CN114573357A - 一种SiC纳米线增强SiC陶瓷基复合材料及其制备方法 - Google Patents
一种SiC纳米线增强SiC陶瓷基复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种SiC纳米线气凝胶增强SiC陶瓷基复合材料及其制备方法。本发明的制备方法包括如下步骤：首先采用化学气相沉积法制备SiC纳米线，然后采用纤维冻结成型方法将SiC纳米线自组装成层状结构、纤维紧密交联缠绕的SiC纳米线气凝胶，再通过化学气相渗透在SiC纳米线表面沉积热解碳界面涂层，最后采用真空压力辅助先驱体浸渍热解法，在SiC纳米线气凝胶中原位复合SiC基体。本发明利用SiC纳米线气凝胶的交联网络结构与微纳米多级孔隙分布显著提高SiC陶瓷力学性能，满足航空航天领域高温装备用轻质高强结构材料需求。
Description
技术领域
本发明涉及一种陶瓷基复合材料及其制备方法，特别涉及一种SiC纳米线增强SiC陶瓷基复合材料及其制备方法。
背景技术
SiC陶瓷具有抗氧化性能强、热稳定性能强、热膨胀系数小、抗辐照性能好、耐磨、耐腐蚀，已广泛应用于航空航天、军事、汽车等领域。但是由于SiC陶瓷的高硬度，质地较脆的特性，导致其加工性、应用性较差，这在很大程度上限制了SiC陶瓷在力学性能要求较高的范围内使用，例如发动机的涡轮叶片、防弹装甲等。
SiC纳米线具备柔韧性、弹性、高杨氏模量和拉伸强度，最大弯曲强度可达惊人的53.4GPa，是碳纤维的十倍，因此可作为一种优异的纳米增强体，被广泛应用于复合材料中。将SiC纳米线引入SiC陶瓷基体中形成SiC陶瓷复合材料，可以让两者优势互补，增加强度的同时还可以提高断裂韧性，但是如果简单地将SiC纳米线直接引入SiC陶瓷基体中，由于二者物理化学性质极其相似，导致结合强度过高，不能充分将发挥SiC纳米线的韧性，导致脆性改善不佳。再者，若SiC纳米线在SiC陶瓷基体中复合不均匀，会引起空洞等缺陷，反而会降低SiC陶瓷复合材料的强度。申请号为202010876982.6的中国专利公开了一种SiC纳米线增强SiC陶瓷，其优点在于采用碳涂层包覆来降低SiC纳米线与SiC陶瓷基体之间的结合强度，改善了陶瓷的脆性。但是在SiC纳米线与SiC陶瓷基体的复合过程中不能保证SiC纳米线均匀的复合在SiC陶瓷基体中，有可能大幅降低陶瓷基复合材料的强度。
发明内容
本发明的目的旨在克服现有技术的不足，提供一种SiC纳米线增强SiC陶瓷基复合材料及其制备方法，该方法制得的SiC纳米线纤维增强SiC复合材料具有低密度、耐高温、优异的力学性能等。
为实现上述目的，本发明提供了一种SiC纳米线纤维增强SiC复合材料，体积密度小于2.4g/cm3，由SiC纳米线气凝胶、热解碳界面层与SiC基体组成，其特征在于采用化学气相沉积法制备SiC纳米线，采用纤维冻结成型方法将SiC纳米线自组装成层状结构、纤维紧密交联缠绕的SiC纳米线气凝胶，再通过化学气相渗透在SiC纳米线表面沉积热解碳界面涂层，最后采用真空压力辅助先驱体浸渍热解法，在SiC气凝胶中原位复合SiC基体。所述的SiC纳米线，长度为20nm～2cm，直径为10～100nm；所述的SiC纳米线气凝胶孔隙率75～96％，热解碳界面层厚度为10～500nm，SiC纳米线体积分数3～20％。
一种SiC纳米线气凝胶增强SiC陶瓷基复合材料的制备方法，包括以下顺序步骤：
(1)将聚碳硅烷、二茂铁、活性炭混合，再球磨得到均匀的粉末先驱体，然后将粉末先驱体倒入石墨坩埚，放入高温烧结炉，升温到1200～1700℃生长SiC纳米线；
(2)将步骤(1)中的SiC纳米线加入到去离子水中，经超声形成均匀的分散液，将分散液加热，并在搅拌中加入聚乙烯醇溶液，将该溶液冷却至室温并加入肌醇六磷酸，得到胶体溶液，其中分散液、聚乙烯醇、肌醇六磷酸的体积比为100∶10～25∶0.5～2；
(3)将步骤(2)中的胶体溶液倒入模具中，进行液氮浴冷冻，然后冷冻干燥，即可得到SiC纳米线气凝胶，冷冻干燥温度为-80～-20℃、冷冻干燥时间为2～10天；
(4)将步骤(3)中的SiC纳米线气凝胶在丙烯为碳源、氩气气氛下进行化学气相渗透过程，此过程可在SiC纳米线表面沉积热解碳界面涂层，化学气相渗透温度为600～1200℃，压力为1～10kPa，丙烯和氩气的比例为1～6∶1；
(5)以聚碳硅烷为先驱体溶液，采用真空压力辅助先驱体浸渍裂解法在步骤(4)中制备的SiC纳米线气凝胶内部原位生成SiC基体，固化温度为80～300℃，固化时间为6～20h，热解温度800～1400℃，热解时间1～6h，真空浸渍的真空度为0.05～0.1MPa，真空浸渍时间5h，压力浸渍压力1～3MPa，压力浸渍时间1～6h，循环浸渍-固化-裂解工艺直至浸渍干燥后复合材料增重≤1％，将基体致密的复合材料坯体在高温炉中烧结，烧结温度为900～1300℃，保温时间为1～5h，获得SiC纳米线增强SiC陶瓷基复合材料。
有益效果
(1)利用SiC纳米线钉扎作用，使得SiC纳米线增强SiC复合材料能够获得优异的力学性能(弯曲强度、断裂韧性)。
(2)SiC纳米线具有紧密交联的网络结构、微纳米多级孔隙结构，提高增强相强化效果，复合材料具有的低密度、耐高温等性能特点，使其能够满足航空航天领域高温装备用高性能结构材料需求。
(3)采用化学气相渗透法，制备热解碳界面层，可有效改善SiC纳米线增强SiC陶瓷复合材料界面结合作用、提高断裂韧性。
(4)采用先驱体浸渍热解法，可使SiC基体均匀的填充到气凝胶内部，得到复合均匀和有较低界面结合作用的SiC纳米线增强SiC陶瓷基复合材料。
具体实施方式
下面结合具体实施例，进一步阐明本发明，应理解这些实施例仅用于说明本发明而不用于限制本发明的范围，在阅读了本发明之后，本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定。
实施例1
(1)将聚碳硅烷、二茂铁、活性炭混合，再球磨得到均匀的粉末先驱体，然后将粉末先驱体倒入石墨坩埚，放入高温烧结炉，升温到1500℃生长SiC纳米线；
(2)将步骤(1)中的SiC纳米线加入到去离子水中，经超声形成均匀的分散液，将分散液加热，并在搅拌中加入聚乙烯醇溶液，将该溶液冷却至室温并加入肌醇六磷酸，得到胶体溶液，分散液、聚乙烯醇、肌醇六磷酸的体积比为100∶16∶1；
(3)将步骤(2)中的胶体溶液倒入模具中，进行液氮浴冷冻，然后冷冻干燥机中冷冻干燥，即可得到SiC纳米线气凝胶，冷冻干燥温度为-50℃、冷冻干燥时间为5天；
(4)将步骤(3)中的SiC纳米线气凝胶在丙烯为碳源、氩气气氛下进行化学气相渗透过程，此过程可在SiC纳米线表面沉积热解碳界面层，化学气相渗透温度为900℃，压力为2kPa，丙烯和氩气的比例为3∶1；
(5)将步骤(4)中的SiC纳米线气凝胶在聚碳硅烷与二甲苯先驱体溶液中真空浸渍，然后进行固化、氩气气氛下热解，此过程重复多次，得到SiC纳米线增强SiC陶瓷基复合材料，固化温度为200℃，固化时间为6h，热解温度900℃，热解时间2h，真空浸渍的真空度为0.06MPa，真空浸渍时间5h，压力浸渍压力2MPa，压力浸渍时间4h，循环浸渍-固化-裂解工艺直至浸渍干燥后复合材料增重≤1％，将基体致密的复合材料坯体在高温炉中烧结，烧结温度为1200℃，保温时间为3h，获得SiC纳米线增强SiC陶瓷基复合材料。
该实施例制备的SiC纳米线增强SiC陶瓷基复合材料抗弯强度达到360MPa，断裂强度为4.5MPa·m1/2，在航空航天、军事、汽车等领域具有重要使用价值。
实施例2
(1)将聚碳硅烷、二茂铁、活性炭混合，再球磨得到均匀的粉末先驱体，然后将粉末先驱体倒入石墨坩埚，放入高温烧结炉，升温到1500℃生长SiC纳米线；
(2)将步骤(1)中的SiC纳米线加入到去离子水中，经超声形成均匀的分散液，将分散液加热，并在搅拌中加入聚乙烯醇溶液，将该溶液冷却至室温并加入肌醇六磷酸，得到胶体溶液，分散液、聚乙烯醇、肌醇六磷酸的体积比为100∶18∶1；
(3)将步骤(2)中的胶体溶液倒入模具中，进行液氮浴冷冻，然后冷冻干燥机中冷冻干燥，即可得到SiC纳米线气凝胶，冷冻干燥温度为-50℃、冷冻干燥时间为5天；
(4)将步骤(3)中的SiC纳米线气凝胶在丙烯为碳源、氩气气氛下进行化学气相渗透过程，此过程可在SiC纳米线表面沉积热解碳界面层，化学气相渗透温度为850℃，压力为2kPa，丙烯和氩气的比例为4∶1；
(5)将步骤(4)中的SiC纳米线气凝胶在聚碳硅烷与二甲苯先驱体溶液中真空浸渍，然后进行固化、氩气气氛下热解，此过程重复多次，得到SiC纳米线增强SiC陶瓷基复合材料，固化温度为200℃，固化时间为6h，热解温度900℃，热解时间2h，真空浸渍的真空度为0.06MPa，真空浸渍时间5h，压力浸渍压力2MPa，压力浸渍时间4h，循环浸渍-固化-裂解工艺直至浸渍干燥后复合材料增重≤1％，将基体致密的复合材料坯体在高温炉中烧结，烧结温度为1200℃，保温时间为3h，获得SiC纳米线增强SiC陶瓷基复合材料。
该实施例制备的SiC纳米线增强SiC陶瓷基复合材料抗弯强度达到410MPa，断裂强度为4.8MPa·m1/2，在航空航天、军事、汽车等领域具有重要使用价值。
上述仅为本发明的具体实施方式，但本发明的设计构思并不局限于此，凡利用此构思对本发明进行非实质性的改动，均应属于侵犯本发明保护的范围的行为。但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何形式的简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。
Claims (2)
1.一种SiC纳米线气凝胶增强SiC陶瓷基复合材料，其特征在于包括SiC纳米线气凝胶、热解碳界面层与SiC基体；其特征在于采用化学气相沉积法制备SiC纳米线，采用纤维冻结成型方法将SiC纳米线自组装成层状结构、纤维紧密交联缠绕的SiC纳米线气凝胶，再通过化学气相渗透在SiC纳米线表面沉积热解碳界面涂层，最后采用真空压力辅助先驱体浸渍热解法，在SiC气凝胶中原位复合SiC基体，所述的SiC纳米线，长度为20nm～2cm，直径为10～100nm；所述的SiC纳米线气凝胶孔隙率75～96％，热解碳界面层厚度为10～500nm，SiC纳米线体积分数3～20％。
2.一种SiC纳米线气凝胶增强SiC陶瓷基复合材料的制备方法，包括以下顺序步骤：
(1)将聚碳硅烷、二茂铁、活性炭混合，再球磨得到均匀的粉末先驱体，然后将粉末先驱体倒入石墨坩埚，放入高温烧结炉，升温到1200～1700℃生长SiC纳米线；
(2)将步骤(1)中的SiC纳米线加入到去离子水中，经超声形成均匀的分散液，将分散液加热，并在搅拌中加入聚乙烯醇溶液，将该溶液冷却至室温并加入肌醇六磷酸，得到胶体溶液，其中分散液、聚乙烯醇、肌醇六磷酸的体积比为100∶10～25∶0.5～2；
(3)将步骤(2)中的胶体溶液倒入模具中，进行液氮浴冷冻，然后冷冻干燥，即可得到SiC纳米线气凝胶，冷冻干燥温度为-80～-20℃、冷冻干燥时间为2～10天；
(4)将步骤(3)中的SiC纳米线气凝胶在丙烯为碳源、氩气气氛下进行化学气相渗透过程，此过程可在SiC纳米线表面沉积热解碳界面涂层，化学气相渗透温度为600～1200℃，压力为1～10kPa，丙烯和氩气的比例为1～6∶1；
(5)以聚碳硅烷为先驱体溶液，采用真空压力辅助先驱体浸渍热解法在步骤(4)中制备的SiC纳米线气凝胶内部原位生成SiC基体，固化温度为80～300℃，固化时间为6～20h，热解温度800～1400℃，热解时间1～6h，真空浸渍的真空度为0.05～0.1MPa，真空浸渍时间5h，压力浸渍压力1～3MPa，压力浸渍时间1～6h，循环浸渍-固化-裂解工艺直至浸渍干燥后复合材料增重≤1％，将基体致密的复合材料坯体在高温炉中烧结，烧结温度为900～1300℃，保温时间为1～5h，获得SiC纳米线增强SiC陶瓷基复合材料。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115253938A (zh) * | 2022-08-10 | 2022-11-01 | 航天特种材料及工艺技术研究所 | 一种耐高温抗辐射弹性碳化硅纳米纤维气凝胶材料及其制备方法 |
| CN115259161A (zh) * | 2022-08-10 | 2022-11-01 | 航天特种材料及工艺技术研究所 | 一种套环状碳化硅纳米纤维气凝胶材料及其制备方法 |
| CN116425559A (zh) * | 2023-04-24 | 2023-07-14 | 福建立亚新材有限公司 | 一种定向多孔陶瓷基复合材料的制备方法 |
| CN116814005A (zh) * | 2023-07-03 | 2023-09-29 | 无菌时代复合新材料(苏州)有限公司 | 一种耐高温的碳化硅气凝胶母粒及其制备方法 |
| CN117923936A (zh) * | 2024-03-22 | 2024-04-26 | 中国科学院金属研究所 | 化学气相渗透工艺改性碳纤维制备碳气凝胶复合材料及方法 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807357A (zh) * | 2012-07-13 | 2012-12-05 | 中国科学院研究生院 | 一种块体气凝胶复合材料及其制备方法 |
| CN104803685A (zh) * | 2015-04-08 | 2015-07-29 | 西北工业大学 | 一种微纳米纤维/陶瓷基复合材料的制备方法 |
| CN106898881A (zh) * | 2017-02-20 | 2017-06-27 | 西北工业大学 | 一种三维定向碳化硅纳米线/碳吸波气凝胶的制备方法 |
| CN108117403A (zh) * | 2017-12-13 | 2018-06-05 | 南京航空航天大学 | 一种SiC纳米线增强SiC陶瓷基复合材料及其制备方法 |
| CN108328617A (zh) * | 2018-01-20 | 2018-07-27 | 南京航空航天大学 | 一种碳化硅纳米线气凝胶及其制备方法 |
| CN109020628A (zh) * | 2018-08-04 | 2018-12-18 | 南京航空航天大学 | 一种SiC纳米线增强多孔陶瓷复合材料及其制备方法 |
| KR20200048314A (ko) * | 2018-10-29 | 2020-05-08 | 한국원자력연구원 | 화학기상증착을 이용한 SiC 나노와이어 균일 성장에 의한 고밀도의 탄화규소 복합체 제조 방법 및 이의 의해 제조된 탄화규소 복합체 |
-
2022
- 2022-02-28 CN CN202210189502.8A patent/CN114573357A/zh active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807357A (zh) * | 2012-07-13 | 2012-12-05 | 中国科学院研究生院 | 一种块体气凝胶复合材料及其制备方法 |
| CN104803685A (zh) * | 2015-04-08 | 2015-07-29 | 西北工业大学 | 一种微纳米纤维/陶瓷基复合材料的制备方法 |
| CN106898881A (zh) * | 2017-02-20 | 2017-06-27 | 西北工业大学 | 一种三维定向碳化硅纳米线/碳吸波气凝胶的制备方法 |
| CN108117403A (zh) * | 2017-12-13 | 2018-06-05 | 南京航空航天大学 | 一种SiC纳米线增强SiC陶瓷基复合材料及其制备方法 |
| CN108328617A (zh) * | 2018-01-20 | 2018-07-27 | 南京航空航天大学 | 一种碳化硅纳米线气凝胶及其制备方法 |
| CN109020628A (zh) * | 2018-08-04 | 2018-12-18 | 南京航空航天大学 | 一种SiC纳米线增强多孔陶瓷复合材料及其制备方法 |
| KR20200048314A (ko) * | 2018-10-29 | 2020-05-08 | 한국원자력연구원 | 화학기상증착을 이용한 SiC 나노와이어 균일 성장에 의한 고밀도의 탄화규소 복합체 제조 방법 및 이의 의해 제조된 탄화규소 복합체 |
Non-Patent Citations (1)
| Title |
|---|
| DAOYANG HAN等: "Porous SiCnw/SiC ceramics with unidirectionally aligned channels produced by freeze-drying and chemical vapor infiltration", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115253938A (zh) * | 2022-08-10 | 2022-11-01 | 航天特种材料及工艺技术研究所 | 一种耐高温抗辐射弹性碳化硅纳米纤维气凝胶材料及其制备方法 |
| CN115259161A (zh) * | 2022-08-10 | 2022-11-01 | 航天特种材料及工艺技术研究所 | 一种套环状碳化硅纳米纤维气凝胶材料及其制备方法 |
| CN115253938B (zh) * | 2022-08-10 | 2023-04-18 | 航天特种材料及工艺技术研究所 | 一种耐高温抗辐射弹性碳化硅纳米纤维气凝胶材料及其制备方法 |
| CN116425559A (zh) * | 2023-04-24 | 2023-07-14 | 福建立亚新材有限公司 | 一种定向多孔陶瓷基复合材料的制备方法 |
| CN116814005A (zh) * | 2023-07-03 | 2023-09-29 | 无菌时代复合新材料(苏州)有限公司 | 一种耐高温的碳化硅气凝胶母粒及其制备方法 |
| CN116814005B (zh) * | 2023-07-03 | 2024-01-30 | 无菌时代复合新材料(苏州)有限公司 | 一种耐高温的碳化硅气凝胶母粒及其制备方法 |
| CN117923936A (zh) * | 2024-03-22 | 2024-04-26 | 中国科学院金属研究所 | 化学气相渗透工艺改性碳纤维制备碳气凝胶复合材料及方法 |
| CN117923936B (zh) * | 2024-03-22 | 2024-05-28 | 中国科学院金属研究所 | 化学气相渗透工艺改性碳纤维制备碳气凝胶复合材料及方法 |
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