CN109415275B - 陶瓷基复合材料的制造方法 - Google Patents

陶瓷基复合材料的制造方法 Download PDF

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CN109415275B
CN109415275B CN201780040385.6A CN201780040385A CN109415275B CN 109415275 B CN109415275 B CN 109415275B CN 201780040385 A CN201780040385 A CN 201780040385A CN 109415275 B CN109415275 B CN 109415275B
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ceramic
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powder
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金泽真吾
佐藤彰洋
沟上阳介
中村武志
垣内良二
长见祐弥
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Abstract

一种陶瓷基复合材料的制造方法，包括：使包含含有SiC的增强纤维和粉末中的任一种以上的陶瓷成型体成型，使含有Y的三元以上的多元系Si合金铸块附着于陶瓷成型体，加热至合金熔融的温度，使合金浸渍在陶瓷成型体中。

Description

陶瓷基复合材料的制造方法
技术领域
本公开涉及用于飞机用喷气式发动机等必需高温强度的机器的陶瓷基复合材料的制造方法。
背景技术
陶瓷具有极高的耐热性，但另一方面，多数陶瓷有脆的缺点。为了克服脆性，以往，进行了使陶瓷纤维与由其他陶瓷、金属形成的母材(基质)复合化的尝试。
为了复合化，提出了气相浸渍(CVI)、液相浸渍(例如聚合物熔融浸渍热分解(PIP))、固相浸渍(SPI)、熔融金属浸渍(MI)等方法。例如，根据MI法，使成为基质的原料的金属铸块附着于由碳化硅(SiC)等增强纤维形成的织物，使其熔融，从而与增强纤维复合化。
还提出了将这些方法组合的技术。专利文献1公开了相关技术。
现有技术文献
专利文献
专利文献1：日本特开2013-147366号公报
发明内容
MI法必然使增强纤维暴露于高温，因而有时会引起增强纤维不可忽视的劣化。例如，考虑将硅(Si)熔融浸渍，Si的熔点为1414℃，因而为了熔融浸渍，必须使增强纤维暴露于至少比该熔点高的高温。此外，这样的高温对反应炉也产生了相当大的负担。
以下公开的制造方法是鉴于上述问题而创造的。根据一个方面，陶瓷基复合材料的制造方法包括：使包含含有SiC的增强纤维和粉末中的任一种以上的陶瓷成型体成型；使含有Y的三元以上的多元系Si合金铸块附着于前述陶瓷成型体；加热至前述合金熔融的温度，使前述合金浸渍在前述陶瓷成型体中。
优选前述Si合金含有2at％以上30at％以下的Y以及2at％以上15at％以下的Ti或Hf。或者，前述Si合金包含2at％以上18at％以下的Y、2at％以上15at％以下的Ti或Hf以及不可避免的杂质和作为余量的Si。或者，优选前述Si合金中，Y的含量在2at％以上6at％以下的范围。此外优选前述Si合金中，Ti的含量在6at％以上10at％以下的范围。更优选制造方法进一步包括在附着前述铸块以前，使由SiC和C中的任一种以上形成的粉末浸渍在前述陶瓷成型体中。
发明效果
能够防止熔融工序中的高温导致的增强纤维的劣化。
附图说明
图1为概括性说明根据一个实施方式的陶瓷基复合材料的制造方法的流程图。
图2A为示意性显示熔融工序中使铸块附着于成型体的形态的截面图。
图2B为示意性显示熔融工序中铸块浸渍于成型体的过程的截面图。
图2C为示意性显示熔融工序中铸块浸渍于成型体结束时的形态的截面图。
图3为显示铸块的组成对浸渍率的影响的图表。
图4为显示铸块的钇浓度对耐氧化性的影响的图表。
图5为显示铸块的钛浓度对杨氏模量的影响的图表。
具体实施方式
以下，参照所附附图，对几个实施方式进行说明。
根据一个实施方式的陶瓷基复合材料的合适的用途，是像飞机用喷气式发动机的构成部件那样暴露于高温环境的机械部件，可以例示涡轮叶片、燃烧器、加力燃烧器等。当然，也可以适用于其他用途。
根据一个实施方式的陶瓷基复合材料大体上是，由像碳化硅(SiC)那样的陶瓷形成的增强纤维和粉末中的任一种以上形成成型体，通过在该成型体中熔融浸渍三元系或三元以上的多元系硅(Si)合金来形成。浸渍Si合金而生成的基质使SiC织物和/或粉末彼此相互结合，从而形成陶瓷基复合材料。此外，形成基质时，可以进一步组合气相浸渍(CVI)、液相浸渍(例如聚合物熔融浸渍热分解(PIP))、固相浸渍(SPI)中的任一种以上。
主要参照图1对陶瓷基复合材料的制造方法进行说明。首先，使陶瓷成型体成型为根据用途确定的规定形状(步骤S1)。由陶瓷形成的增强纤维可以保持纤维束的状态，也可以预先织成织物，此外还可以预先在其中浸渍了陶瓷粉末。作为陶瓷，例如可以例示SiC，或者，也可以是碳(C)、氮化硼(BN)或其他合适的陶瓷，此外也可以是它们的混合物。进一步，增强纤维与浸渍的粉末可以为同种陶瓷，也可以为不同种陶瓷。此外，该织物可以是二维织造而成，也可以是三维织物。
可以对增强纤维实施涂布。作为涂层，可以例示C、BN，但不一定限定于此。作为涂布的方法，可以利用气相法、浸渍法等公知的任何方法。此外，涂布可以在成型工序之前实施，也可以在成型工序之后实施。表面涂布会防止龟裂从基质向纤维传播，使韧性增大。
在用专门的陶瓷粉末制造陶瓷成型体的情况下，例如可以通过在将粉末加压成型后预烧而制造。
陶瓷成型体在由含有陶瓷粉末的增强纤维形成的情况下以及由专门的陶瓷粉末形成的情况下，均可以含有与这些陶瓷粉末不同种类的第2陶瓷粉末。例如可以进一步含有C粉末。C粉末与熔融的Si合金反应，生成SiC，这有助于陶瓷基复合材料强度的改善。
在陶瓷成型体的成型同时，制成用来熔融浸渍的合金铸块(步骤S3)。合金例如像钇(Y)-钛(Ti)-Si合金那样为三元系Si合金。如上所述，也可以是三元以上的多元系Si合金。
这些Si合金中，由于合金化而发生熔点下降，因而其熔点比纯Si的熔点(1414℃)低。另一方面，多数增强纤维在超过1400℃的高温下迅速劣化，劣化是符合阿伦尼乌斯方程的化学反应，是对温度敏感的现象，因而在1400℃附近，即使温度稍有降低，劣化速度也会显著变慢。即，合金化导致的该熔点降低能够用于抑制增强纤维的劣化。
与任何元素单独添加于Si相比，复合添加是更优选的。例如单独添加Ti的情况下，添加相对于Si为15at％的Ti，最终熔点不过是降低至1330℃。该组成是Si-Ti系中的所谓共晶组成，1330℃是该体系中最低的熔点，即所谓共晶点。如果在浸渍的过程中，Si由于碳化反应而被消耗，熔融合金中的组成比共晶组成向富Ti侧偏移，则熔点会上升，阻碍在此基础上的浸渍的进行。Y与Ti复合添加时，例如即使添加2at％左右，也能够防止该现象，能够期待充分的浸渍。如果Y添加过多，则熔点反而上升，因而优选为30at％以下，或者，为作为共晶组成的18at％或其以下。
另一方面，根据本发明人等的研究，Y的添加对于陶瓷基复合材料的耐氧化性似乎是不利的，添加Ti或Hf对提高耐氧化性而言是优选的。因此，从提高浸渍性和提高耐氧化性两者方面来看，将较少量的Y与Ti或Hf一起添加在Si中是合理的。如上所述，铸块可以优选利用含有Y的三元以上的多元系Si合金，例如含有Y和Ti的多元系Si合金。
即，步骤S3中，优选制成三元以上的多元系Si合金的铸块。对于铸块，考虑所附着的陶瓷成型体的形状而成型为合适的形状和尺寸。参照图2A，使制成的铸块3附着于陶瓷成型体1，插入反应炉中。优选炉抽气至真空，或者用氩等非活性气体进行吹扫。
再次参考图1，为了使铸块3熔融浸渍于陶瓷成型体1(步骤S5)，在炉中，加热陶瓷成型体1和铸块3。
加热的温度曲线例如如下。升温速度例如为10℃/min，其可以适当选择。升温的过程中，可以包括暂时停止升温而保温的阶段。此外还可以在达到加热的最高温度Tmax前将升温速度抑制至例如5℃/min。
加热的最高温度Tmax应当根据三元以上的多元系Si合金的组成，选择作为足以引起其熔融的高温的、防止增强纤维的劣化的合适的温度。Tmax例如可以定为1395℃，或者以熔点+20℃的方式相对于熔点适当确定。
如果达到熔点，则如图2B中示意性显示的那样，铸块3开始熔融，如符号5所示那样逐渐浸渍于陶瓷成型体1。该过程在较短时间内完成，如图2C中示意性显示的那样，得到合金浸渍于其整体的陶瓷基复合材料10。
为了引起充分的浸渍，在最高温度保持的时间长较好。但如果过长，则增强纤维的劣化进行，因而保持时间应当适当缩短。保持时间可以考虑这些因素而确定。
然后，缓慢冷却后，陶瓷基复合材料10从炉中取出(步骤S7)。为了避免急剧的热休克，可以设定适当的冷却速度。
得到的陶瓷基复合材料通常进行精加工而制成最终制品。出于防腐蚀、提高耐热性或者防止外来物质的附着等目的，可以在精加工后进一步实施涂布。
为了验证本实施方式带来的效果，实施了几项试验。
分别准备通过固相浸渍法在由SiC纤维形成的织物中浸渍SiC粉末而得的几个陶瓷成型体，此外分别准备表1列出的组成的铸块。
[表1]
表1供试验的铸块
Figure BDA0001925409860000051
将各铸块分别与上述陶瓷成型体组合，在真空中加热，熔融浸渍。温度曲线如上所述，除了试样D以外，Tmax均为1395℃，试样D中为1250℃。
分别将得到的陶瓷基复合材料切断，对截面研磨，利用扫描型电子显微镜(SEM)进行截面观察。
试样B(Si-15at％Ti)和试样E(Si-9.2at％Hf)中，截面中明显确认到空隙，很明显，Si合金的浸渍不充分。而试样C(Si-10at％Y)中未确认到明显的空隙。此外试样F或O(三元系合金)中也未确认到明显的空隙。即，很明显，Y-Si合金或含有Y的三元系Si合金浸渍性优异。
通过图像解析识别截面中的空隙部分，测量其面积。将浸渍率设为(总面积-空隙的面积)/总面积×100％，关于各试样，算出浸渍率。将结果示于图3。
确认到试样F或O(三元系Si合金)和试样C的浸渍率均比试样B、E(二元系Si合金)高。如上所述，可以确认，通过复合添加，不仅熔点下降，而且浸渍性也提高。至少与Ti复合添加的条件下，添加2at％以上的Y对抑制陶瓷基复合材料的缺陷是有效的。
利用EPMA进行截面中的元素分析。探头直径设为
Figure BDA0001925409860000062
分别随机测定25个点，将除了1个点以外的24个点的组成平均，示于表2。
[表2]
表2利用EPMA得到的组成分析结果
Figure BDA0001925409860000061
进一步对各试样实施在1100℃的大气中暴露100小时的试验，测定氧化导致的减薄。用减薄除以暴露时间，算出氧化速度，示于图4。
图4中，横轴设为Y浓度，因而该图显示的是Y浓度对耐氧化性的影响。确认到，氧化速度相对于Y浓度具有正的斜率。即，至少在与Ti复合添加的条件下，Y的添加对陶瓷基复合材料的耐氧化性是不利的，特别优选Y的添加为6at％以下。
此外对各试样进行研磨，制作50(长度)×10(宽度)×2(厚度)mm的长方形试验片，分别基于共振法测定杨氏模量。将结果示于图5。
图5中，横轴设为Ti浓度，因而该图显示的是Ti浓度对杨氏模量的影响。确认到，杨氏模量相对于Ti浓度具有正的斜率。即，至少在与Y复合添加的条件下，Ti的添加对杨氏模量的增大是有利的。尤其是添加至6at％时，添加的效果显著，在该值以上，杨氏模量的增大缓慢。即，从增大杨氏模量的观点出发，Ti的添加优选为6at％以上，考虑到效果的饱和，优选为10at％以下。
虽然说明了几个实施方式，但是，基于上述公开内容，具有本技术领域通常技术的人员是可以对实施方式进行修正或变形的。
产业可利用性
提供防止熔融工序中的高温导致的增强纤维的劣化的陶瓷基复合材料的制造方法。

Claims (5)

1.一种制造方法，是陶瓷基复合材料的制造方法，包括：
使包含含有SiC的增强纤维和粉末中的任一种以上的陶瓷成型体成型，
使含有Y的三元以上的多元系Si合金铸块附着于所述陶瓷成型体，
加热至所述合金熔融的温度，使所述合金浸渍在所述陶瓷成型体中，
并且，所述Si合金含有2at％以上30at％以下的Y以及2at％以上15at％以下的Ti或Hf。
2.根据权利要求1的制造方法，所述Si合金包含：
2at％以上18at％以下的Y，和
不可避免的杂质和作为余量的Si。
3.根据权利要求1的制造方法，所述Si合金中，Y的含量在2at％以上6at％以下的范围。
4.根据权利要求1至3中任一项的制造方法，所述Si合金中，Ti的含量在6at％以上10at％以下的范围。
5.根据权利要求1的制造方法，进一步包括在附着所述铸块之前，使由SiC和C中的任一种以上形成的粉末浸渍在所述陶瓷成型体中。
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