技术领域technical field
本发明涉及一种高体积分数碳化硅纳米线增强陶瓷基复合材料及其制备方法，特别涉及高体积分数一维SiC纳米材料的致密化，属于纳米材料领域。The invention relates to a high volume fraction silicon carbide nanowire reinforced ceramic matrix composite material and a preparation method thereof, in particular to the densification of a high volume fraction one-dimensional SiC nanomaterial, belonging to the field of nanomaterials.
背景技术Background technique
自1991年碳纳米管的发现后，一维纳米材料由于其优异的性能而备受关注。一维纳米材料在电学、热学和磁学等方面具有传统材料无法企及的性能，有望成为复合材料的新型增强材料，实现结构材料功能化。其中，碳化硅纳米线备受瞩目，其强度、模量与热学性能均优于碳化硅晶须及块体材料，作为增强相有望提高复合材料力学性能并增强热导性能。Since the discovery of carbon nanotubes in 1991, one-dimensional nanomaterials have attracted much attention due to their excellent properties. One-dimensional nanomaterials have properties beyond the reach of traditional materials in terms of electricity, heat, and magnetism, and are expected to become new reinforcement materials for composite materials and realize the functionalization of structural materials. Among them, silicon carbide nanowires have attracted much attention. Its strength, modulus and thermal properties are superior to silicon carbide whiskers and bulk materials. As a reinforcing phase, it is expected to improve the mechanical properties of composite materials and enhance thermal conductivity.
碳化硅纳米线的应用障碍受限于体积分数偏低，界面难调控，基体难以致密化。目前，碳化硅纳米线的应用有两种；一种是在材料内部生长碳化硅纳米线，这种方法有其自身的局限性，纳米线无法在材料内部达到一个均匀的分散效果，生长的纳米线质量参差不齐，杂质残留在基体影响材料性能的发挥；其次，对于纤维和纳米线的协同增强作用，界面的制备难以同时达到最优化；另外，这种方法制备的纳米线增强复合材料，其纳米线体积分数难以控制，纳米线体积分数不足时无法发挥较佳的增强效果。第二种是选用纯化的纳米线原料对其进行基体的制备。这种方法避免了生长纳米线带来的杂质，纳米线分散均匀，体积分数存在一定的可调控性。传统的纳米线增强复合材料方法直接将纳米线与陶瓷粉体混合，纳米线的分散性不佳。粉体烧结也容易破坏纳米线结构而导致性能下降。The barriers to the application of SiC nanowires are limited by the low volume fraction, difficult control of the interface, and difficulty in densifying the matrix. At present, there are two applications of silicon carbide nanowires; one is to grow silicon carbide nanowires inside the material. This method has its own limitations. The nanowires cannot achieve a uniform dispersion effect inside the material. The wire quality is uneven, and impurities remaining in the matrix affect the performance of the material; secondly, for the synergistic reinforcement effect of fibers and nanowires, it is difficult to optimize the preparation of the interface at the same time; in addition, the nanowire-reinforced composite materials prepared by this method, Its volume fraction of nanowires is difficult to control, and when the volume fraction of nanowires is insufficient, a better enhancement effect cannot be exerted. The second is to use purified nanowire raw materials to prepare the matrix. This method avoids the impurity brought by growing nanowires, the nanowires are uniformly dispersed, and the volume fraction has certain controllability. The traditional method of nanowire-reinforced composite materials directly mixes nanowires with ceramic powder, and the dispersion of nanowires is not good. Powder sintering is also easy to destroy the nanowire structure and lead to performance degradation.
发明内容Contents of the invention
针对SiC纳米线应用障碍，本发明的目的是为了提出一种高体积分数碳化硅纳米线增强陶瓷基复合材料及其制备方法。Aiming at obstacles to the application of SiC nanowires, the purpose of the present invention is to propose a high volume fraction silicon carbide nanowire reinforced ceramic matrix composite material and a preparation method thereof.
一方面，本发明提供了一种高体积分数碳化硅纳米线增强陶瓷基复合材料的制备方法，包括：In one aspect, the present invention provides a method for preparing a high volume fraction silicon carbide nanowire-reinforced ceramic matrix composite, comprising:
(1)将碳化硅纳米线和分散剂分散于溶剂中，得到碳化硅纳米线悬浮液；(1) dispersing the silicon carbide nanowire and the dispersant in a solvent to obtain a silicon carbide nanowire suspension;
(2)将所得碳化硅纳米线悬浮液经抽滤后，得到碳化硅纳米线预制体；(2) After suction filtering the obtained silicon carbide nanowire suspension, a silicon carbide nanowire prefabricated body is obtained;
(3)采用化学气相沉积工艺或化学气相渗透工艺对所得碳化硅纳米线预制体进行界面修饰；(3) Using a chemical vapor deposition process or a chemical vapor infiltration process to modify the interface of the obtained silicon carbide nanowire preform;
(4)采用化学气相渗透工艺和有机前驱体浸渍裂解工艺中至少一种对所得碳化硅纳米线预制体进行致密化处理，得到所述高体积分数碳化硅纳米线增强陶瓷基复合材料。(4) Using at least one of a chemical vapor infiltration process and an organic precursor immersion cracking process to densify the obtained silicon carbide nanowire preform to obtain the high volume fraction silicon carbide nanowire reinforced ceramic matrix composite material.
本发明中，利用抽滤得到的碳化硅纳米线预制体，保证了碳化硅纳米线高的体积分数，CVI或制备界面使得纳米线在复合材料中更好的发挥增强效果。单纯的CVI工艺易使表面气孔堵塞而内部仍存在大量孔隙，单纯的PIP工艺需要薄片有一定的致密度、力学强度和气孔率。CVI结合PIP的混合工艺将两种工艺的特点和结合发挥到极致，使碳化硅纳米线预制体达到较高的致密度。In the present invention, the silicon carbide nanowire prefabricated body obtained by suction filtration ensures a high volume fraction of the silicon carbide nanowire, and the CVI or preparation interface enables the nanowire to play a better reinforcing effect in the composite material. The simple CVI process is easy to block the pores on the surface and there are still a lot of pores inside. The simple PIP process requires the sheet to have a certain density, mechanical strength and porosity. The hybrid process of CVI combined with PIP maximizes the characteristics and combination of the two processes, so that the silicon carbide nanowire preform can achieve higher density.
较佳地，步骤(1)中，所述碳化硅纳米线的直径为0.02～0.6μm，长度为10～200μm，长径比大于100，所述分散剂选自十二烷基磺酸钠、异丙醇、聚乙烯吡咯烷酮、乙二醇丁醚中的至少一种；优选地，所述分散剂和碳化硅纳米线的质量比为1:(0.1～30)。Preferably, in step (1), the silicon carbide nanowires have a diameter of 0.02-0.6 μm, a length of 10-200 μm, and an aspect ratio greater than 100, and the dispersant is selected from sodium dodecylsulfonate, At least one of isopropanol, polyvinylpyrrolidone, and ethylene glycol butyl ether; preferably, the mass ratio of the dispersant to the silicon carbide nanowire is 1:(0.1-30).
较佳地，步骤(1)中，所述溶剂为无水乙醇、去离子水、丙酮和甲醛中的至少一种。Preferably, in step (1), the solvent is at least one of absolute ethanol, deionized water, acetone and formaldehyde.
较佳地，步骤(1)中，所述分散的方式为超声处理；所述超声处理的功率为10～1000W，时间为0.1～2小时。Preferably, in step (1), the dispersion method is ultrasonic treatment; the power of the ultrasonic treatment is 10-1000W, and the time is 0.1-2 hours.
较佳地，步骤(2)中，步骤(2)中，采用抽滤机进行，所述抽滤机的工作参数为20～60L/min，功率为160～500W；优选地，优选地，在抽滤之后，在0.1～10MPa的压力下进行压缩处理(对抽滤后所得初步的碳化硅纳米线预制体进行压缩处理)。较佳地，所述碳化硅纳米线预制体的厚度为0.5mm～10mm。Preferably, in step (2), in step (2), use a suction filter, the operating parameters of the suction filter are 20-60L/min, and the power is 160-500W; preferably, preferably, in After the suction filtration, compression treatment is performed under a pressure of 0.1-10 MPa (compression treatment is performed on the preliminary silicon carbide nanowire preform obtained after the suction filtration). Preferably, the thickness of the silicon carbide nanowire preform is 0.5mm-10mm.
较佳地，步骤(3)中，所述界面修饰所得界面层为热解碳界面层、碳化硅界面层、氮化硼界面层、氮化硅界面层中的至少一种；所述界面层的厚度5～100nm。Preferably, in step (3), the interface layer obtained by the interface modification is at least one of a pyrolytic carbon interface layer, a silicon carbide interface layer, a boron nitride interface layer, and a silicon nitride interface layer; the interface layer The thickness of 5 ~ 100nm.
较佳地，步骤(4)中，所述化学气相渗透工艺的参数包括：采用甲基三氯硅烷MTS作为有机前驱体100～400sccm，氢气为载气和稀释气体速率为10～90sccm；温度为1000～1100℃，压强为1.5～6KPa，时间为300～1000分钟。Preferably, in step (4), the parameters of the chemical vapor infiltration process include: using methyltrichlorosilane MTS as an organic precursor of 100 to 400 sccm, hydrogen as a carrier gas and a dilution gas rate of 10 to 90 sccm; the temperature is 1000-1100°C, pressure 1.5-6KPa, time 300-1000 minutes.
较佳地，步骤(4)中，所述有机前驱体浸渍裂解工艺的参数包括：有机前驱体种类选自聚碳硅烷、聚硅氧烷、聚硅氮烷中至少一种；裂解温度为700～1100℃。Preferably, in step (4), the parameters of the organic precursor immersion cracking process include: the type of organic precursor is selected from at least one of polycarbosilane, polysiloxane, and polysilazane; the cracking temperature is 700 ~1100°C.
另一方面，本发明提供了一种根据上述得制备方法制备的高体积分数碳化硅纳米线增强陶瓷基复合材料，所述高体积分数碳化硅纳米线增强陶瓷基复合材料中碳化硅纳米线的体积分数为10～37vol％。In another aspect, the present invention provides a high volume fraction silicon carbide nanowire-reinforced ceramic matrix composite material prepared according to the above preparation method, the high volume fraction silicon carbide nanowire-reinforced ceramic matrix composite material The volume fraction is 10-37vol%.
有益效果：Beneficial effect:
针对SiC纳米线的应用存在分散性，体积分数，界面调控，纳米孔道致密等难题，本发明利用抽滤获得高体积分数网状SiC纳米线薄片，采用化学气相渗透或其他方法对SiC纳米线进行界面层的制备，采用CVI结合PIP的方法使所得碳化硅纳米线增强陶瓷基复合材料有达到较高的致密度，密度达到2.74g/cm3，三点弯曲强度达到273±32MPa，纳米压痕显示模量494±14GPa，以实现碳化硅纳米线在陶瓷基复合材料中的实效应用。本发明是以碳化硅为基体，碳化硅纳米线做增强相制备碳化硅纳米线增韧碳化硅陶瓷基复合材料。本发明在保证碳化硅纳米线高体积分数的同时，避免传统工艺制备基体时对其性能的损坏，以及仅CVI难以达到较高致密度，仅PIP无法直接对纳米线薄片致密的情况，使碳化硅纳米线在复合材料中性能充分发挥。Aiming at the problems of dispersibility, volume fraction, interface control, and dense nanopores in the application of SiC nanowires, the present invention uses suction filtration to obtain high-volume fraction reticulated SiC nanowire flakes, and uses chemical vapor infiltration or other methods to process SiC nanowires. The preparation of the interface layer adopts the method of CVI combined with PIP to make the obtained silicon carbide nanowire reinforced ceramic matrix composite material have a higher density, the density reaches 2.74g/cm3 , the three-point bending strength reaches 273±32MPa, and the nano-indentation The display modulus is 494±14GPa, in order to realize the practical application of silicon carbide nanowires in ceramic matrix composites. The invention uses silicon carbide as a matrix and silicon carbide nanowires as a reinforcing phase to prepare silicon carbide nanowire toughened silicon carbide ceramic matrix composite materials. While ensuring a high volume fraction of silicon carbide nanowires, the present invention avoids damage to its performance when preparing the substrate by traditional techniques, and it is difficult to achieve higher density with only CVI, and only PIP cannot directly compact the nanowire flakes, making carbonization Silicon nanowires are fully functional in composite materials.
附图说明Description of drawings
图1为实施例1中SiC纳米线经过抽滤干燥(1)、界面制备(2)、CVI基体制备(3)和PIP基体(4)制备后的复合材料的外观图；Fig. 1 is the appearance diagram of the composite material prepared by SiC nanowires in Example 1 after suction filtration drying (1), interface preparation (2), CVI matrix preparation (3) and PIP matrix (4);
图2为实施例1中SiC纳米线薄片基体制备经过不同时长CVI和PIP下样品质量的变化，其中(a)不同CVI时长下质量的变化，(b)、(c)、(d)和(e)分别对应(a)图中20小时、40小时、50小时和60小时CVI；(f)为50小时CVI结合3次PIP后样品断面电镜图；Fig. 2 is the change of sample quality under different time length CVI and PIP for the preparation of SiC nanowire flake substrate in embodiment 1, wherein (a) the change of quality under different CVI time lengths, (b), (c), (d) and ( e) Corresponding to the 20-hour, 40-hour, 50-hour and 60-hour CVI in (a) respectively; (f) is the cross-sectional electron microscope image of the sample after 50-hour CVI combined with 3 times of PIP;
图3为实施例1中抽滤后制备的网状碳化硅纳米线的SEM照片；Fig. 3 is the SEM photograph of the mesh silicon carbide nanowire prepared after suction filtration in embodiment 1;
图4为实施例1中CVI和PIP结合致密后复合材料的断面的SEM照片。Fig. 4 is the SEM photograph of the section of the composite material after CVI and PIP are combined and dense in Example 1.
具体实施方式Detailed ways
以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。The present invention will be further described below through the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, not to limit the present invention.
本发明充分利用碳化硅纳米线性能，有利于制备具有优异力学、热学性能的高体积分数碳化硅纳米线增强陶瓷基复合材料，其可调控性强、应用前景大。The invention makes full use of the properties of silicon carbide nanowires, which is beneficial to the preparation of high-volume silicon carbide nanowire-reinforced ceramic-based composite materials with excellent mechanical and thermal properties, which has strong controllability and great application prospects.
碳化硅纳米线悬浮液的制备。调控碳化硅纳米线和分散剂的比例，分散于溶剂中，获得均匀分散的碳化硅纳米线悬浮液。碳化硅纳米线的直径可为0.02～0.6μm，长度为10～200μm，长径比大于100。作为优选，所述碳化硅纳米线直径为0.02～0.1μm，长度为10～100μm，长径比大于100。所述溶剂为无水乙醇、去离子水、丙酮、甲醛中的至少一种。所述的分散剂包含十二烷基磺酸钠、异丙醇、聚乙烯吡咯烷酮、乙二醇丁醚中的至少一种。分散剂与碳化硅纳米线的质量比可为1:0.1～1:30。作为一个示例，调控碳化硅纳米线和分散剂的比例，采用机械搅拌或/和超声处理等工艺将碳化硅纳米线分散于溶剂中，获得均匀分散的碳化硅纳米线悬浮液。超声处理的功率为10～1000W，时间为0.1h～2h。Preparation of SiC Nanowire Suspensions. Regulate the ratio of silicon carbide nanowires and dispersant, disperse in a solvent, and obtain a uniformly dispersed silicon carbide nanowire suspension. The silicon carbide nanowires can have a diameter of 0.02-0.6 μm, a length of 10-200 μm, and an aspect ratio greater than 100. Preferably, the silicon carbide nanowires have a diameter of 0.02-0.1 μm, a length of 10-100 μm, and an aspect ratio greater than 100. The solvent is at least one of absolute ethanol, deionized water, acetone, and formaldehyde. The dispersant includes at least one of sodium dodecylsulfonate, isopropanol, polyvinylpyrrolidone and ethylene glycol butyl ether. The mass ratio of the dispersant to the silicon carbide nanowire can be 1:0.1˜1:30. As an example, the ratio of silicon carbide nanowires and dispersant is adjusted, mechanical stirring or/and ultrasonic treatment are used to disperse silicon carbide nanowires in a solvent, and a uniformly dispersed silicon carbide nanowire suspension is obtained. The power of ultrasonic treatment is 10-1000W, and the time is 0.1h-2h.
碳化硅纳米线预制体的制备。采用抽滤机等装置制备高体积分数碳化硅纳米线预制体。具体的抽滤的步骤或参数包括：将碳化硅纳米线与溶剂水、分散剂聚乙烯吡咯烷酮混合，超声后得到的均匀纳米线溶液倒入抽滤瓶中，瓶口放置0.5um孔道大小的滤纸。抽滤得到0.5mm厚度的碳化硅纳米线薄片。抽滤机的工作参数可为20～60L/min，功率可为160～500W。经干燥得到无水的网状碳化硅纳米线薄片。本发明通过抽滤得到纯的碳化硅纳米线薄片，保证了SiC纳米线的高体积分数。优选，同时对其稍加压缩至一定厚度，可以改变纳米线间孔隙大小，进一步调控碳化硅纳米线的体积分数。该压缩的压力大小可为0.1～10MPa。Preparation of silicon carbide nanowire preforms. A device such as a suction filter is used to prepare a silicon carbide nanowire preform with a high volume fraction. The specific steps or parameters of suction filtration include: mixing silicon carbide nanowires with solvent water and dispersant polyvinylpyrrolidone, pouring the uniform nanowire solution obtained after ultrasonication into a suction filtration bottle, and placing a filter paper with a pore size of 0.5um at the mouth of the bottle . SiC nanowire flakes with a thickness of 0.5 mm were obtained by suction filtration. The working parameters of the suction filter can be 20-60L/min, and the power can be 160-500W. Anhydrous network silicon carbide nanowire flakes were obtained after drying. The invention obtains pure silicon carbide nanowire flakes through suction filtration, which ensures a high volume fraction of SiC nanowires. Preferably, at the same time, compressing it slightly to a certain thickness can change the size of the pores between the nanowires and further regulate the volume fraction of the silicon carbide nanowires. The compression pressure can be 0.1-10 MPa.
界面层的制备。用化学气相渗透(CVI)或化学气相沉积(CVD)等工艺对碳化硅纳米线预制体进行界面修饰，得到界面层。其中界面层包括但不限于热解碳、碳化硅、氮化硼、氮化硅等界面。界面层的厚度在5～100nm之间最佳。Preparation of interface layer. The interface layer of the silicon carbide nanowire preform is modified by chemical vapor infiltration (CVI) or chemical vapor deposition (CVD). Wherein the interface layer includes but not limited to pyrolytic carbon, silicon carbide, boron nitride, silicon nitride and other interfaces. The thickness of the interface layer is optimal between 5 and 100 nm.
致密化过程。利用CVI和有机前驱体浸渍裂解(PIP)等单一或混合工艺对碳化硅纳米线预制体进行致密化处理，获得高体积分数碳化硅纳米线改性的陶瓷基复合材料，实现碳化硅纳米线宏观应用并充分发挥其优异的性能。优选结合CVI与PIP工艺优势，对纳米材料进行致密，最大限度发挥两者的优点，使复合材料达到较高的致密度。其中，PIP选用前驱体PCS引入碳化硅纳米线预制体，前驱体种类包括但不限于聚碳硅烷、聚硅氧烷、聚硅氮烷等，裂解温度为700～1100℃，裂解所得基体材料组分为SiC。其中，化学气相渗透工艺的参数包括：采用甲基三氯硅烷MTS作为有机前驱体100～400sccm，氢气为载气和稀释气体10～90sccm；温度为1000～1100℃，压强为1.5～6KPa，时间为300～1000分钟，得到初步致密碳化硅纳米线增强的碳化硅陶瓷基复合材料。化学气相渗透工艺所得基体材料组分为SiC。densification process. Using CVI and organic precursor impregnation cracking (PIP) and other single or mixed processes to densify the SiC nanowire preform, obtain a high volume fraction SiC nanowire modified ceramic matrix composite material, and realize the macroscopic SiC nanowire Apply and give full play to its excellent performance. It is preferable to combine the advantages of CVI and PIP technology to densify nanomaterials, and maximize the advantages of both, so that the composite material can achieve higher densification. Among them, PIP uses the precursor PCS to introduce the silicon carbide nanowire prefabricated body. The types of precursors include but are not limited to polycarbosilane, polysiloxane, polysilazane, etc., and the cracking temperature is 700-1100 ° C. The matrix material group obtained by cracking Divided into SiC. Among them, the parameters of the chemical vapor infiltration process include: using methyltrichlorosilane MTS as the organic precursor 100-400 sccm, hydrogen as the carrier gas and dilution gas 10-90 sccm; temperature 1000-1100 °C, pressure 1.5-6KPa, time The time is 300 to 1000 minutes, and a silicon carbide ceramic matrix composite material reinforced with dense silicon carbide nanowires is obtained. The matrix material component obtained by the chemical vapor infiltration process is SiC.
在本发明中，高体积分数碳化硅纳米线增强陶瓷基复合材料中碳化硅纳米线的体积分数为10～37vol％，致密度为73％以上，密度达到2.74g/cm3，三点弯曲强度达到316MPa，纳米压痕显示模量高达514GPa。In the present invention, the volume fraction of silicon carbide nanowires in the high volume fraction silicon carbide nanowire reinforced ceramic matrix composite material is 10-37vol%, the density is more than 73%, the density reaches 2.74g/cm3 , and the three-point bending strength reaching 316MPa, and nanoindentation shows a modulus as high as 514GPa.
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。Examples are given below to describe the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art according to the above contents of the present invention all belong to the present invention scope of protection. The specific process parameters and the like in the following examples are only examples of suitable ranges, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values exemplified below.
实施例1：Example 1:
(1)采用十二烷基磺酸钠作为分散剂(0.1g)，控制碳化硅纳米线与十二烷基磺酸钠质量比为5:1，利用超声工艺将碳化硅纳米线均匀分散于去离子水中，获得无序碳化硅纳米线悬浮液，超声功率为300W，超声时间为1h；(1) Sodium dodecylsulfonate was used as a dispersant (0.1g), the mass ratio of silicon carbide nanowires to sodium dodecylsulfonate was controlled to be 5:1, and the silicon carbide nanowires were uniformly dispersed in the Obtain a suspension of disordered silicon carbide nanowires in deionized water, the ultrasonic power is 300W, and the ultrasonic time is 1h;
(2)使用真空抽滤的方法将碳化硅纳米线制备成网状薄膜，抽滤机工作参数20L/min，功率160W，在0.15MPa的压力下压缩处理，使得薄膜的厚度控制在0.5mm～1.2mm。经干燥得到网状碳化硅纳米线薄片；(2) Prepare silicon carbide nanowires into a mesh film by vacuum filtration. The suction filter has working parameters of 20L/min and a power of 160W. It is compressed under a pressure of 0.15MPa so that the thickness of the film is controlled at 0.5mm~ 1.2mm. Obtain the network-like silicon carbide nanowire flakes through drying;
(3)将(2)中得到的薄膜置于CVI炉中进行热解碳或氮化硼界面的制备，热解碳界面层(厚度为5nm)制备工艺：CH4流速为50sccm，温度1100℃，压强3KPa，反应时间60min。氮化硼界面工艺参数：BCl3流速10sccm，NH3流速30sccm，H2流速60sccm，温度800℃，压强0.5KPa，反应时间45min；(3) The film obtained in (2) is placed in a CVI furnace to prepare pyrolytic carbon or boron nitride interface, and the preparation process of pyrolytic carbon interface layer (thickness is 5nm): CHThe flow rate is 50sccm, and the temperature is 1100°C , pressure 3KPa, reaction time 60min. Boron nitride interface process parameters: BCl3 flow rate 10sccm, NH3 flow rate 30sccm, H2 flow rate 60sccm, temperature 800°C, pressure 0.5KPa, reaction time 45min;
(4)将(3)中得到的薄膜继续CVI沉积碳化硅基体，工艺参数MTS载气H2混合气体速率208sccm，调节MTS气压罐出气伐，保持压强维持在0刻度左右，即进气和出气的速率相同。稀释H2流速62sccm，温度1100℃，压强3KPa，反应时间300～1000min；(4) Continue CVI deposition of the silicon carbide substrate on the film obtained in (3), the process parameter MTS carrier gas H2 mixed gas rate of 208 sccm, adjust the gas outlet of the MTS pressure tank, and keep the pressure at about 0 scale, that is, the intake and output the same rate. The dilute H2 flow rate is 62sccm, the temperature is 1100°C, the pressure is 3KPa, and the reaction time is 300-1000min;
(5)将(4)得到块体继续3～7次碳化硅前驱体PCS浸渍裂解循环，至碳化硅纳米线增强碳化硅陶瓷基复合材料质量变化在1％以内。(5) The block obtained in (4) is continued for 3 to 7 cycles of immersion and cracking of the silicon carbide precursor PCS until the mass change of the silicon carbide nanowire-reinforced silicon carbide ceramic matrix composite material is within 1%.
实施例2：Example 2:
与实施例1相同的部分不再描述，不同之处是，在实施例1中步骤(4)后对样品进行切割，对其表面打磨，断面切割使孔道暴露出来，继续过程(5)实现碳化硅纳米线增强的碳化硅陶瓷基复合材料致密化，多次浸渍裂解实现碳化硅纳米线增强陶瓷基复合材料质量变化在1％以内。The same part as in Example 1 is no longer described, and the difference is that the sample is cut after step (4) in Example 1, its surface is polished, the section cutting exposes the channel, and the process (5) is continued to realize carbonization The silicon carbide ceramic matrix composite material reinforced by silicon nanowires is densified, and the mass change of the silicon carbide nanowire reinforced ceramic matrix composite material is within 1% through multiple dipping and cracking.
实施例3：Example 3:
与实施例1中相同部分不再陈述，在步骤(5)中选用熔渗的方法对其渗硅处理，使其达到较高的致密度。The same part as in Example 1 will not be stated again. In the step (5), the method of infiltration is selected for siliconizing treatment to make it reach a higher density.
实施例4：Example 4:
与实施例1中相同部分不再陈述，在步骤(1)后加入PMMA(0.3g)于溶液中，加热搅拌得到半干的胶体，对其进行铸模，凝固得到一定形状块状体。将得到的块状体置于真空或惰性气体炉中脱模得到一定形状的网状纳米线薄片。继续实施例1中步骤(3)、(4)、(5)对网状SiC纳米线致密处理，直至碳化硅纳米线增强陶瓷基复合材料质量变化在1％以内。The same part as in Example 1 is no longer stated, and PMMA (0.3g) is added in the solution after step (1), heated and stirred to obtain a semi-dry colloid, which is molded and solidified to obtain a certain shape block. The obtained block is placed in a vacuum or an inert gas furnace for demolding to obtain a mesh-shaped nanowire sheet of a certain shape. Continue the steps (3), (4) and (5) in Example 1 to densify the meshed SiC nanowires until the mass change of the SiC nanowire-reinforced ceramic matrix composite is within 1%.
表1为本发明制备的高体积分数碳化硅纳米线增强陶瓷基复合材料的性能参数：Table 1 is the performance parameter of the high volume fraction silicon carbide nanowire reinforced ceramic matrix composite material prepared by the present invention:
图1为实施例1中SiC纳米线经过抽滤干燥(1)、界面制备(2)、CVI基体制备(3)和PIP基体(4)制备后的复合材料的外观图，从图中可知样品经过抽滤后的薄片有较高的纳米线体积分数，热解碳界面制备后外观变为黑色，经过CVI基体制备，样品有较为致密的陶瓷特征，最后经过PIP工艺，样品致密度进一步增加，在其表面有少量碳化硅浮渣生成。CVI碳化硅为均匀吸附于纳米线上，PIP碳化硅以块状填充孔隙为主；Fig. 1 is the appearance diagram of the composite material after the SiC nanowire in Example 1 is dried by suction filtration (1), interface preparation (2), CVI matrix preparation (3) and PIP matrix (4). The flakes after suction filtration have a higher volume fraction of nanowires, and the appearance of the pyrolytic carbon interface becomes black. After the preparation of the CVI matrix, the sample has relatively dense ceramic characteristics. Finally, the density of the sample is further increased after the PIP process. A small amount of silicon carbide scum is formed on its surface. CVI silicon carbide is evenly adsorbed on nanowires, and PIP silicon carbide is mainly filled with pores in blocks;
图2为实施例1中SiC纳米线薄片基体制备经过不同时长CVI和PIP下样品质量的变化，其中(a)不同CVI时长下质量的变化(b)、(c)、(d)和(e)分别对应(a)图中20小时、40小时、50小时和60小时CVI；(f)为50小时CVI结合3次PIP后样品断面电镜图，从图中可知薄片的质量随着CVI时间的增加而增加，从(b)、(c)、(d)和(e)中可以看出薄片的致密度和纳米线的直径逐渐增加，表明CVI对其有一定的致密效果，图(f)显示薄片经过3次PIP后，样品达到较高的致密效果，几乎看不到孔隙；Fig. 2 is the SiC nanowire flake matrix preparation in embodiment 1 and passes through the change of sample mass under different time length CVI and PIP, wherein (a) the change of quality under different CVI time length (b), (c), (d) and (e ) respectively correspond to 20 hours, 40 hours, 50 hours and 60 hours CVI in (a); (f) is the cross-sectional electron microscope image of the sample after 50 hours CVI combined with 3 times of PIP. From (b), (c), (d) and (e), it can be seen that the density of the flakes and the diameter of the nanowires gradually increase, indicating that CVI has a certain densification effect on it. Figure (f) It shows that after three times of PIP, the sample achieves a high densification effect, and almost no pores can be seen;
图3为实施例1中抽滤后制备的网状碳化硅纳米线的SEM照片，从图中可知纳米线交错排列形成均匀的孔道；Fig. 3 is the SEM picture of the mesh silicon carbide nanowire prepared after suction filtration in embodiment 1, it can be seen from the figure that the nanowires are arranged in a staggered manner to form uniform channels;
图4为实施例1中CVI和PIP结合致密后复合材料的断面的SEM照片，从图中可知断面存在很少的孔隙，CVI结合PIP工艺对网状碳化硅纳米线薄片有较好的致密效果。Fig. 4 is the SEM photograph of the cross-section of the composite material after CVI and PIP are combined and densified in Example 1. It can be seen from the figure that there are few pores in the cross-section. .
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| Country | Link |
|---|---|
| CN (1) | CN110304931A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111205100A (en)* | 2020-03-02 | 2020-05-29 | 西北工业大学 | A method for in situ growth of silicon carbide nanowires by impregnation cracking method without catalytic precursor |
| CN111662091A (en)* | 2020-06-15 | 2020-09-15 | 中国科学院上海硅酸盐研究所 | Short carbon fiber reinforced Csf/SiC ceramic matrix composite material and preparation method thereof |
| CN117534495A (en)* | 2023-11-02 | 2024-02-09 | 浙江理工大学 | Method for preparing ceramic matrix composite by combining precursor dipping, cracking and reaction infiltration |
| CN118185525A (en)* | 2024-05-16 | 2024-06-14 | 江苏斯瑞达材料技术股份有限公司 | High-shear-strength thermosetting pressure-sensitive adhesive and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005112702A (en)* | 2003-10-10 | 2005-04-28 | National Institute For Materials Science | SiC composites reinforced by SiC nanowires |
| KR20090110126A (en)* | 2008-04-17 | 2009-10-21 | 한국원자력연구원 | Method for preparing fiber reinforced composite of uniform density by growth of silicon carbide one-dimensional nanostructure with concentration gradient and fiber reinforced composite prepared using the same |
| CN105474791B (en)* | 2012-12-14 | 2015-02-18 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of silicon carbide fiber reinforced ceramic matric composite |
| CN105016759A (en)* | 2015-07-01 | 2015-11-04 | 西北工业大学 | Rapid preparation method for C/SiC composite material |
| CN105237021A (en)* | 2015-09-11 | 2016-01-13 | 西北工业大学 | Method for preparing ceramic matrix composite material through SiC nano-wire modified ceramic matrix composite material interface |
| CN106045571A (en)* | 2016-05-31 | 2016-10-26 | 中钢集团洛阳耐火材料研究院有限公司 | Manufacturing method of gradient porous silicon carbide ceramic tube |
| CN109053195A (en)* | 2018-09-03 | 2018-12-21 | 航天特种材料及工艺技术研究所 | A kind of composite material and preparation method of the method preparing anti-oxidant compound interface layer on fiber preform and excellent combination property |
| CN109095926A (en)* | 2018-08-01 | 2018-12-28 | 中国科学院上海硅酸盐研究所 | A kind of high-volume fractional graphene enhancing carborundum based material and preparation method thereof |
| CN109251049A (en)* | 2018-09-13 | 2019-01-22 | 中国科学院上海硅酸盐研究所 | A method of limitation matrices of composite material propagation of internal cracks |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005112702A (en)* | 2003-10-10 | 2005-04-28 | National Institute For Materials Science | SiC composites reinforced by SiC nanowires |
| KR20090110126A (en)* | 2008-04-17 | 2009-10-21 | 한국원자력연구원 | Method for preparing fiber reinforced composite of uniform density by growth of silicon carbide one-dimensional nanostructure with concentration gradient and fiber reinforced composite prepared using the same |
| CN105474791B (en)* | 2012-12-14 | 2015-02-18 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of silicon carbide fiber reinforced ceramic matric composite |
| CN105016759A (en)* | 2015-07-01 | 2015-11-04 | 西北工业大学 | Rapid preparation method for C/SiC composite material |
| CN105237021A (en)* | 2015-09-11 | 2016-01-13 | 西北工业大学 | Method for preparing ceramic matrix composite material through SiC nano-wire modified ceramic matrix composite material interface |
| CN106045571A (en)* | 2016-05-31 | 2016-10-26 | 中钢集团洛阳耐火材料研究院有限公司 | Manufacturing method of gradient porous silicon carbide ceramic tube |
| CN109095926A (en)* | 2018-08-01 | 2018-12-28 | 中国科学院上海硅酸盐研究所 | A kind of high-volume fractional graphene enhancing carborundum based material and preparation method thereof |
| CN109053195A (en)* | 2018-09-03 | 2018-12-21 | 航天特种材料及工艺技术研究所 | A kind of composite material and preparation method of the method preparing anti-oxidant compound interface layer on fiber preform and excellent combination property |
| CN109251049A (en)* | 2018-09-13 | 2019-01-22 | 中国科学院上海硅酸盐研究所 | A method of limitation matrices of composite material propagation of internal cracks |
| Title |
|---|
| RUAN JING 等: "Interfacial optimization of SiC nanocomposites reinforced by SiC nanowires with high volume fraction", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》* |
| TAO PENGFEI 等: "Improved thermal conductivity of silicon carbide fibers-reinforced silicon carbide matrix composites by chemical vapor infiltration method", 《CERAMICS INTERNATIONAL》* |
| 秦浩 等: "PIP法制备SiC纳米线增强SiCf/SiC复合材料及其力学性能", 《硅酸盐学报》* |
| 陈照峰: "《无机非金属材料学》", 29 February 2016, 西北工业大学出版社* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111205100A (en)* | 2020-03-02 | 2020-05-29 | 西北工业大学 | A method for in situ growth of silicon carbide nanowires by impregnation cracking method without catalytic precursor |
| CN111662091A (en)* | 2020-06-15 | 2020-09-15 | 中国科学院上海硅酸盐研究所 | Short carbon fiber reinforced Csf/SiC ceramic matrix composite material and preparation method thereof |
| CN117534495A (en)* | 2023-11-02 | 2024-02-09 | 浙江理工大学 | Method for preparing ceramic matrix composite by combining precursor dipping, cracking and reaction infiltration |
| CN118185525A (en)* | 2024-05-16 | 2024-06-14 | 江苏斯瑞达材料技术股份有限公司 | High-shear-strength thermosetting pressure-sensitive adhesive and preparation method thereof |
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