CN117881644A - 用于处理碳化硅纤维的方法 - Google Patents
用于处理碳化硅纤维的方法 Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 55
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 125
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 62
- 239000002344 surface layer Substances 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- 239000011159 matrix material Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000002787 reinforcement Effects 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 24
- 239000012530 fluid Substances 0.000 description 15
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 14
- 229910052582 BN Inorganic materials 0.000 description 9
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 229910000085 borane Inorganic materials 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009954 braiding Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical group [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011153 ceramic matrix composite Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000000626 liquid-phase infiltration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XLTGUTCKZSCTDF-UHFFFAOYSA-N CCN(CC)[Ta]=NC(C)(C)C Chemical compound CCN(CC)[Ta]=NC(C)(C)C XLTGUTCKZSCTDF-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
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- 231100000167 toxic agent Toxicity 0.000 description 1
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Abstract
本发明涉及一种用于处理至少一根碳化硅纤维(16)的方法,所述碳化硅纤维包括包含碳和/或碳氧化硅的表面层,其中所述该处理包括通过将所述纤维与处于超临界状态的氨相(22)相接触来从所述纤维至少去除表面层。
Description
技术领域
本发明涉及一种用于处理至少一根碳化硅纤维的方法,所述碳化硅纤维具有在该纤维的表面上形成涂层之前要被去除的表面层。
背景技术
陶瓷基体复合材料(“CMC材料”)具有良好的机械性能,使其适合形成结构元件并在高温下有利地保持这些性能。它们是常用的金属部件的一种受关注的替代品,因为它们可以使结构变轻。
CMC材料可以通过形成纤维预制件来生产,其形状类似于最终部件的形状,然后通过陶瓷基体进行致密化。CMC材料的功能需要对纤维和基体之间的界面键进行特定的管理,以获得最终复合材料难以损坏的性质。这种界面调制通常通过在纤维和基体之间设置中间相来实现。在热结构应用的背景下,与热解碳(PyC)相比,使用氮化硼作为中间相可能是有利的,原因在于它更有利的氧化行为。
已知,在中间相沉积步骤之前,对纤维进行表面处理以消除表面存在的非均匀性,可以显著改善最终复合材料的性能。特别是已知文件US2018194686A1。该文件公开了一种在形成中间相之前将“Hi-Nicalon S”类型的SiC纤维的表面剥离的方法。在此方法中,纤维的表面首先被氧化以形成二氧化硅表面层,然后通过包含至少氢氟酸(HF)的酸性液体介质进行处理,以去除所形成的二氧化硅层。经过这种处理后,获得具有均匀碳化硅表面的剥皮纤维,从而改善了经处理的纤维与沉积的中间相之间的结合。这种解决方案提供了令人满意的结果。然而,使用HF酸的这种方法的环境兼容性还有待提高。此外,这种方法需要执行各种纤维操作步骤:冲洗和干燥经处理的纤维,或将纤维从一个室移动到另一个室。因此,希望有一种更简单、更快地进行的处理方式。
发明内容
本发明涉及用于处理至少一根碳化硅纤维的方法,所述碳化硅纤维包含含有碳和/或碳氧化硅的表面层,其中处理包括通过在大于或等于100℃的温度和大于或等于1巴的压力下将该纤维与氨相接触来至少从该纤维上去除表面层。
据发明人所知,在文献中尚未已知或建议使用这样的氨相来消除包含表面非均匀性的表面层。该解决方案提供了用于去除纤维的表面层的良好结果,该表面层导致在纤维上形成的涂层的附着力低,同时避免了使用有毒化合物。氨相可以是气态、液态或超临界状态。
使用超临界氨相具有优势。去除纤维表面存在的碳类物种的动力学在超临界条件下明显更大,这是由于组合应用了高温和高氨浓度,这种组合有利于反应。在使用气相或液相的技术中,只采用其中一种效果:在气体处理的情况下高温但氨浓度低,或者在使用液相期间浓度高但温度低,这会使得处理速度较低。此外,如果存在表面碳和其他氧化物污染物,使用超临界氨将去除它们,则它们将不再粘附并会被去除。与使用气态氨相比,使用超临界氨具有回收的优势,在处理后返回其初始状态,从而能够回收氨并再次使用,而高温气态氨会裂解成不可再利用的副产物。此外,这些副产物(诸如HCN)需要在废液中中和,而使用超临界氨则可以避免这种处理。因此,在超临界相中的处理可以实现对碳化硅纤维更高效、更简单的处理。
在一个实施方案中,表面层的去除在处理室中进行,并且该处理还包括,在处理室中,在该去除之后在所述至少一根纤维上由包含至少氨的处理介质形成涂层。
这个特点有利地使得有可能在同一室中进行消除非均匀性和执行涂覆操作,从而可以避免纤维返回空气环境并减少了操作。它还可以避免纤维端面官能化的风险,并获得更好的涂层与纤维之间的附着力。此外,两种情况下都使用了氨,消除了两个步骤之间的化学兼容性问题。
在一个示例性实施方案中,氨相的温度可以大于或等于600℃,例如600℃至1600℃。
使用这样的温度是有利的,因为它进一步激活了碳和氨之间的反应,从而提高了处理的动力学。
具体来说,氨相的温度在800℃至1200℃之间,氨相的压力可以在100巴和150巴之间。一般来说,氨相的压力可以大于临界压力。
这样的特性可以使处理与工业规模操作相兼容。
在一个示例性实施方案中,所述至少一根纤维在处理期间通过微波加热。
微波场可以将经处理的纤维的表面带到足够高的温度以局部达到所需的条件。微波场可以加热整个纤维以确保均匀的处理。此外,由于纤维被直接加热而不是整个处理室加热,所以用于处理纤维需要的能量降低了。然而,如果使用另一种加热方式(诸如来自感受器(susceptor)的辐射),也不超出本发明的范围。
在一种示例性实施方案中,所述至少一根纤维在处理期间移动通过处理室。纤维在处理室中的移动可以相对于氨相或处理介质的循环以相同方向或逆流进行。
使用上述的氨相(其可以加速动力学过程),对于在处理室中移动的纤维上进行连续沉积是特别有利的,并因此极大地提高了处理速率。
在一个示例性实施方案中,所述至少一根纤维由氧含量小于或等于1%(原子百分比)的碳化硅制成。
本发明还涉及一种制造复合材料部件的方法,包括至少在纤维增强体的孔中形成基体,所述纤维增强体的纤维已经通过实施上述方法进行处理。
需要注意的是,所述纤维增强体可以在按照上述方式处理多根纤维之后获得。或者,所述纤维增强体可以先由多根纤维形成,然后以上述方式对该增强体进行处理。
复合材料部件可以是例如涡轮机部件,例如涡轮机桨叶(blade)或叶片(vane)或涡轮机环形片。
附图说明
[图1]图1示意性地表示了在本发明方法的上下文或实施例中,纤维在处理室中的处理过程。
[图2]图2是示意性地表示最初具有表面层的碳化硅纤维结构的剖视图。
[图3]图3是示意性地表示在去除表面层之后和沉积涂层之前的图2的碳化硅纤维的结构的剖视图。
[图4]图4是示意性地表示经处理的涂覆的纤维的结构的剖视图。
[图5]图5示意性地表示可用于实施本发明方法的处理设施的实施例。
具体实施方式
图1示出了对纤维16进行的处理,使其表面得以处理以消除非均匀性,以便随后在同一室内用涂层(例如用硼氮化物中间相)对其进行涂覆。
经处理的纤维由碳化硅制成,任选地氧含量小于或等于1%(原子百分比)。这样的纤维包括例如以“Hi-Nicalon S”或“Hi-Nicalon”为名销售的纤维。或者,可以处理氧含量较高的Si-C-O纤维。这样的纤维包括例如以“Nicalon”为名销售的纤维。
图2非常示意性地示出了在预处理之前的碳化硅纤维16的横截面。纤维16具有表面层12,该表面层12包括碳氧化硅(由硅、碳和氧组成)和/或碳,优选在沉积涂层之前将表面层12去除。与碳化硅的化学计量相比,表面层12可以富含碳。表面层12可以主要由碳形成,表面层12中的碳的原子比例大于50%,例如大于或等于60%。表面层12的厚度e12通常可以在1nm和1mm之间,例如在1nm和1μm之间。碳化硅纤维16由碳化硅芯11和位于纤维16的表面附近的表面层12组成。表面层12呈异质的表面状态。表面层12可能使得纤维对覆盖其上的涂层的粘附质量降低。
在考虑的实施例中,纤维16在处理期间沿着图1中箭头D指示的方向移动通过处理室10。纤维的处理可以连续进行,而不中断纤维的移动。或者,也可以一段一段地处理纤维,将待处理的段固定在处理室10中并去除该纤维的表面层,然后将相邻的纤维段16引入到室10中以从这个相邻的段去除表面层。
经处理的纤维16从卷轴(未显示)上展开,穿过处理室10,然后在处理后被缠绕到卷轴上。纤维16在处理室10中的行进速度可以在0.1cm/s至50cm/s之间。
处理室10中充满了包含氨的流体介质20,例如基本上由氨构成。流体介质20可以是液体形式。流体介质20可以被加压,例如在大于或等于氨的临界压力的压力下。纤维16在处理室10中的处理期间被浸没在流体介质20中。在所示实施例中,纤维16被直接加热,例如通过施加微波场。加热使得至少在纤维16附近的温度升高,以获得用于处理的氨相22。
执行处理的氨相22的温度大于或等于100℃,压力大于或等于1巴。通过将纤维16在600℃至1600℃的温度和1巴至300巴的压力下与氨相相接触,可以去除表面层12。氨相的温度可以大于或等于800℃。氨相的压力可以大于或等于100巴,例如在100巴至150巴之间。使纤维16首先可以在1巴至300巴之间的压力下与加压氨接触,然后进行对纤维的加热,以使氨达到所需的温度,从而来去除表面层12。在处理期间,氨可以连续注入室10,也可以不连续注入。当在所有或部分处理期间流体介质连续循环的情况下,可以施加大于或等于0.00016s-1的[引入室的流体介质的流量]/[室的容积]比率,例如在0.0016s-1和0.016s-1之间或在0.0016s-1和0.16s-1之间。纤维16的表面碳可以与氨反应以形成被去除的氰化氢(HCN)。碳氧化物化合物也被氨介质去除。因此,获得了具有改善的表面状态(例如不存在非均匀性)的纤维11,如图3所示,并且其将准备进行涂覆。去除表面层12的处理的持续时间可以大于或等于10秒,例如在5分钟至30分钟之间。
如上所述,该方法可以继续进行,以便在去除表面层12后在同一室10中涂覆所获得的纤维11。通常,可以从包含溶解在氨中的至少一种待形成的涂层的前体的处理介质开始,于处理室10中在纤维上形成涂层。处理介质可以是气态、液态或超临界状态。氨可以是待形成的涂层的前体的溶剂。因此,例如,可以从包含溶解在氨中的硼烷氨(化学式为BH3NH3)的流体介质沉积氮化硼中间相。通过微波直接加热纤维可以引发与如此加热的纤维接触的硼烷氨的分解,并形成氮化硼中间相。该中间相是通过在温度作用下硼烷氨的分解形成的。这种分解可以用于获得六方氮化硼并释放分子氢气。特别地,在使用溶解在氨中的硼烷氨的情况下,处理介质的温度可以大于或等于600℃,例如在600℃至1600℃之间,并且处理介质的压力可以大于或等于10巴,例如在10巴至300巴之间。处理介质的温度尤其可以大于或等于800℃,或者大于或等于900℃,例如在800℃至1600℃之间,或者在900℃至1600℃之间,并且处理介质的压力可以大于或等于100巴,例如在100巴至150巴之间。这些条件构成了一种折衷方案,使得可以在利用硼烷氨的高溶解性的同时受益于改善的传质以及由此得到的更高的沉积动力学。此外,这些压力对于该方法的工业发展是可行的。
包含涂层的前体的流体介质可以连续移动通过处理室10,或者处理室10可以最初充满流体介质,然后在不将流体介质引入处理室或未排空的情况下进行处理。在包含该前体的流体介质持续循环的情况下,在全部或部分处理期间,可以施加大于或等于0.00016s-1的[引入室的流体介质的流量]/[室的容积]比率,例如在0.0016s-1至0.016s-1之间,或在0.0016s-1至0.16s-1之间。例如,对于容积在0.1mL至100mL之间的处理室10,在全部或部分处理期间,流体介质可以以在0.1mL/分钟至10mL/分钟之间,例如在0.1mL/分钟至3mL/分钟之间的流速引入处理室10中。一般来说,流体介质20中涂层前体的摩尔浓度可以大于或等于0.001mol/L,例如在0.001mol/L至10mol/L之间。
中间相24的厚度e24可以大于或等于1nm,例如大于或等于10nm(见图4)。厚度e24可以在10nm至1mm之间,例如在10nm至10μm之间。得到的中间相24在经处理的纤维的整个圆周上具有可控和均匀的厚度,其中硼:氮的化学计量比接近于1。获得的硼氮化物可以是结晶的。使用晶体材料是有益的,以便提高裂纹偏转性能。可以获得六边形硼氮化物中间相。纤维的涂层处理的持续时间可以大于或等于10秒,例如在5分钟至30分钟之间,或在1分钟至10分钟之间。
适才描述了在处理室10中由包含氨的介质形成氮化硼中间相。其他类型的涂层也是可能的,诸如由包含溶解在氨中的例如(二乙基氨基)(叔丁基亚氨基)钽TBTDET的处理介质沉积氮化钽(TaN)涂层。根据这个变型,处理介质的温度可以大于或等于200℃,例如在200℃至1600℃之间,并且处理介质的压力可以大于或等于10巴,例如在10巴至300巴之间。
这种处理的优点在于在同一室10中执行消除非均匀性和进行涂层的步骤,这使得避免纤维返回环境空气并减少操作成为可能。此外,氨还用于形成涂层,从而消除了两个步骤之间的任何化学兼容性问题。
一旦涂层被沉积,可以通过以0.5mL/分钟至10mL/分钟的流速注入加压的液态氨来清洁处理室10,以便去除未反应的过量前体。
将在下文中进行描述的图5更完整地图示了一个可以用来实施本发明方法的设备的实施例。
图5中所示的设备1包括注射泵4,它可以以恒定的流量或压力工作。还包括用于产生能够通过这种辐射加热纤维11的微波的装置,以及由对微波透明的材料制成并且其中包含要加热的纤维11的管9。设备1包括压力调节器15,当注射泵以恒定流速运行时,该压力调节器可以固定整个装置的压力。
在对纤维11进行处理以去除氮化硼中间相的情况下,储罐6首先填充硼烷氨,然后将其连接到装置的其余部分。注射泵4被溶剂充满,并通过低温恒温器进行冷却。然后打开注射泵4,关闭阀门7、8、13和14。注射泵以恒定压力工作,从而以工作压力将氨填充到储罐6中。然后关闭储罐5的阀门,打开阀门7,使整个装置处于压力下。接着,打开阀门13,并注射泵在恒流模式下使用。然后通过压力调节器15固定压力。一旦系统中的压力稳定,关闭阀门7,并打开储罐5的阀门及阀门8,以便将由硼烷氨和溶剂组成的溶液注入处理室10。当恒流流速操作稳定时,使用微波加热装置在给定时间内将包含在室10中的纤维11加热到工作温度。当所有前体都被注入后,注入加压溶剂(通过注射泵)以去除可能残留的任何前体的痕迹。对于通过氨相的处理,使用类似的操作模式,以便在不使用硼烷氨的情况下去除表面层。
适才描述了根据本发明的方法的一个实施例,其中一根纤维被处理。然而,如果同时处理多根纤维以去除它们的表面层并任选地在每根纤维上形成涂层,这当然不会超出本发明的范围。需要注意的是,每根纤维可以呈包含多个细丝的粗纱的形式。如果不再是处理一根纤维或处理未连接在一起的多根纤维,而是处理包含在处理室中可移动或不可移动的多根纤维的已成型纹理(texture),这也不超过本发明的范围。因此,纤维可以以任何形式进行处理,例如线、粗纱、股线、连线、纤维织物、毡、垫和甚至二维或三维纹理。根据本发明的方法处理的纤维可以有利地用于生产复合材料部件的纤维预制件。无论纤维是以何种形式处理的,上述处理条件仍然适用。
适才描述了碳化硅纤维的处理,以使用氨相去除其表面层,然后在以这种方式清洁的纤维表面上形成涂层。接下来将努力描述从如此处理的纤维获得复合材料部件的其他方法。
经过上述处理后获得的纤维然后可以用于形成要获得的部件的纤维预制件。纤维预制件的形成使用本身已知的纺织操作,例如编织,任选地为三维编织。因此,预制件可以例如具有“互锁”编织方式,换句话说,编织方式为每层纬纱连接多层经纱,同列纬纱的所有纱线在同一编织平面内具有相同的运动。当然可以使用其他类型的三维编织来生产该预制件。如上所述,如果预制件首先由纤维形成,然后对如此获得的预制件的纤维进行上述处理,这也不会超出本发明的范围。
该方法可以通过在纤维预制件的孔中形成至少一种基体相来进行,该纤维预制件的纤维已经经过上述处理。
所得基体可以至少部分由陶瓷制成,例如主要由陶瓷制成,例如完全由陶瓷制成。基体的形成使用本身已知的技术,例如通过液体致密化(通过基体的前体树脂的浸渍以及通过交联和热解转化,该过程是可重复的)或气态技术(基体的化学气相渗透),或者甚至通过熔体浸渗法(MI)进行。
本发明特别适用于生产由陶瓷基体复合材料制成的部件,所述陶瓷基体复合材料由具有通过陶瓷基体(特别是耐火碳化物、氮化物或氧化物)进行致密化的碳化硅纤维的纤维增强体形成。这种CMC材料的典型实例是SiC-SiC材料(由碳化硅纤维制成的增强体和由碳化硅制成的基体)。
所得部件可以是航空或工业涡轮机部件。例如,该部件可以是涡轮机桨叶或叶片或涡轮机环形片。
实施例
如图1中示意性示出的,一根纤维穿过处理室10,该处理室具有1cm3的体积。所处理的纤维是氧含量小于或等于1%原子百分比的碳化硅纤维,对应于以“Hi-Nicalon S”名称销售的纤维。在处理之前,该纤维在其表面上具有厚度约为100nm的表面层12。
首先对该纤维进行预处理步骤,通过将其在室10中暴露于超临界氨相。在预处理期间,通过微波场加热纤维,使得温度达到1000℃,并且将超临界氨相的压力提高到120巴。在预处理期间,以6mL/min的流速连续向处理室注入氨,并且以30cm/分钟的速度移动纤维。因此获得了剥除表面的碳化硅,如图3所示。
然后在同一处理室中,氮化硼中间相沉积在所述剥皮的纤维上。在此沉积期间,纤维以30cm/分钟的速度在处理室内移动。将氨和硼烷氨的混合物(在混合物中的摩尔浓度为1moL/L)以1mL/min的流量连续引入到处理室中。在处理期间,通过微波场将纤维表面的温度升高到1100℃,并且流体介质处于120巴的压力下。在15分钟的时间段内进行处理,并且以这种方式在碳化硅纤维的表面上获得1000nm的BN中间相。
表达“在……之间”应理解为包括极限值。
Claims (8)
1.一种用于处理至少一根碳化硅纤维(16)的方法,所述碳化硅纤维包含含有碳和/或碳氧化硅的表面层(12),所述处理包括通过将纤维与处于超临界状态的氨相(22)接触来至少从所述纤维去除所述表面层。
2.根据权利要求1所述的方法,其中所述表面层(12)的去除在处理室(10)中进行,并且其中所述处理还包括在所述去除之后,在所述处理室中由至少包含氨的处理介质在所述至少一根纤维(11)上形成涂层(24)。
3.根据权利要求1或2所述的方法,其中所述氨相(22)的温度大于或等于600℃。
4.根据权利要求3所述的方法,其中所述氨相(22)的温度为800℃至1200℃,并且所述氨相的压力为100巴至150巴。
5.根据权利要求1至4中的任一项所述的方法,其中所述至少一根纤维(16;11)在所述处理期间由微波加热。
6.根据权利要求1至5中的任一项所述的方法,其中所述至少一根纤维(16;11)在所述处理期间移动通过处理室(10)。
7.根据权利要求1或6中的任一项所述的方法,其中所述至少一根纤维(16;11)由氧含量小于或等于1%原子百分比的碳化硅制成。
8.一种制造复合材料部件的方法,至少包括在纤维增强体的孔中形成基体,所述纤维增强体的纤维(11)已经通过实施根据权利要求1至7中任一项所述的方法进行了处理。
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PCT/FR2022/051187 WO2022269178A1 (fr) | 2021-06-23 | 2022-06-20 | Procede de traitement d'une fibre de carbure de silicium |
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