CN108698940A - 由化学反应生产陶瓷的方法 - Google Patents

由化学反应生产陶瓷的方法 Download PDF

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Publication number
CN108698940A
CN108698940A CN201680082251.6A CN201680082251A CN108698940A CN 108698940 A CN108698940 A CN 108698940A CN 201680082251 A CN201680082251 A CN 201680082251A CN 108698940 A CN108698940 A CN 108698940A
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China
Prior art keywords
powder
chemical reaction
ceramic
amount
silicon
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Inventor
L·马勒
J·罗杰
Y·勒培提克普斯
B·瑞尼尔
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Centre National de la Recherche Scientifique CNRS
Safran Ceramics SA
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Centre National de la Recherche Scientifique CNRS
Safran Ceramics SA
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Abstract

本发明涉及用于生产陶瓷材料的方法，所述方法包括以下步骤：通过实施至少在金属间化合物的第一粉末和反应性气相之间第一化学反应来形成陶瓷材料，在第一化学反应期间在第一粉末的颗粒周围存在液相，所述液相通过使得第二粉末熔融、或在第一粉末的至少一种元素和第二粉末的至少一种金属元素之间进行第二化学反应由金属化合物的第二粉末来获得，工作温度足够低，以防止第一粉末在陶瓷材料形成过程中熔化。

Description

由化学反应生产陶瓷的方法
发明背景
本发明涉及制造陶瓷材料的方法以及可以通过实施该方法获得的产品。
已知化学气相渗透(CVI)方法用于使得纤维预制件致密化。此类方法包括将含有形成所述材料的所有元素的气体混合物渗透进多孔预成形件中以将其致密化。例如，申请FR 2 784 695中描述了该类型的方法。化学气相渗透源自化学气相沉积(CVD)技术，并且具有随时间恒定的沉积速率。这是一种为材料提供良好性能的方法。然而，为了获得均匀的陶瓷基质复合物(CMC)，同时避免在预制件周围过早堵塞，必须在低压下和相对低的温度(≤1100℃)下操作，以降低生长速率。这导致了CMC部件的制造持续时间长，并使得该方法昂贵。可能需要加工以重新打开周边的孔，从而使气体进入芯。然而，一旦孔隙率达到接10％至15％的值，由于大孔的存在，基质致密化可能停止。
浆料或陶瓷或溶胶-凝胶技术也是已知的，其包括用浆料或溶胶(亚微米尺寸的陶瓷微粒、烧结添加剂和液体溶剂的混合物)浸渍纤维预制件，然后整个进行干燥并在1600℃至1800℃的压力下进行烧结。例如，该方法描述于EP 0 675 091以及J.Magnant,L.Maillé,R.Pailler,J-C.Ichard,A.Guette,F.Rebillat和E.Philippe的标题为“用于复合材料的碳纤维/反应-粘结碳化物基质——制造和表征(Carbon fiber/reaction-bonded carbidematrix for composite materials-Manufacture and characterization)”的出版物，其公开于J.Europ.Ceram.Soc.32(16)2012，第4497-4505页。然而，制备碳干凝胶可能涉及使用归类为CMR(致癌、致突变、或对于生殖有毒性)的物质，这可能使工业生产变得困难。
各种已知技术可以独立使用，或者它们可以彼此组合以形成混合方法。下面描述混合方法的各种示例。
已经知道浆料技术(不含烧结添加剂)与气态技术相结合的浆料和CVI混合方法。在用浆料浸渍纤维预制件之后，基质可以随后通过使用绿色复合材料通过常规CVI进行致密化。然而，聚集的(亚)微米粉末的高密实度构成了对于良好渗透阻碍。因为材料周边处的孔过早闭合，材料的芯致密化不良。反应性物质难以渗透到小孔中，并且它们的浓度从周边到芯下降非常快速，从而大大减慢并且随后阻止了固结层的生长。然而，Tang等人(S.F.Tang、J.Y.Deng、S.J.Wang、W.C.Liu和K.Yang的《超高温陶瓷复合材料的烧蚀行为(Ablation behaviors of ultra-high temperature ceramic composites)》，《材料科学与工程(Materials Science and Engineering)》A 465(2007)，第1-7页)由通过热解碳CVI固结的ZrB2、SiC、HfC和TaC的微米粉末的压坯制备复合材料。在该情况下，连续基质相由热解碳制成。通过用脉冲CVI代替传统CVI，可以将微米粉末(4微米(μm)至5μm)固结，形成毫米厚度的生坯(N.K.Sugiyama和Y.Ohsawa“通过使用脉冲CVI技术渗透BN来固结Si3N4粉末-预制件”，《材料与科学通信杂志(Journal of Materials and Science Letters)》7(1988)，第1221-1224页)。吹扫和填充生坯可以周期性地降低芯和周边之间气态物质的自然浓度梯度。但是，尚未报道亚微米粉末的可行性，并且该方法似乎难以工业化。
预陶瓷浆料和树脂混合方法可以由经浸渍的粉末和预陶瓷树脂制备基质(PeterGreil，《聚合物衍生陶瓷的净形制造(Net shaped manufacturing of polymer derivedceramics)》，J.Europ.Ceram.Soc.18 1998，第1905-1914页)。粉末体积的增加可以部分补偿热解过程中树脂体积的收缩。
近来已开展工作(Matrices nanostructuréesélaborées par voie liquide:application aux compositesàmatrice céramique[由液体技术制备的纳米结构基质：应用于陶瓷基质复合物(Nanostructured matrices prepared by a liquid technique:application to ceramic matrix composites)]，论文4323UniversitéBordeaux 1,2011，和L.Maillé,M.A.Dourges,S.Le Ber,P.Weisbecker,F.Teyssandier,Y.Le Petitcorps,R.Pailler的“TiSi2粉末的氮化过程研究(Study of the nitridation process ofTiSi2powder)”，应用表面科学(Applied Surface Science)260(2012)，第29-31页)，用于通过使在预制件内的经浸渍的粉末与气体反应通过体积膨胀来制备基质。迄今为止研究过的体系是在常压下用氮分子来氮化TiSi2粉末，导致最大体积增量之一，为约60％。在该工作中，目标是通过使用在1100℃以上不稳定的纤维制备低成本基质，并且在氮化期间使用低于或等于1100℃的处理温度。该工作显示出在该条件下，粉末的氮化相对缓慢且不完全。该问题涉及氮化硅，因为转化率低。
因此，需要具有以低成本制造陶瓷材料的新方法，其适用于以工业规模使用，并且其中可以使用相对低的处理温度使用。
特别是，需要具有使得纤维预制件致密化的新方法，其可以在工业规模上使用并且具有相对低的成本和工作温度。
还需要具有以低成本制造陶瓷材料的新方法，其中所使用的化学反应是彻底的。
还需要具有制造陶瓷材料的新方法，其中所获得的材料基本上不含残留的游离硅。
还需要具有新颖的陶瓷材料，其具有非常令人满意的机械性能和均匀的微观结构。
发明目的和概述
为此，在第一方面中，本发明提供了制造陶瓷材料的方法，所述方法包括以下步骤：
-通过实施至少在金属二硅化物的第一粉末和反应性气相之间第一化学反应来形成陶瓷材料，在第一化学反应期间在第一粉末的颗粒周围存在由第二粉末获得的液相，在陶瓷材料形成过程中施加工作温度，所述温度足够低，以避免第一粉末熔化，并且满足以下两个特征中的一个：
-第二粉末是镍粉末，并且液相由于第一粉末的至少一种元素和第二粉末的镍之间的第二化学反应而获得；或者
-第二粉末是铝和硅的合金粉末，并且液相是通过所述铝和硅的合金熔化而获得的。
金属二硅化物是具有化学式MSi2的化合物，其中，M是金属元素，例如，M可以是过渡金属。例如，所述第一粉末可以是TiSi2粉末、CrSi2粉末、ZrSi2粉末、或VSi2粉末。
在本发明中，第二粉末促进反应性气相和第一粉末之间的反应。在第一化学反应期间，第一粉末通过形成一个或多个新的相(氮化物、氧化物、碳化物、……)而体积膨胀，由此产生陶瓷材料。使用根据本发明的第二粉末用于获得第一化学反应期间的液相有利地通过促进试剂扩散更大并因此促进反应产物的快速晶体生长来加速第一化学反应的速率。尽管使用相对低的工作温度，但使用这种第二粉末构成了用于加速第一化学反应的策略。这有利地提供了一种制造陶瓷材料的方法，该方法具有低成本的性能，同时能够相对快速地进行化学反应。此外，本发明有利地用于形成一种或多种热稳定相，并且获得完全的化学反应。而且，所形成的陶瓷材料不需要具有分散在其中的任意微粒增强物。
当液相通过熔化铝和硅的合金形成时，选择所述铝和硅的合金，使得熔融温度足够低，从而在工作温度下形成液相。为此目的，一旦选择了第一粉末和反应性气相的工作温度和化学性质，只要选择熔化温度足够低以在第一化学反应过程中获得液相的铝和硅的合金就足够了。例如，这样的实施方式对应于在下文中详述的ZrSi2和AS13合金体系。当液相通过熔化铝和硅的合金形成时，所述合金可在用反应性气相处理第一粉末期间或在第一化学反应开始之前的预加热处理期间熔化。
当由于第二化学反应形成液相时，第一粉末和第二镍粉末之间可以直接发生化学反应。在该情况下，在第一化学反应之前获得含有第一粉末和第二镍粉末的混合物。在一变体中，第二镍粉末首先熔化以形成熔融的镍，然后，第一粉末通过熔融的镍浸渍，以进行第二化学反应并形成液相。
当由于第二化学反应形成液相时，液相至少包括第一粉末中的至少一种元素和镍。在该情况下，由于至少第一粉末的硅和第二粉末的镍之间的化学反应获得液相。在该情况下，液相可以至少包含镍和硅。液相还可以由于第一粉末的硅、第一粉末的金属元素M和第二粉末的镍之间的化学反应而获得。在该情况下，液相可以至少包含镍、金属元素M和硅。例如，对于与第一粉末TiSi2和第二镍粉末相对应的体系，液相至少包含硅、镍和钛。
当由于第二化学反应形成液相时，构成第二粉末的镍与第一粉末的至少一种其它元素结合时，其形成了具有相图的体系，所述相图显示出在工作温度下形成液相。例如，对于与第一粉末TiSi2和第二镍粉末相对应的体系，Ni-Si体系的二相图显示出在956℃形成的液相(参见图1)，并且在1100℃下的Ni-Ti-Si体系的三相图也显示出形成液相的可能性(参见图2)。因此，例如，在1100℃的工作温度下，可以使用第二镍粉末和第一粉末TiSi2并由此在第一化学反应期间获得液相的存在。因此，相图使得所关心的各体系可以识别当由于第二化学反应形成液相时获得液相所需要的成分的相对含量。
当由于第二化学反应形成液相时，当第二镍粉末与硅结合时，其可以形成具可以形成一个体系，其相图显示出在工作温度下的液相形成。
当由于第二化学反应形成液相时，当第二镍粉末与第一粉末的金属元素结合时，其可以形成具可以形成一个体系，其相图显示出在工作温度下的液相形成。
优选地，所述第一粉末可以是TiSi2粉末，并且第二粉末可以是镍粉末。在该体系中，由于进行第二化学反应获得液相。
该体系是特别有利的，因为如上所述在Ni-Si体系内存在低熔点。此外，该体系可以有利地使得可以获得总的转化率和具有令人满意的机械性能以及均匀的微结构的陶瓷材料。此外，通过使用第二镍粉末有利地促进第一粉末和反应性气相的反应，其用于在颗粒周围获得富硅液相，从而有助于反应物质的扩散。
例如，在该体系中采用的反应性气相可以包含元素N，例如，可以包含N2。这获得了基本包含(即，含有超过90重量％)TiN、Si3N4、和Ni4Ti4Si7的材料。由于第一化学反应的体积上的增加可以大于或等于40％，例如，可以为约50％。此外，形成Ni4Ti4Si7化合物是有利的，因为该化合物是难熔化合物和抗氧化剂。
在一实施方式中，在第一化学反应开始前，第一粉末材料的量可以大于第二粉末材料的量。
术语“材料的量”用于表示以摩尔(mol)测定带的材料的量。
该特征意味着在第一化学反应开始之前，第一粉末的原子分数大于第二粉的原子分数。
在第一化学反应开始前，可以采用如下比率：
-(第一粉末材料的量)除以(第一粉末材料的量加上第二粉末材料的量)的比率大于82.5％且小于92.5％；和
-(第二粉末材料的量)除以(第一粉末材料的量加上第二粉末材料的量)的比率大于7.5％且小于17.5％。
在第一化学反应开始前，(第一粉末材料的量)除以(第一粉末材料的量加上第二粉末材料的量)的比率可以在范围82.5％至92.5％之间。
在第一化学反应开始前，(第二粉末材料的量)除以(第一粉末材料的量加上第二粉末材料的量)的比率可以在范围10％至15％之间。
涉及所用第一和第二粉末的量的该比例可能是有效的，特别是当第一粉末是TiSi2粉末并且第二粉末是镍粉末时尤为如此。
在一变体中，所述第一粉末可以是CrSi2粉末，并且第二粉末可以是镍粉末。在一变体中，所述第一粉末可以是VSi2粉末，并且第二粉末可以是镍粉末。在这两种体系中，由于进行第二化学反应而获得液相。
在这后两个体系中使用的反应性气相可以例如包含元素N或元素C，例如，气相可以包括N2或CH4。
在一实施方式中，第二粉末可以是AlSi13合金粉末(铝和硅的合金，其基本具有13重量％的硅)。
优选地，第一粉末可以是ZrSi2粉末，第二粉末可以是铝和硅的合金粉末，并且在这种情况下，第二粉末可以是例如AS13合金(AlSi13)的粉末。
该体系有利地用于获得总的转化率和具有令人满意的机械性能以及均匀的微结构的陶瓷材料。此外，通过使用第二粉末AS13合金有利地促进第一粉末和反应性气相的反应，其用于在颗粒周围获得液相，从而有助于反应物质的扩散。
如上所述，当第一粉末是ZrSi2粉末并且第二粉末是AS13合金粉末时，液相通过使得AS13合金熔化形成。AS13合金具有577℃的熔点。
例如，在该体系中使用的反应性气相可以包含元素N，例如，可以包含N2。
在一变体中，所述第一粉末可以是VSi2粉末，并且第二粉末可以是AS13合金粉末。在该情况下，液相也可以通过使得AS13合金熔化形成。
在该体系中使用的反应性气相可以例如包含元素N或元素C，例如，气相可能包括N2或CH4。
如上所述，反应性气相可以包含元素N或元素C。当气相包含元素N时，第一化学反应是氮化反应。当气相包含元素C时，第一化学反应是碳化反应。在一个实施方式中，反应性气相可以包含以下气体中的至少一种：NH3、N2、O2、气态烃(例如，CH4)、或四甲基硅烷(Si(CH3)4)。气态烃和四甲基硅烷可以用于进行碳化。
有利的是形成的陶瓷材料可以具有小于或等于1％的残留游离硅重量含量。
该1％阈值对应于一特定阈值，低于该阈值则不能通过X射线衍射(XRD)在陶瓷材料中检测到残留的游离硅。
在一些实施方式中，工作温度可以低于或等于1150℃，或者实际上为1100℃。使用该温度值可能是有利的，例如，当希望通过实施本发明的方法形成陶瓷基质并且纤维增强材料包括Si-C-O纤维(纤维)时尤为如此，其中，该温度温度避免使得这些纤维降解。然而，本发明并不限于用该工作温度值实施。
在一实施方式中，第一化学反应可以在范围3毫巴(mbar)至10巴的压力下实施。该压力可以例如在3毫巴至常压(1.01325巴)范围内，或者在一变体中，该压力可以在常压至10巴的范围内。
在一实施方式中，特别是当希望通过实施本发明的方法形成陶瓷基质时，所用的第一和第二粉末中各粉末的颗粒的平均粒度可以小于或等于1μm。
除非明确相反指出，术语“平均粒度”用于表示半数统计学粒度分布所给出的尺寸，称为D50。
本发明还提供了一种制造陶瓷基质复合材料部件的方法，所述方法包括以下步骤：
-在纤维预制件的孔中形成陶瓷基质，所述陶瓷基质通过实施如上所述方法形成。然后，由于第一化学反应形成陶瓷基质。
在该情况下，实施本发明是特别有利的，因为这使得可以在相对低的温度(例如，低于或等于1100℃)下制备陶瓷基质，并因此可以获得满足以下条件的方法：不损害纤维增强物的纤维也不损害界面涂层(如果其存在)，同时还通过进行膨胀的化学反应填充了所述纤维增强物的孔。因此可能有利地获得具有非常低孔隙率的陶瓷基质复合材料。此外，当实施本发明以形成陶瓷基质时，其有利地用于通过实施相对低成本的方法制备致密且均匀的基质，例如，由氮化物、碳化物、硼化物、或氧化物制成所述基质。
在一实施方式中，纤维预制件可以包括多种陶瓷纤维和/或碳纤维。
陶瓷纤维可以包括氮化物型纤维、碳化物型纤维(例如，碳化硅纤维)、氧化物型纤维、或这些纤维的混合物。例如，碳化硅纤维可以包含氧，并且是Si-C-O纤维。
在一实施方式中，纤维预制件的纤维可以用界面涂层涂覆。
界面涂层可以包括如下物质、并且特别是由如下物质组成：热解碳(PyC)、BC或BN。
但是，本发明不限于在纤维预制件的孔中形成陶瓷基质。
具体来说，本发明还提供质一种制造用陶瓷材料涂覆其表面的部件的方法，所述方法包括如下步骤：通过实施如上所述方法在部件表面上形成所述涂层。在该情况下，涂层由于第一化学反应而形成。
在该情况下，所述部件可由复合材料制成，例如由陶瓷基质复合材料制成。
以此方式获得的涂层可以形成用于例如保护部件免于氧化的环境屏障层。涂层也可以形成热屏障层或使得下面部件表面平滑的光滑化涂层。
本发明还提供了一种制造陶瓷材料块的方法，所述方法包括如下步骤：通过实施如上所述的方法形成所述块。在该情况下，块由第一化学反应而形成。以此方式形成的块可以是任意形状的。
本发明还提供一种制造涡轮机的方法，所述方法包括如下步骤：至少通过实施如上所述方法制造涡轮机元件，随后，将由此制造的元件与一个或多个其它元件组装以获得涡轮机。
该涡轮机可以形成航空发动机的整体部分。例如，上述涡轮机元件可以构成涡轮机后体，例如，航空发动机后体。
本发明还提供了一种陶瓷材料，其基本包含TiN、Si3N4和Ni4Ti4Si7，并且具有小于或等于1％的残余游离硅重量含量。
该材料可以通过实施如上所述方法获得。
本发明还提供一种陶瓷基质复合材料部件，其包含：
-纤维增强物；和
-存在于纤维增强物孔中的基质，所述基质包含如上所述的陶瓷材料。
本发明还提供一种涡轮机，其包含该陶瓷材料以及/或者该陶瓷基质复合物部件。
本发明还提供一种航空发动机，其包含该陶瓷材料以及/或者该陶瓷基质复合物部件。
附图说明
通过参照附图的下文描述，本发明的其它特征和优势将变得明显，其中：
-图1是Ni-Si体系的二相图；
-图2是Ni-Si-Ti体系的在1100℃下的三相图；
-图3A至3C是在实施本发明方法后获得的陶瓷材料的照片；
-图4是在实施本发明方法后获得的陶瓷材料的XRD图；
-图5A至5C是照片，其显示在实施用于形成陶瓷基质的本发明方法后形成的纤维预制件的纤维、界面、和基质；
-图6A和6B是在实施本发明方法后获得的陶瓷材料的照片；
-图7A和7B是在实施非本发明方法后获得的陶瓷材料的照片；并且
-图8显示了比较本发明方法和非本发明方法获得的结果的热重分析测定。
实施例
实施例1(本发明)
图3A至3C的照片显示了通过在常压下用N2在1100℃下处理40小时(h)使得初始组成为90原子％TiSi2+10原子％Ni的样品转化后获得的材料。在处理结束时存在的相是TiN、Si3N4和Ni4Ti4Si7(参见图4)。应该观察到在处理结束时，不存在游离硅和残留的TiSi2。该反应伴有约50％的体积增加。
图5B和5C的照片具体显示了通过在纤维预制件中在常压下用N2在1100℃下处理40小时(h)使得初始组成为90原子％TiSi2+10原子％Ni的浸渍过的粉末(d50＝300纳米(nm))转化所获得的基质。所形成的相与上述相同(TiN、Si3N4和Ni4Ti4Si7)。并未在粉末和用PyC/SiC界面涂覆的Nicalon？纤维之间观察到反应。
同样，图5A还显示当在相同的操作条件下处理以PyC界面涂覆的碳纤维预制件时，粉末和界面涂覆的纤维之间不存在反应。
不存在反应性、特别是液相的反应性可归因于倾向于促进氮化的氮气气氛。由此获得部件，其中，纤维和界面都不会通过氮化而降解，同时具有致密且刚性且具有均匀微观结构的基质。还应当观察到界面和基质之间的良好粘附性。
图6A和6B是使用混合物中12.5％的镍初始原子含量，在实施本发明方法后获得的陶瓷材料的照片。获得的材料坚硬、致密且均匀，仅含有TiN，Si3N4和Ni4Ti4Si7。在该实施例中，Ni4Ti4Si7的摩尔含量等于2％，重量含量等于14％，体积含量等于10％。
下表1列出了使用TiSi2+Ni体系用N2以及各种浓度的镍在1100℃下40小时所获得的结果。
表1
这些实施方式导致反应是完全的，形成TiN+Si3N4+Ni4Ti4Si7。还应该观察到不存在杂质例如游离硅、TiSi2、或NiSi/NiSi2。
实施例2(比较例)
通过本发明方法所获得的结构与通过其中不使用第二粉末的非本发明方法获得的结果进行比较。下面描述获得复合材料并在该比较例中使用的非本发明方法：
-将TiSi2粉末浸渍到纤维预制件中；
-在氮分子条件下进行热处理：氮化反应，以形成TiN和Si3N4。
为了避免预制件的SiC纤维降解，处理温度限制在1100℃。在图7A和7B中给出了在1100℃的反应温度下进行的非本发明测试的结果。在该温度下，发明人观察到氮化反应缓慢且不完全，因为在低于或等于1100℃的温度下Si3N4的形成可能相对困难。获得的体积增量较小，并且观察到存在机械和化学上不期望的金属硅。
图8显示了在1100℃下用N2处理后获得的热重分析(TGA)测定：
-混合物(100-x)原子％TiSi2+x原子％Ni，并且x＝10、12.5和15的镍(本发明)；或者
-仅TiSi2：不使用第二粉末并且不形成液相(非本发明)。
可以看出，本发明的实施例促进了在1100℃的较低温度下使硅氮化。通过第二镍粉末的存在促进硅的氮化，这使得可以在颗粒周围获得富含硅的液相。与不含镍的体系相比，添加镍会改良并大大增加转化率。
实施例3(比较例)
在该比较例中使用的非本发明方法对应于氮化的方法，其中，在本发明中可使用的镍粉被Ni3Al粉末代替。更确切地说，该比较试验评估了添加1体积％Ni3Al的影响，如Zhang等人的出版物中所教导的(“加入1体积％Ni3Al对烧结和反应结合的Si3N4的机械性能的影响(Influence of 1 vol％Ni3Al addition on sintering and mechanicalproperties of reaction-bonded Si3N4)”，欧洲陶瓷学会期刊(Journal of the EuropeanCeramic Society)15(1995)，第1065-1070页)关于硅的氮化反应。
得到含有硅和1体积％含量的Ni3Al粉末混合物的粒料。粒料具有10毫米(mm)的直径和3mm的厚度。如上述实施例1和2所述，粒料用N2处理，同时施加1100℃的温度。在处理30小时后获得以下结果：
-残留硅的重量含量：约86.8％；
-αSi3N4的重量含量：11.6％；并且
-βSi3N4的重量含量：1.6％。
用X射线衍射确定重量含量。
可以看出，通过使用如Zhang等人的上述出版物中所教导的比例的Ni3Al，同时施加1100℃的相对低的工作温度，引起氮化反应的进步程度，所述氮化反应的进步程度显著小于根据本发明的实施例1添加镍粉末所获得的。
实施例4
ZrSi2粒料在常压氮分子和1100℃的温度下氮化40小时。
当向混合物中加入10原子％的镍时，在氮化40小时后，主相是ZrN和Si3N4。观察到少数ZrSi2、ZrSi2Si和NiZr的存在。未观察到游离硅的存在。
在未添加镍(不是本发明)的情况下，在氮化40小时后，主相是ZrN和ZrSi2。检测到Si3N4，但它构成少数相。还检测到游离硅。
因此，添加镍促进了金属二硅化物ZrSi2的氮化，即使在1100℃的较低工作温度下也是如此。
实施例5
ZrSi2粒料在常压氮分子和1100℃的温度下氮化40小时。
当向混合物中加入10原子％的AS13合金粉末时，在氮化40小时后，主相是ZrN、Si3N4和ZrSi2。观察到存在最小量的游离硅。
在未添加AS13粉末的情况下，在氮化40小时后，主相是ZrN和ZrSi2，并且观察到少量Si3N4。还检测到游离硅。
因此，向硅添加铝合金促进了金属二硅化物ZrSi2的氮化，即使在1100℃的较低工作温度下也是如此。
实施例6
VSi2粒料在常压氮分子和1100℃的温度下氮化40小时。
当向混合物中加入10原子％的AS13合金粉末时，在氮化40小时后，主相是VSi2、VN和Si3N4。观察到存在最小量的V4.75Si3N0.58。
在未添加AS13粉末的情况下，在氮化40小时后，主相是VSi2、VN、Si3N4，并且观察到少量V4.75Si3N0.58。
因此，添加铝和硅的合金促进了金属二硅化物VSi2的氮化，即使在1100℃的较低工作温度下也是如此。
实施例7
通过使用ThermoCalc软件进行模拟来评估在常压下在1100℃下用甲烷使得TiSi2+10％Ni的混合物碳化的可能性。模拟结果显示形成了SiC、Ti3SiC2和Ni4Ti4Si7，并且不存在残留硅或TiSi2。
术语"在…至…范围内"应理解为包括端值。

Claims (20)

1.一种制造陶瓷材料的方法，所述方法包括以下步骤：
-通过实施至少在金属二硅化物的第一粉末和反应性气相之间第一化学反应来形成陶瓷材料，在第一化学反应期间在第一粉末的颗粒周围存在由第二粉末获得的液相，在陶瓷材料形成过程中施加工作温度，所述温度足够低，以避免第一粉末熔化，并且满足以下两个特征中的一个：
-第二粉末是镍粉末，并且液相由于第一粉末的至少一种元素和第二粉末的镍之间的第二化学反应而获得；或者
-第二粉末是铝和硅的合金粉末，并且液相是通过所述铝和硅的合金熔化而获得的。
2.如权利要求1所述的方法，其特征在于，所述第一粉末是TiSi2粉末、CrSi2粉末、ZrSi2粉末、或VSi2粉末。
3.如权利要求2所述的方法，其特征在于，所述第一粉末是TiSi2粉末，并且第二粉末是镍粉末。
4.如权利要求2所述的方法，其特征在于，所述第一粉末是ZrSi2粉末，并且第二粉末是铝和硅的合金粉末。
5.如权利要求1、2、和4中任一项所述的方法，其特征在于，所述第二粉末是铝和硅的合金粉末AlSi13，其基本含有13重量％的硅。
6.如权利要求1至5中任一项所述的方法，其特征在于，在第一化学反应开始前，第一粉末材料的量大于第二粉末材料的量。
7.如权利要求6所述的方法，其特征在于，在第一化学反应开始前，满足以下条件：
-(第一粉末材料的量)除以(第一粉末材料的量加上第二粉末材料的量)的比率大于82.5％且小于92.5％；和
-(第二粉末材料的量)除以(第一粉末材料的量加上第二粉末材料的量)的比率大于7.5％且小于17.5％。
8.如权利要求1至7中任一项所述的方法，其特征在于，第一化学反应是氮化反应，反应性气相包含元素N。
9.如权利要求1至8中任一项所述的方法，其特征在于，第一化学反应是碳化反应，反应性气相包含元素C。
10.如权利要求1至9中任一项所述的方法，其特征在于，所述反应性气相包含以下气体中的至少一种：NH3、N2、O2、气态烃、或四甲基硅烷。
11.如权利要求1至10中任一项所述的方法，其特征在于，工作温度低于或等于1150℃。
12.如权利要求1至11中任一项所述的方法，其特征在于，第一化学反应在3毫巴至10巴的压力下进行。
13.一种通过实施如权利要求1至12中任一项所述的方法来制造陶瓷基质复合材料部件的方法，并且其包括如下步骤：通过进行所述第一化学反应在所述纤维预制件的孔中形成陶瓷基质。
14.如权利要求13所述的方法，其特征在于，纤维预制件包含Si-C-O陶瓷纤维。
15.一种通过实施如权利要求1至12中任一项所述的方法来制造陶瓷材料块的方法，并且其包括如下步骤：通过进行所述第一化学反应形成所述块。
16.一种制造部件的方法，其通过实施如权利要求1至12中任一项所述的方法用陶瓷材料涂层涂覆该部件的表面，并且其包括如下步骤：通过进行所述第一化学反应在部件表面形成所述涂层。
17.一种制造涡轮机的方法，所述方法包括如下步骤：至少通过实施如权利要求1至12中任一项所述的方法制造涡轮机元件，随后，将由此制造的元件与一个或多个其它元件组装以获得涡轮机。
18.一种陶瓷材料，基本包含TiN、Si3N4和Ni4Ti4Si7，并且具有小于或等于1％的残留游离硅重量含量。
19.一种陶瓷基质复合材料部件，其包含：
纤维增强物；和
-存在于纤维增强物孔中的基质，所述基质包含如权利要求18所述的陶瓷材料。
20.一种涡轮机，其包括如权利要求18所述的陶瓷材料和/或如权利要求19所述的部件。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3114318B1 (fr) * 2020-09-23 2023-02-24 Safran Ceram Poudre de particules pour un procédé de fabrication directe d’un matériau composite.
CN112624766B (zh) * 2020-12-29 2021-11-16 哈尔滨工业大学 一种氮化硅@碳化硅@氮化硼复合纤维毡的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1028977A (en) * 1962-02-24 1966-05-11 Eric Campbell Shears Improvements in or relating to the manufacture of silicon nitride and oxynitride
JPH05330921A (ja) * 1992-06-02 1993-12-14 Honda Motor Co Ltd 窒化ケイ素反応焼結体の製造方法
CN101096272A (zh) * 2007-06-04 2008-01-02 哈尔滨工业大学 氮化硅基复合材料燃烧合成方法
CN101326139A (zh) * 2005-12-08 2008-12-17 斯奈克玛 一种位于金属部件和碳化硅基和/或碳基陶瓷材料部件之间的装配件
CN104271894A (zh) * 2012-03-29 2015-01-07 赫拉克勒斯公司 航空器发动机艉部的部件集成
CN106116586A (zh) * 2016-06-14 2016-11-16 中南大学 一种钼合金MoSi2‑ZrO2‑Y2O3涂层及其制备方法和应用

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0520520B1 (en) 1987-04-10 1996-09-11 Hitachi, Ltd. Ceramic composite and process for production thereof
JP2587807B2 (ja) * 1993-02-22 1997-03-05 プラクスエア エス ティ テクノロジー インコーポレイテッド 炭化物皮膜の形成方法および同皮膜を有する物品
EP0675091B1 (en) 1994-03-29 1998-11-18 European Atomic Energy Community (Euratom) Composite material for sliding purposes, process for its preparation and use thereof
JP3390773B2 (ja) 1994-03-30 2003-03-31 黒崎播磨株式会社 黒鉛電極用導電性酸化防止材
US5882561A (en) 1996-11-22 1999-03-16 Drexel University Process for making a dense ceramic workpiece
FR2784695B1 (fr) 1998-10-20 2001-11-02 Snecma Densification de structures poreuses par infiltration chimique en phase vapeur
RU2239613C1 (ru) 2003-02-10 2004-11-10 Федеральное государственное унитарное предприятие "Обнинское научно-производственное предприятие "Технология" Способ получения изделий на основе нитрида кремния
JP4292255B2 (ja) * 2003-03-18 2009-07-08 独立行政法人産業技術総合研究所 α−サイアロン焼結体及びその製造方法
RU2382690C1 (ru) 2008-09-30 2010-02-27 Томский научный центр Сибирского отделения Российской академии наук (ТНЦ СО РАН) Способ получения композиционного керамического порошка на основе нитрида кремния и нитрида титана
RU2490232C1 (ru) 2012-02-17 2013-08-20 Мансур Хузиахметович Зиатдинов СПОСОБ ПОЛУЧЕНИЯ ОГНЕУПОРНОГО МАТЕРИАЛА НА ОСНОВЕ БЕТА-НИТРИДА КРЕМНИЯ β-Si3N4
FR3008968B1 (fr) 2013-07-23 2016-12-09 Herakles Procede de fabrication de pieces en materiau composite par impregnation a basse temperature de fusion

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1028977A (en) * 1962-02-24 1966-05-11 Eric Campbell Shears Improvements in or relating to the manufacture of silicon nitride and oxynitride
JPH05330921A (ja) * 1992-06-02 1993-12-14 Honda Motor Co Ltd 窒化ケイ素反応焼結体の製造方法
CN101326139A (zh) * 2005-12-08 2008-12-17 斯奈克玛 一种位于金属部件和碳化硅基和/或碳基陶瓷材料部件之间的装配件
CN101096272A (zh) * 2007-06-04 2008-01-02 哈尔滨工业大学 氮化硅基复合材料燃烧合成方法
CN104271894A (zh) * 2012-03-29 2015-01-07 赫拉克勒斯公司 航空器发动机艉部的部件集成
CN106116586A (zh) * 2016-06-14 2016-11-16 中南大学 一种钼合金MoSi2‑ZrO2‑Y2O3涂层及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIN S等: "Comparative Studies of Metal Additives on the Nitridation of Silicon", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》 *
ROGER J等: "Isothermal nitridation kinetics of TiSi2 powders", 《JOURNAL OF SOLID STATE CHEMISTRY》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627507A (zh) * 2019-09-18 2019-12-31 广东工业大学 一种低温碳化硅陶瓷及其制备方法和应用
CN110627507B (zh) * 2019-09-18 2022-02-25 广东工业大学 一种低温碳化硅陶瓷及其制备方法和应用
CN112125675A (zh) * 2020-08-14 2020-12-25 中国科学院金属研究所 一种ZrB2-SiC-VSi2超高温陶瓷复合材料及其制备方法
CN112125675B (zh) * 2020-08-14 2022-05-31 中国科学院金属研究所 一种ZrB2-SiC-VSi2超高温陶瓷复合材料及其制备方法

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