CN107963882A - 具有平行排列石墨烯/陶瓷复合材料及低成本制备方法 - Google Patents

具有平行排列石墨烯/陶瓷复合材料及低成本制备方法 Download PDF

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CN107963882A
CN107963882A CN201711118839.5A CN201711118839A CN107963882A CN 107963882 A CN107963882 A CN 107963882A CN 201711118839 A CN201711118839 A CN 201711118839A CN 107963882 A CN107963882 A CN 107963882A
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万春磊
潘伟
孙川
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Abstract

本发明涉及一种具有平行排列石墨烯/陶瓷复合材料及低成本制备方法，属于陶瓷基复合材料技术领域。本方法以可膨胀石墨和陶瓷前驱体为原料，首先对原料可膨胀石墨在常压下加热，得到膨胀石墨；将膨胀石墨与原料陶器前驱体放置于同一容器中，使陶瓷前驱体完全浸润膨胀石墨，真空除泡后得到由膨胀石墨和陶瓷前驱体共同组成的固液混合物；对其进行磁力搅拌，得到石墨烯在陶瓷前驱体中的悬浊液；将乙醇溶液加入悬浊液中并干燥、烘干和烧结，得到石墨烯平行排列的陶瓷基复合材料。本方法使用原料成本低，制备工艺简单、时间短，而且可以多种陶瓷基复合材料，制备的陶瓷基复合材料的力学性能良好，具有良好的电磁屏蔽效能。

Description

具有平行排列石墨烯/陶瓷复合材料及低成本制备方法
技术领域
本发明涉及一种具有平行排列石墨烯/陶瓷复合材料及低成本制备方法，属于陶瓷基复合材料技术领域。
背景技术
石墨烯是一种由sp2杂化的碳原子以六边形周期排列形成的二维结构，其厚度只有0.335nm，是目前世界上发现的最薄却最坚硬的材料，同时也是其他维度碳材料的基本结构单元。陶瓷基复合材料是一种以陶瓷为基体与其它材料复合而成的材料，其中陶瓷基体可为氧化硅、氧化铝、氧化锆或氧化钛等氧化物陶瓷，也可为碳化硅、碳化硼或硼化钛等非氧化物陶瓷。这些陶瓷材料大多具有耐高温、高强度和刚度、相对重量较轻、抗腐蚀等优异性能，而其致命的弱点是具有脆性，处于应力状态时，会产生裂纹，而裂纹极易发生扩展，致使整个材料断裂失效。而采用石墨烯与基体复合，是提高陶瓷韧性和使用可靠性的有效方法。石墨烯的加入对裂纹尖端有着桥连作用，并能够延长裂纹扩展的路径，从而得到有优良力学性能的石墨烯增强陶瓷基复合材料。石墨烯本身可作为一种电磁屏蔽材料，但无法单独使用，而与某些陶瓷材料复合之后，就能够成为一种轻质高强的电磁屏蔽材料。
目前广泛采用的石墨烯/陶瓷复合材料的制备方法是以石墨烯分散液和超细陶瓷粉体为原料，通过长时间的超声和球磨等方式加以混合，再进行烧结，得到石墨烯增强陶瓷基复合材料。这种制备方法的不足之处在于：所涉及的原料价格高昂，无法大量制备复合材料；混合过程不仅耗时耗能，而且破坏了石墨烯原有的片状结构；所制备出的复合材料中，石墨烯分布混乱不均，没有明显的择优取向；复合材料力学性能的改善不够明显，尤其是无法使断裂韧性和抗弯强度同时提高；随机不均的分布也无法发挥石墨烯对电磁波的屏蔽作用。
发明内容
本发明的目的是提出一种具有平行排列石墨烯/陶瓷复合材料及低成本制备方法，以较低的成本制备出具有良好力学性能和电磁屏蔽效能的平行石墨烯增强陶瓷基复合材料，并使制备方法简便易行、成本低廉，适用与工业生产。
本发明提出的具有平行排列石墨烯/陶瓷复合材料，复合材料中的石墨烯处于彼此平行的状态，复合材料中的陶瓷基体为SiO2、Al2O3、ZrO2或SiC中的任何一种。
本发明提出的具有平行排列石墨烯/陶瓷复合材料的低成本制备方法，包括以下步骤：
(1)以可膨胀石墨和陶瓷前驱体为原料，按照可膨胀石墨与陶瓷前驱体的质量比为1︰(400～200)进行称量，所述的陶瓷前驱体为正硅酸乙酯、乙氧基铝或异丙醇锆，陶瓷前驱体在室温下呈液态；
(2)对上述步骤(1)中的原料可膨胀石墨在常压下进行加热，加热温度为750～950℃，加热时间20～30秒，得到膨胀石墨；
(3)将上述步骤(2)的膨胀石墨与原料陶器前驱体放置于同一容器中，使陶瓷前驱体完全浸润膨胀石墨，并用真空除泡，真空度为8～12Pa，真空除泡时间为15～30分钟，得到由膨胀石墨和陶瓷前驱体共同组成的固液混合物；
(4)对上述步骤(3)的固液混合物进行磁力搅拌，搅拌功率为100～200W，转速为1200～1400r/min，搅拌时间2.5～4.5小时，得到石墨烯在陶瓷前驱体中的悬浊液；
(5)配置乙醇与水的质量比为1︰1的乙醇溶液，将乙醇溶液加入到上述步骤(4)的悬浊液中，然后将产物在旋转状态下进行干燥，旋转转速为30～40r/min，干燥温度为60～70℃，干燥时间为45～60分钟；
(6)将上述步骤(5)的产物进行烘干，烘干温度60～90℃，烘干时间为24～30小时，得到干燥的石墨烯/陶瓷混合粉体；
(7)将上述石墨烯/陶瓷混合粉体过200目筛，在压力30～50MPa下，以50～150℃/min的升温速率，升温至烧结温度1300～1500℃，保温3～10分钟，对石墨烯/陶瓷混合粉体进行烧结后得到石墨烯平行排列的陶瓷基复合材料。
本发明提出的具有平行排列石墨烯/陶瓷复合材料及低成本制备方法，其优点是：本发明的制备方法使用原料成本低，制备工艺简单，制备过程时间短，因此可以利用目前绝大多数陶瓷材料制备出多种陶瓷基复合材料。利用本发明方法制备的陶瓷基复合材料中，石墨烯横向尺寸大，石墨烯具有规则的平行排列，因此陶瓷基复合材料的力学性能良好，具有良好的电磁屏蔽效能，可以应用于无线通讯领域。
附图说明
图1是本发明实施例1所制备的石墨烯/SiO2复合材料的显微结构，可以看到平行排列的石墨烯以及石墨烯的横向尺寸。
图2是本发明实施例1所制备的石墨烯/SiO2复合材料的断裂韧性。
图3是本发明实施例1所制备的石墨烯/SiO2复合材料的抗弯强度。
图4是本发明实施例1所制备石墨烯/SiO2复合材料的电磁屏蔽效能。
图5是本发明实施例2所制备的石墨烯/Al2O3复合材料的显微结构，可以看到平行排列的石墨烯以及石墨烯的横向尺寸。
图6是本发明实施例2所制备的石墨烯/SiO2复合材料的力学性能。
图7是本发明实施例3所制备的石墨烯/ZrO2复合材料的显微结构，可以看到平行排列的石墨烯以及石墨烯的横向尺寸。
图8是本发明实施例4所制备的石墨烯/SiC复合材料的显微结构，可以看到平行排列的石墨烯以及石墨烯的横向尺寸。
具体实施方式
本发明提出的具有平行排列石墨烯/陶瓷复合材料，复合材料中的石墨烯处于彼此平行的状态，复合材料中的陶瓷基体为SiO2、Al2O3、ZrO2或SiC中的任何一种。
本发明提出的具有平行排列石墨烯/陶瓷复合材料的低成本制备方法，包括以下步骤：
(1)以可膨胀石墨和陶瓷前驱体为原料，按照可膨胀石墨与陶瓷前驱体的质量比为1︰(400～200)进行称量，所述的陶瓷前驱体为正硅酸乙酯、乙氧基铝或异丙醇锆，陶瓷前驱体在室温下呈液态；
(2)对上述步骤(1)中的原料可膨胀石墨在常压下进行加热，加热温度为750～950℃，加热时间20～30秒，得到膨胀石墨；
(3)将上述步骤(2)的膨胀石墨与原料陶器前驱体放置于同一容器中，使陶瓷前驱体完全浸润膨胀石墨，并用真空除泡，真空度为8～12Pa，真空除泡时间为15～30分钟，得到由膨胀石墨和陶瓷前驱体共同组成的固液混合物；
(4)对上述步骤(3)的固液混合物进行磁力搅拌，搅拌功率为100～200W，转速为1200～1400r/min，搅拌时间2.5～4.5小时，得到石墨烯在陶瓷前驱体中的悬浊液；
(5)配置乙醇与水的质量比为1︰1的乙醇溶液，将乙醇溶液加入到上述步骤(4)的悬浊液中，然后将产物在旋转状态下进行干燥，旋转转速为30～40r/min，干燥温度为60～70℃，干燥时间为45～60分钟；
(6)将上述步骤(5)的产物进行烘干，烘干温度60～90℃，烘干时间为24～30小时，得到干燥的石墨烯/陶瓷混合粉体；
(7)将上述石墨烯/陶瓷混合粉体过200目筛，在压力30～50MPa下，以50～150℃/min的升温速率，升温至烧结温度1300～1500℃，保温3～10分钟，对石墨烯/陶瓷混合粉体进行烧结后得到石墨烯平行排列的陶瓷基复合材料。
以下介绍本发明方法的实施例：
实施例1：制备石墨烯/SiO2复合材料：
(1)以可膨胀石墨和正硅酸乙酯为原料，按照可膨胀石墨与正硅酸乙酯的质量比为1︰380进行称量；
(2)对上述步骤(1)中的原料可膨胀石墨在常压下进行加热，加热温度为800℃，加热时间20s，得到膨胀石墨；
(3)将上述步骤(2)的膨胀石墨与原料正硅酸乙酯放置于同一容器中，使陶正硅酸乙酯完全浸润膨胀石墨，并用真空除泡，真空度为8Pa，真空除泡时间为30min，得到由膨胀石墨和正硅酸乙酯共同组成的固液混合物；
(4)对上述步骤(3)的固液混合物进行磁力搅拌，搅拌功率为100W，转速为1200r/min，搅拌时间2.5h，得到石墨烯在正硅酸乙酯中的悬浊液；
(5)配置乙醇与水的质量比为1︰1的乙醇溶液，将乙醇溶液加入到上述步骤(4)的悬浊液中，然后将产物在旋转状态下进行干燥，旋转转速为30r/min干燥温度为60℃，干燥时间为45min；
(6)将上述步骤(5)的产物进行烘干，烘干温度60℃，烘干时间为30小时，得到干燥的石墨烯/SiO2混合粉体；
(7)将上述石墨烯/SiO2混合粉体过200目筛，在压力30MPa下，以60℃/min的升温速率，升温至烧结温度1300℃，保温3分钟，对石墨烯/SiO2混合粉体进行烧结，得到石墨烯平行排列的SiO2基复合材料。
本实施例制备的石墨烯/SiO2复合材料的显微结构如图1所示，其中的石墨烯彼此平行排列。石墨烯的含量根据原料的配比，可在2～6vol.％之间进行调节。石墨烯/SiO2复合材料的断裂韧性如图2所示，相比纯SiO2陶瓷，提高了2～3倍。石墨烯/SiO2复合材料的抗弯强度如图3所示，相比纯SiO2陶瓷，提高了28～46％。石墨烯/SiO2复合材料的电磁屏蔽效能如图4所示，其中石墨烯含量为5vol.％的复合材料的电磁屏蔽效能达到了37dB，说明该材料是一种良好的电磁屏蔽材料，可用于一般工业或商业用电子产品。
实施例2：制备石墨烯/Al2O3复合材料：
(1)以可膨胀石墨和乙氧基铝为原料，按照可膨胀石墨与陶瓷前驱体的质量比为1︰300进行称量；
(2)对上述步骤(1)中的原料可膨胀石墨在常压下进行加热，加热温度为900℃，加热时间25s，得到膨胀石墨；
(3)将上述步骤(2)的膨胀石墨与原料乙氧基铝放置于同一容器中，使乙氧基铝完全浸润膨胀石墨，并用真空除泡，真空度为10Pa，真空除泡时间为20min，得到由膨胀石墨和乙氧基铝共同组成的固液混合物；
(4)对上述步骤(3)的固液混合物进行磁力搅拌，搅拌功率为150W，转速为1300r/min，搅拌时间3h，得到石墨烯在乙氧基铝的悬浊液；
(5)配置乙醇与水的质量比为1︰1的乙醇溶液，将乙醇溶液加入到上述步骤(4)的悬浊液中，然后将产物在旋转状态下进行干燥，旋转转速为35r/min干燥温度为65℃，干燥时间为50min；
(6)将上述步骤(5)的产物进行烘干，烘干温度75℃，烘干时间为28小时，得到干燥的石墨烯/Al2O3混合粉体；
(7)将上述石墨烯/Al2O3混合粉体过200目筛，在压力40MPa下，以100℃/min的升温速率，升温至烧结温度1450℃，保温6分钟，对石墨烯/Al2O3混合粉体进行烧结，得到石墨烯平行排列的Al2O3基复合材料。
本实施例制备的石墨烯/Al2O3复合材料的显微结构如图5所示，其中的石墨烯彼此平行排列。石墨烯的含量根据原料的配比，可在3～6vol.％之间进行调节。石墨烯/Al2O3复合材料的力学性能如图6所示，相比纯Al2O3陶瓷，断裂韧性提高了40～100％，抗弯强度提高了10～30％。
实施例3：制备石墨烯/ZrO2复合材料：
(1)以可膨胀石墨和异丙醇锆为原料，按照可膨胀石墨与异丙醇锆的质量比为1︰240进行称量；
(2)对上述步骤(1)中的原料可膨胀石墨在常压下进行加热，加热温度为950℃，加热时间20s，得到膨胀石墨；
(3)将上述步骤(2)的膨胀石墨与原料异丙醇锆放置于同一容器中，使异丙醇锆完全浸润膨胀石墨，并用真空除泡，真空度为12Pa，真空除泡时间为15min，得到由膨胀石墨和异丙醇锆共同组成的固液混合物；
(4)对上述步骤(3)的固液混合物进行磁力搅拌，搅拌功率为180W，转速为1400r/min，搅拌时间4h，得到石墨烯在异丙醇锆中的悬浊液；
(5)配置乙醇与水的质量比为1︰1的乙醇溶液，将乙醇溶液加入到上述步骤(4)的悬浊液中，然后将产物在旋转状态下进行干燥，旋转转速为40r/min干燥温度为69℃，干燥时间为60min；
(6)将上述步骤(5)的产物进行烘干，烘干温度90℃，烘干时间为30h，得到干燥的石墨烯/ZrO2混合粉体；
(7)将上述石墨烯/ZrO2混合粉体过200目筛，在压力50MPa下，以150℃/min的升温速率，升温至烧结温度1420℃，保温8分钟，对石墨烯/ZrO2混合粉体进行烧结，得到石墨烯平行排列的ZrO2基复合材料。
本实施例制备的石墨烯/ZrO2复合材料的显微结构如图7所示，其中的石墨烯彼此平行排列。石墨烯含量为5vol.％的复合材料的断裂韧性为7.44MPa·m1/2，抗弯强度为510Mpa，相比纯ZrO2陶瓷，分别提高了120％和31％。
实施例4：制备石墨烯/SiC复合材料：
(1)以可膨胀石墨和正硅酸丙酯为原料，按照可膨胀石墨与正硅酸丙酯的质量比为1︰390进行称量；
(2)对上述步骤(1)中的原料可膨胀石墨在常压下进行加热，加热温度为850℃，加热时间18s，得到膨胀石墨；
(3)将上述步骤(2)的膨胀石墨与原料正硅酸丙酯放置于同一容器中，使陶正硅酸丙酯完全浸润膨胀石墨，并用真空除泡，真空度为12Pa，真空除泡时间为28min，得到由膨胀石墨和正硅酸丙酯共同组成的固液混合物；
(4)对上述步骤(3)的固液混合物进行磁力搅拌，搅拌功率为120W，转速为1250r/min，搅拌时间3h，得到石墨烯在正硅酸丙酯中的悬浊液；
(5)配置乙醇与水的质量比为1︰1的乙醇溶液，将乙醇溶液加入到上述步骤(4)的悬浊液中，然后将产物在旋转状态下进行干燥，旋转转速为35r/min干燥温度为65℃，干燥时间为50min；
(6)将上述步骤(5)的产物进行烘干，烘干温度65℃，烘干时间为28小时，得到干燥的石墨烯/SiC混合粉体；
(7)将上述石墨烯/SiC混合粉体过200目筛，在压力35MPa下，以120℃/min的升温速率，升温至烧结温度1500℃，保温9分钟，对石墨烯/SiC混合粉体进行烧结，得到石墨烯平行排列的SiC基复合材料。
本实施例制备的石墨烯/SiO2复合材料的显微结构如图8所示，其中的石墨烯彼此平行排列。石墨烯的含量根据原料的配比，可在2～6vol.％之间进行调节。石墨烯含量为5vol.％的复合材料的断裂韧性为6.9MPa·m1/2，抗弯强度为550Mpa，相比纯SiC陶瓷，分别提高了75％和40％。

Claims (2)

1.一种具有平行排列石墨烯/陶瓷复合材料，其特征在于该复合材料中的石墨烯处于彼此平行的状态，复合材料中的陶瓷基体为SiO2、Al2O3、ZrO2或SiC中的任何一种。
2.如权利要求1所述的具有平行排列石墨烯/陶瓷复合材料的低成本制备方法，其特征在于该制备方法包括以下步骤：
(1)以可膨胀石墨和陶瓷前驱体为原料，按照可膨胀石墨与陶瓷前驱体的质量比为1︰(400～200)进行称量，所述的陶瓷前驱体为正硅酸乙酯、乙氧基铝或异丙醇锆，陶瓷前驱体在室温下呈液态；
(2)对上述步骤(1)中的原料可膨胀石墨在常压下进行加热，加热温度为750～950℃，加热时间20～30秒，得到膨胀石墨；
(3)将上述步骤(2)的膨胀石墨与原料陶器前驱体放置于同一容器中，使陶瓷前驱体完全浸润膨胀石墨，并用真空除泡，真空度为8～12Pa，真空除泡时间为15～30分钟，得到由膨胀石墨和陶瓷前驱体共同组成的固液混合物；
(4)对上述步骤(3)的固液混合物进行磁力搅拌，搅拌功率为100～200W，转速为1200～1400r/min，搅拌时间2.5～4.5小时，得到石墨烯在陶瓷前驱体中的悬浊液；
(5)配置乙醇与水的质量比为1︰1的乙醇溶液，将乙醇溶液加入到上述步骤(4)的悬浊液中，然后将产物在旋转状态下进行干燥，旋转转速为30～40r/min，干燥温度为60～70℃，干燥时间为45～60分钟；
(6)将上述步骤(5)的产物进行烘干，烘干温度60～90℃，烘干时间为24～30小时，得到干燥的石墨烯/陶瓷混合粉体；
(7)将上述石墨烯/陶瓷混合粉体过200目筛，在压力30～50MPa下，以50～150℃/min的升温速率，升温至烧结温度1300～1500℃，保温3～10分钟，对石墨烯/陶瓷混合粉体进行烧结后得到石墨烯平行排列的陶瓷基复合材料。
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