CN109023338B - 一种铌合金表面耐高温多组元硅化物涂层及其制备方法 - Google Patents

一种铌合金表面耐高温多组元硅化物涂层及其制备方法 Download PDF

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CN109023338B
CN109023338B CN201810696860.1A CN201810696860A CN109023338B CN 109023338 B CN109023338 B CN 109023338B CN 201810696860 A CN201810696860 A CN 201810696860A CN 109023338 B CN109023338 B CN 109023338B
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张平
冯培忠
陈正
沈承金
任宣儒
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China University of Mining and Technology CUMT
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Abstract

本发明公开了一种铌合金表面耐高温多组元硅化物涂层及其制备方法，该涂层的组成相为[(Nb1‑x‑yTixCry)1‑z，Rz]Si2，R为金属元素Mo,W,Zr,Hf,Ta中的一种或多种，其中x,y,z分别表示对应元素的摩尔数，且0.05≤x≤0.2,0.05≤y≤0.3,0.05≤z≤0.4；首先按摩尔比为[(Nb1‑x‑ yTixCry)1‑z，Rz]：Si＝1：2.01～2.1的比例，分别称取各金属单质粉末和硅单质粉末，投入混料机中充分混合12～24h；用混合好的多组元金属粉末将铌合金工件包埋后放在石墨坩埚中，然后将石墨坩埚置入放电等离子烧结炉中进行烧结；将烧结后的涂层试样在真空或保护气氛下进行均匀化热处理，即可。本发明提出了放电等离子烧结+均匀化热处理的复合制备工艺，工艺简单、涂层组织均匀、成分可控，涂层在1200‑1600℃下具有优良的抗高温氧化能力。

Description

一种铌合金表面耐高温多组元硅化物涂层及其制备方法
技术领域
本发明涉及一种金属材料表面高温抗氧化涂层及其制备方法，特别是一种铌合金表面耐高温涂层及其制备方法。
背景技术
铌合金以其高熔点、低密度以及良好的高低温力学性能，被认为是航空、航天与核工业中高温结构件的重要候选材料，但其抗氧化性能较差，而在表面制备防护涂层是提高铌合金抗氧化性能的最有效途径。硅化物涂层是最适用于铌合金的高温抗氧化涂层体系。
目前国内外研究的铌合金高温抗氧化硅化物涂层主要有两大体系，即 Si-Ti-Cr/Si-Fe-Cr基硅化物涂层体系和难熔硅化物(NbSi2，MoSi2)涂层体系。如中国专利CN101200801公开了一种在铌合金表面首先采用真空料浆烧结制备钼层，然后再包埋渗硅制备MoSi2涂层的方法，该涂层在1650℃静态抗氧化时间可达25小时；中国专利CN102719713A公开了一种通过将含有Si、Mo、Ti、 HfO2和Al等多种合金元素的涂层料浆涂覆于铌合金上，然后在高温真空下熔烧制备高温抗氧化硅化物涂层的方法，该涂层有效解决了铌合金在800℃以上，尤其是在1100℃上下大气环境中剧烈氧化问题；中国专利CN104561882A公开了一种采用高能等离子喷涂工艺在铌合金表面制备具有底涂层 Mo1-xWx(Si1-y-zAlyBz)2+面涂层Mo1-xWx(Si1-y-zAlyBz)2-(10-20)wt.％HfSi2的双层结构的涂层，该涂层在1500-1800℃具有优异的抗高温氧化性能。由此可见，多组元硅化物涂层是铌合金表面高温防护涂层的未来发展方向。尽管其中一些体系已经成功地应用到航空航天领域中铌合金高温保护上，但是简化涂层制备工艺流程，提高涂层组织均匀性、成分结构的可控性以及制备更高性能的保护涂层一直是铌合金表面抗氧化硅化物涂层研究的重点。
放电等离子烧结工艺是近年来备受重视的一种新的粉末冶金烧结技术，具有在加压过程中烧结的特点，脉冲电流产生的等离子体及烧结过程中的加压有利于降低粉末的烧结温度。同时低电压、高电流的特征，能使粉末快速烧结致密。它的工艺优势十分明显：加热均匀，升温速度快，烧结温度低，烧结时间短，生产效率高，产品组织细小均匀，能保持原材料的自然状态，可以得到高致密度的材料。目前已有科研工作者尝试采用放电等离子烧结工艺在铌合金表面制备抗氧化涂层，但涂层组织致密性欠缺，且涂层中存在较大的内应力，高温氧化过程中容易产成大的裂纹，甚至严重时会发生涂层崩落，从而失去保护作用。
发明内容
本发明的目的是提供一种铌合金表面耐高温多组元硅化物涂层，组织结构均匀，组成成分可控，具有良好的抗高温氧化能力。
本发明的目的是提供上述铌合金表面耐高温多组元硅化物涂层的制备方法，制备工艺简单。
为实现上述目的，本发明采用的技术方案如下：
一种铌合金表面耐高温多组元硅化物涂层，该涂层的组成相为 [(Nb1-x- yTixCry)1-z，Rz]Si2，R为金属元素Mo,W,Zr,Hf,Ta中的一种或多种，其中 x,y,z分别表示对应元素的摩尔数，且0.05≤x≤0.2，0.05≤y≤0.3，0.05≤z≤0.4。
本发明提供的铌合金表面耐高温多组元硅化物涂层的制备方法，具体实施步骤如下：
(1)首先按摩尔比[(Nb1-x-yTixCry)1-z，Rz]：Si＝1：2.01～2.1的比例，分别称取各金属单质粉末和硅单质粉末，投入混料机中充分混合12～24h；R为金属元素Mo,W,Zr,Hf,Ta中的一种或多种，其中x,y,z分别表示对应元素的摩尔数，且0.05≤x≤0.2，0.05≤y≤0.3，0.05≤z≤0.4；
(2)用混合好的多组元金属粉末将铌合金工件包埋后放在石墨坩埚中，然后将石墨坩埚置入放电等离子烧结炉中进行烧结；
(3)将烧结后的涂层试样再真空或保护气氛下进行均匀化热处理，即可形成耐高温多组元硅化物涂层。
进一步地，步骤(2)中，所述烧结的具体参数为：升温速率为50～100℃/s, 压力为25～50MPa，烧结温度为1250～1500℃，烧结时间为5～20min。
进一步地，步骤(3)中，所述热处理的具体参数为：温度为800～1250℃，时间为2～8h。
优选的，所述金属单质粉末和硅单质粉末的纯度≥99.0％，粒度≤50μm。
与现有技术相比，本发明具有如下有益效果：
1.本发明提出的铌合金表面耐高温多组元硅化物涂层，以NbSi2相为基体相，通过添加Ti,Cr,Mo,W,Zr,Hf,Ta等元素对其进行改性，其中Ti,Cr的添加可有效抑制单一NbSi2涂层的中温“pest”氧化现象且提高其室温韧性，而难熔金属Mo,W,Zr,Hf,Ta等元素的添加生成的MoSi2,WSi2,ZrSi2,HfSi2,TaSi2等高熔点硅化物相可进一步提高涂层的耐高温氧化能力。经1450℃氧化100h后涂层样品形成的表面氧化膜致密、完整，能较好地保护基体合金免于氧化。
2.本发明提出了放电等离子烧结+均匀化热处理的复合制备工艺，该工艺制备的涂层可进一步实现多组元涂层的组织成分可控，并有效降低涂层在烧结过程中产生的内应力，从而抑制涂层中裂纹的产生，提高涂层高温抗氧化性能。
附图说明
图1为本发明实施例3制备的铌合金表面耐高温[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]Si2涂层的表面XRD图谱；
图2为本发明实施例3制备的铌合金表面耐高温[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]Si2涂层的横截面BSE像；
图3为本发明实施例3制备的铌合金表面耐高温[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]Si2涂层的元素面分布；其中(A)元素Nb；(B)元素Si；(C)元素Ti；(D)元素 Cr；(E)元素W。
具体实施方式
下面以在铌合金表面制备[(Nb1-x-yTixCry)1-z，Rz]Si2涂层为例，结合附图和具体实施方式对本发明作进一步详细说明。
以下实施例中各金属单质粉末和硅单质粉末的纯度≥99.0％，粒度≤50μm。
实施例1：制备[(Nb0.75Ti0.05Cr0.2)0.95,W0.05]Si2涂层
(1)首先按摩尔比[(Nb0.75Ti0.05Cr0.2)0.95,W0.05]:Si＝1:2.03的比例，分别称取各金属单质粉末和硅单质粉末，投入混料机中充分混合12h；
(2)用混合好的多组元金属粉末将铌合金工件包埋后放在石墨坩埚中，然后将石墨坩埚置入放电等离子烧结炉中进行烧结，具体工艺参数为：升温速率为 100℃/s，压力为30MPa，经1400℃烧结5min；
(3)将烧结后的涂层试样在氩气保护气氛下进行均匀化热处理，温度为 1100℃，时间为4h，得到了主要由(Nb-Ti-Cr)Si2和少量WSi2组成的[(Nb0.75Ti0.05Cr0.2)0.95,W0.05]Si2涂层，涂层组织均匀，与基体结合呈冶金形式，成分分析表明涂层中各元素成分基本符合设计成分。
实施例2：制备[(Nb0.75Ti0.05Cr0.2)0.8,W0.2]Si2涂层
(1)首先按摩尔比[(Nb0.75Ti0.05Cr0.2)0.8,W0.2]:Si＝1:2.03的比例，分别称取各金属单质粉末，投入混料机中充分混合18h；
(2)用混合好的多组元金属粉末将铌合金工件包埋后放在石墨坩埚中，然后将石墨坩埚置入放电等离子烧结炉中进行烧结，具体工艺参数为：升温速率为 100℃/s，压力为30MPa，经1450℃烧结5min；
(3)将烧结后的涂层试样在氩气保护气氛下进行均匀化热处理，温度为 1150℃，时间为4h，得到了主要由(Nb-Ti-Cr)Si2和WSi2组成的[(Nb0.75Ti0.05Cr0.2)0.8, W0.2]Si2涂层，涂层组织均匀，与基体结合呈冶金形式，成分分析表明涂层中各元素成分基本符合设计成分。
实施例3：制备[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]Si2涂层
(1)首先按摩尔比[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]:Si＝1:2.03的比例，分别称取各金属单质粉末，投入混料机中充分混合24h；
(2)用混合好的多组元金属粉末将铌合金工件包埋后放在石墨坩埚中，然后将石墨坩埚置入放电等离子烧结炉中进行烧结，具体工艺参数为：升温速率为 100℃/s，压力为30MPa，经1450℃烧结5min；
(3)将烧结后的涂层试样在氩气保护气氛下进行均匀化热处理，温度为 1200℃，时间为4h，即可形成耐高温多组元硅化物涂层。
利用X射线衍射仪(德国Bruker D8ADVANCE XRD)对本实施例所制备的[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]Si2涂层的表面进行测试分析，结果如图1所示。
利用场发射扫描电子显微镜(日立SU8220)和背散射检测器(BSE)对本实施例所制备的[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]Si2涂层的横截面进行成像分析，结果如图2所示，涂层厚度约为500μm，组织较致密，与基体合金界面为冶金结合形式。
利用电子探针显微分析仪(岛津EPMA-8050G)对本实施例所制备的[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]Si2涂层进行元素面分析，结果如图3所示。
由表面XRD分析及电子探针元素面分布分析可知，该涂层主要是由(Nb-Ti-Cr)Si2和WSi2组成的[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]Si2，各元素在涂层中的分布较均匀，实际成分基本符合设计成分。
本发明的铌合金表面①[(Nb0.75Ti0.05Cr0.2)]Si2，②[(Nb0.75Ti0.05Cr0.2)0.95, W0.05]Si2，③[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]Si2涂层经1450℃氧化100h后的宏观形貌。从宏观照片来看，[(Nb0.75Ti0.05Cr0.2)]Si2涂层样品经1450℃氧化100h后表面形成了一层疏松的黄色氧化物，该氧化物容易脱落，对基体合金的保护性有限；而 [(Nb0.75Ti0.05Cr0.2)0.95,W0.05]Si2及[(Nb0.75Ti0.05Cr0.2)0.6,W0.4]Si2涂层样品氧化后形成的表面氧化膜致密、完整，能较好地保护基体合金免于氧化，且氧化100h后的单位面积增重仅分别为2.5mg/cm2和2.1mg/cm2，表现出良好的抗氧化能力。
实施例4：制备[(Nb0.75Ti0.2Cr0.05)0.85,Mo0.15]Si2涂层
(1)首先按摩尔比[(Nb0.75Ti0.2Cr0.05)0.85,Mo0.15]:Si＝1:2.01的比例，分别称取各金属单质粉末，投入混料机中充分混合18h；
(2)用混合好的多组元金属粉末将铌合金工件包埋后放在石墨坩埚中，然后将石墨坩埚置入放电等离子烧结炉中进行烧结，具体工艺参数为：升温速率为 80℃/s，压力为25MPa，经1500℃烧结8min；
(3)将烧结后的涂层试样在氩气保护气氛下进行均匀化热处理，温度为 800℃，时间为6h，得到了主要由(Nb-Ti-Cr)Si2和少量MoSi2组成的 [(Nb0.75Ti0.2Cr0.05)0.85,Mo0.15]Si2涂层，涂层组织均匀，与基体结合呈冶金形式，成分分析表明涂层中各元素成分基本符合设计成分。
实施例5：制备[(Nb0.65Ti0.05Cr0.3)0.9,Zr0.1]Si2涂层
(1)首先按摩尔比[(Nb0.65Ti0.05Cr0.3)0.9,Zr0.1]:Si＝1:2.05的比例，分别称取各金属单质粉末，投入混料机中充分混合12h；
(2)用混合好的多组元金属粉末将铌合金工件包埋后放在石墨坩埚中，然后将石墨坩埚置入放电等离子烧结炉中进行烧结，具体工艺参数为：升温速率为 50℃/s，压力为50MPa，经1450℃烧结10min；
(3)将烧结后的涂层试样在真空条件下进行均匀化热处理，温度为1000℃，时间为8h，得到了主要由(Nb-Ti-Cr)Si2和少量ZrSi2组成的[(Nb0.65Ti0.05Cr0.3)0.9, Zr0.1]Si2涂层，涂层组织均匀，与基体结合呈冶金形式，成分分析表明涂层中各元素成分基本符合设计成分。
实施例6：制备[(Nb0.7Ti0.1Cr0.2)0.95,Hf0.05]Si2涂层
(1)首先按摩尔比[(Nb0.7Ti0.1Cr0.2)0.95,Hf0.05]:Si＝1:2.1的比例，分别称取各金属单质粉末，投入混料机中充分混合18h；
(2)用混合好的多组元金属粉末将铌合金工件包埋后放在石墨坩埚中，然后将石墨坩埚置入放电等离子烧结炉中进行烧结，具体工艺参数为：升温速率为 100℃/s，压力为40MPa，经1500℃烧结10min；
(3)将烧结后的涂层试样在氩气保护气氛下进行均匀化热处理，温度为 1200℃，时间为5h，得到了主要由(Nb-Ti-Cr)Si2和少量HfSi2及单质Si组成的[(Nb0.7Ti0.1Cr0.2)0.95,Hf0.05]Si2涂层，涂层组织均匀，与基体结合呈冶金形式，成分分析表明涂层中各元素成分基本符合设计成分。
实施例7：制备[(Nb0.65Ti0.2Cr0.15)0.7,Ta0.3]Si2涂层
(1)首先按摩尔比[(Nb0.65Ti0.2Cr0.15)0.7,Ta0.3]:Si＝1:2.1的比例，分别称取各金属单质粉末，投入混料机中充分混合24h；
(2)用混合好的多组元金属粉末将铌合金工件包埋后放在石墨坩埚中，然后将石墨坩埚置入放电等离子烧结炉中进行烧结，具体工艺参数为：升温速率为 50℃/s，压力为40MPa，经1450℃烧结15min；
(3)将烧结后的涂层试样在氩气保护气氛下进行均匀化热处理，温度为 1250℃，时间为2h，得到了主要由(Nb-Ti-Cr)Si2，TaSi2和少量单质Si组成的[(Nb0.65Ti0.2Cr0.15)0.7,Ta0.3]Si2涂层，涂层组织均匀，与基体结合呈冶金形式，成分分析表明涂层中各元素成分基本符合设计成分。

Claims (4)

1.一种铌合金表面耐高温多组元硅化物涂层，其特征在于，该涂层的组成相为[(Nb 1-x- y Ti x Cr y ) 1-z ，R z ]Si2，R为金属元素Mo, W, Zr, Hf, Ta中的一种或多种，其中x, y, z分别表示对应元素的摩尔数，且0.05≤x≤0.2，0.05≤y≤0.3，0.05≤z≤0.4；该涂层通过以下步骤制备得到：
（1）首先按摩尔比[(Nb 1-x-y Ti x Cr y ) 1-z ，R z ]：Si=1：2.01~2.1分别称取各金属单质粉末和硅单质粉末，投入混料机中充分混合12~24h；R为金属元素Mo, W, Zr, Hf, Ta中的一种或多种，其中x, y, z分别表示对应元素的摩尔数，且0.05≤x≤0.2， 0.05≤y≤0.3，0.05≤z≤0.4；
（2）用混合好的多组元金属粉末将铌合金工件包埋后放在石墨坩埚中，然后将石墨坩埚置入放电等离子烧结炉中进行烧结；
（3）将烧结后的涂层试样在真空或保护气氛下进行均匀化热处理，即可形成耐高温多组元硅化物涂层。
2.根据权利要求1所述的一种铌合金表面耐高温多组元硅化物涂层，其特征在于，步骤（2）中，所述烧结的具体参数为：升温速率为50~100℃/s，压力为25~50MPa，烧结温度为1250~1500℃，烧结时间为5~20min。
3.根据权利要求1或2所述的一种铌合金表面耐高温多组元硅化物涂层，其特征在于，步骤（3）中，所述热处理的具体参数为：温度为800~1250℃，时间为2~8h。
4.根据权利要求1或2所述的一种铌合金表面耐高温多组元硅化物涂层，其特征在于，所述金属单质粉末和硅单质粉末的纯度 ≥ 99.0%，粒度 ≤ 50μm。
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