得到PSO前驱体浆料。
2)硅氧碳复合涂层的制备:采用提拉浸渍法将步骤1)得到的PSO前驱体浆料在K3高温镍合金基体表面提拉3次,浸渍时间5s,提拉速度1000μm/s,得到硅氧碳复合涂层;
3)将步骤2)得到的包覆了PSO浆料的高温K3镍合金基体放入烘箱中60℃交联2h,在镍合金表面形成均匀的PSO复合涂层;再放入管式炉,再惰性气氛1000℃热解2h,得到SiOC复合涂层。
硅氧碳复合陶瓷涂层表面均匀致密没有明显的裂纹如图1所示。硅氧碳复合陶瓷涂层厚度约150μm,具有多级孔结构,涂层与基体结合紧密没有明显开裂现象如图2所示。硅氧碳复合陶瓷涂层利用热线法测得的室温下热导率为0.314W/(m·K)。利用拉脱法测得硅氧碳复合陶瓷涂层与基体的结合强度为10MPa。
实施例2
1)PSO前驱体浆料配置:称取质量比为1.73g的含氢聚硅氧烷和2.16g四甲基四乙烯基环四硅氧烷,磁力搅拌1h,得到PSO前驱体。称取质量分别为1.25g、2.50g、1.25g、1.25g和1.25g的二氧化硅、氧化铝、氧化硼、铝和镍作为固体填料加入100ml球磨罐中,加入7.5g正己烷使得固含量为50%,使用行星式球磨机400r/min球磨1h,得到固体填料与溶剂组成的球磨浆料;将球磨完的浆料转移至PSO前驱体中,机械搅拌1h,得到PSO前驱体浆料。
2)硅氧碳复合涂层的制备:采用提拉浸渍法将步骤1)得到的PSO前驱体浆料在K3高温镍合金基体表面提拉2次,浸渍时间8s,提拉速度1000μm/s,得到硅氧碳复合涂层。
3)将步骤2)得到的包覆了PSO浆料的高温K3镍合金基体放入烘箱中60℃交联1.5h,在镍合金表面形成均匀的PSO复合涂层;再放入管式炉,再惰性气氛1000℃热解2h,得到SiOC复合涂层。
实施例3
1)PSO前驱体浆料配置:称取质量为1.875g的含氢聚硅氧烷和1.875g四甲基四乙烯基环四硅氧烷,磁力搅拌1h,得到PSO前驱体。称取质量分别为1.25g、1.88g、2.50g、1.25g和1.25g的二氧化硅、氧化铝、氧化硼、铝和镍作为固体填料加入100ml球磨罐中,加入12.20g正己烷使得固含量为40%,使用行星式球磨机400r/min球磨1h,得到固体填料与溶剂组成的球磨浆料;将球磨完的浆料转移至PSO前驱体中,机械搅拌1h,得到PSO前驱体浆料。
2)硅氧碳复合涂层的制备:采用提拉浸渍法将步骤1)得到的PSO前驱体浆料在K3高温镍合金基体表面提拉1次,浸渍时间10s,提拉速度1000μm/s,得到硅氧碳复合涂层。
3)将步骤2)得到的包覆了PSO浆料的高温K3镍合金基体放入烘箱中60℃交联2h,在镍合金表面形成均匀的PSO复合涂层;再放入管式炉,再惰性气氛1000℃热解2h,得到SiOC复合涂层。
实施例4
1)PSO前驱体浆料配置:称取质量为1.5g的含氢聚硅氧烷和2.25g四甲基四乙烯基环四硅氧烷,磁力搅拌1h,得到PSO前驱体。称取质量分别为1.25g、1.25g、1.88g、1.25g和1.25g的二氧化硅、氧化铝、氧化硼、铝和镍作为固体填料加入100ml球磨罐中,加入6.88g正己烷使得固含量为50%,使用行星式球磨机400r/min球磨1h,得到固体填料与溶剂组成的球磨浆料;将球磨完的浆料转移至PSO前驱体中,机械搅拌1h,得到PSO前驱体浆料。
2)硅氧碳复合涂层的制备:采用提拉浸渍法将步骤1)得到的PSO前驱体浆料在K3高温镍合金基体表面提拉3次,浸渍时间5s,提拉速度5000μm/s,得到硅氧碳复合涂层。
3)将步骤2)得到的包覆了PSO浆料的高温K3镍合金基体放入烘箱中100℃交联1h,在镍合金表面形成均匀的PSO复合涂层;再放入管式炉,再惰性气氛1200℃热解2h,得到SiOC复合涂层。
实施例5
1)PSO前驱体浆料配置:称取质量比为0.86g和1.29g的含氢聚硅氧烷和四甲基四乙烯基环四硅氧烷,磁力搅拌1h,得到PSO前驱体。称取质量分别为1.25g、1.88g、1.88g、1.25g和1.25g的二氧化硅、氧化铝、氧化硼、铝和镍作为固体填料加入100ml球磨罐中,加入7.51g正己烷使得固含量为50%,使用行星式球磨机400r/min球磨1h,得到固体填料与溶剂组成的球磨浆料;将球磨完的浆料转移至PSO前驱体中,机械搅拌1h,得到PSO前驱体浆料。
2)硅氧碳复合涂层的制备:采用提拉浸渍法将步骤1)得到的PSO前驱体浆料在K3高温镍合金基体表面提拉3次,浸渍时间5s,提拉速度3000μm/s,得到硅氧碳复合涂层。
3)将步骤2)得到的包覆了PSO浆料的高温K3镍合金基体放入烘箱中60℃交联2h,在镍合金表面形成均匀的PSO复合涂层;再放入管式炉,再惰性气氛1200℃热解2h,得到SiOC复合涂层。
实施例6
1)PSO前驱体浆料配置:称取质量为1.56g的含氢聚硅氧烷和1.56g的四甲基四乙烯基环四硅氧烷,磁力搅拌1h,得到PSO前驱体。称取质量分别为1.25g、1.25g、1.25g、1.25g和1.25g的二氧化硅、氧化铝、氧化硼、铝和镍作为固体填料加入100ml球磨罐中,加入7.64g正己烷使得固含量为45%,使用行星式球磨机400r/min球磨1h,得到固体填料与溶剂组成的球磨浆料。将球磨完的浆料转移至PSO前驱体中,机械搅拌1h,得到PSO前驱体浆料。
2)硅氧碳复合涂层的制备:采用提拉浸渍法将步骤1)得到的PSO前驱体浆料在K3高温镍合金基体表面提拉3次,浸渍时间5s,提拉速度5000μm/s,得到硅氧碳复合涂层。
3)将步骤2)得到的包覆了PSO浆料的高温K3镍合金基体放入烘箱中100℃交联1h,在镍合金表面形成均匀的PSO复合涂层;再放入管式炉,再惰性气氛1100℃热解2h,得到SiOC复合涂层。
实施例7
1)PSO前驱体浆料配置:称取质量比为1.25g的含氢聚硅氧烷和3g四甲基四乙烯基环四硅氧烷,磁力搅拌1h,得到PSO前驱体。称取质量分别为1.25g、1.25g、2.50g、1.25g和1.25g的氧化硅、氧化铝、氧化硼、铝和镍作为固体填料加入100ml球磨罐中,加入9.17g正己烷使得固含量为45%,使用行星式球磨机400r/min球磨1h,得到固体填料与溶剂组成的球磨浆料。将球磨完的浆料转移至PSO前驱体中,机械搅拌1h,得到PSO前驱体浆料。
2)硅氧碳复合涂层的制备:采用提拉浸渍法将步骤1)得到的PSO前驱体浆料在K3高温镍合金基体表面提拉3次,浸渍时间5s,提拉速度1000μm/s,得到硅氧碳复合涂层。
3)将步骤2)得到的包覆了PSO浆料的高温K3镍合金基体放入烘箱中100℃交联2h,在镍合金表面形成均匀的PSO复合涂层;再放入管式炉,再惰性气氛1000℃热解2h,得到SiOC复合涂层。
本发明涉及一种聚合物前驱体转化硅氧碳复合陶瓷热障涂层。以含氢聚硅氧烷和四乙烯基环四硅氧烷为聚合物前驱体,通过加入氧化硅、氧化铝、氧化硼、铝和镍等多种陶瓷、金属和玻璃填料,利用提拉浸渍的方法在高温镍合金基体表面制备涂层,再经交联和高温热解得到致密、无开裂的硅氧碳陶瓷复合涂层。这种陶瓷复合涂层具有较低的热导率0.314W/(m·K),且涂层与基体之间的结合强度大于10MPa,满足目前热障涂层的要求。本发明提供了一种新型硅氧碳复合热障涂层材料的制备方法,进一步拓展了硅氧碳陶瓷在高性能涂层中的应用。硅氧碳热障涂层能够对热端部件提供保护,使其在极端工作环境热力载荷作用下具有较长的工作寿命,减少热侵蚀带来的经济损失。
根据本发明内容记载的工艺参数进行调整,均可实现硅氧碳复合陶瓷涂层的制备,且表现出与实例基本一致的性能。以上所述仅为本申请的优选实施例而已,并不用于限制本申请,对于本领域的技术人员来说,本申请可以有各种更改和变化。凡在本申请的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本申请的保护范围之内。
Claims (7)
1.一种非晶硅氧碳陶瓷复合热障涂层的制备方法: 其特征是,包括以下步骤:
1)PSO前驱体浆料的配制:称取含氢聚硅氧烷和四甲基四乙烯基环四硅氧烷,搅拌均匀得到PSO前驱体;称取氧化硅、氧化铝、氧化硼、铝和镍作为固体填料,加入溶剂混合均匀,然后进行球磨,将球磨结束后得到的固体填料和溶剂的混合物作为球磨浆料;将球磨浆料加入PSO前驱体中得到PSO前驱体浆料;固体填料中的氧化硅、氧化铝、氧化硼、铝和镍的质量比为1:(1-2):(1-2):1:1;
2)硅氧碳陶瓷复合热障涂层的制备:采用提拉浸渍法,将步骤1)得到的PSO前驱体浆料提拉1~3次,每次浸渍5~10s,在基体表面包覆一层均匀的PSO前驱体浆料;
3)PSO前驱体浆料的交联和热解:将步骤2)得到的包覆了PSO前驱体浆料的基体放入烘箱中交联,在基体表面形成均匀的PSO复合涂层;再放入管式炉,在惰性气氛中进行热解,得到非晶硅氧碳陶瓷复合热障涂层;
所述步骤1)中的含氢聚硅氧烷与四甲基四乙烯基环四硅氧烷的质量比为1:(1-2);PSO前驱体与固体填料的质量比为1:(2-4);所述步骤2)基体为高温K3镍合金。
2.如权利要求1所述的一种非晶硅氧碳陶瓷复合热障涂层的制备方法,其特征是步骤1)中的球磨溶剂为正己烷、环己烷或乙醇。
3.如权利要求1所述的一种非晶硅氧碳陶瓷复合热障涂层的制备方法,其特征是步骤1)中的球磨浆料的固含量为40~50%。
4.如权利要求1所述的一种非晶硅氧碳陶瓷复合热障涂层的制备方法,其特征是步骤2)中的提拉速度为1000~5000μm/s。
5.如权利要求1所述的一种非晶硅氧碳陶瓷复合热障涂层的制备方法,其特征是步骤3)中的交联温度60~100℃,交联时间1~2h。
6.如权利要求1所述的一种非晶硅氧碳陶瓷复合热障涂层的制备方法,其特征是步骤3)中的热解温度1000~1200℃,保温时间2h。
7.如权利要求1所述的一种非晶硅氧碳陶瓷复合热障涂层的制备方法,其特征是步骤3)中的升温速率3~5℃/min。
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