CN110066175B - 超轻碳化物陶瓷泡沫的制备方法 - Google Patents

超轻碳化物陶瓷泡沫的制备方法 Download PDF

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CN110066175B
CN110066175B CN201910391861.XA CN201910391861A CN110066175B CN 110066175 B CN110066175 B CN 110066175B CN 201910391861 A CN201910391861 A CN 201910391861A CN 110066175 B CN110066175 B CN 110066175B
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唐秀之
曾冠杰
黄小忠
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Central South University
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Abstract

本发明公开了一种制备超轻碳化物陶瓷泡沫的方法，具体包括如下步骤：以清洁干燥的孔隙率超过95％的有机聚合物泡沫为模板，在高温惰性气氛下热解成同时具有三维网络结构和微纳米孔洞结构的碳泡沫；然后将硅源反应物或硼源反应物在惰性气体下加热至气态，并与所述碳泡沫发生碳热反应生成超轻碳化物陶瓷泡沫。本发明的得到的碳化物陶瓷泡沫体积密度小，形状和三维网络结构保持完整，有一定的力学性能，有优异的隔热效果；其次制备方法相较其他方法更为简单环保，能够实现超高孔隙率轻质碳化物陶瓷泡沫大规模生产。

Description

超轻碳化物陶瓷泡沫的制备方法
技术领域
本发明属于无机材料技术领域，具体涉及一种超轻碳化物陶瓷泡沫的制备方法。
背景技术
碳化物是一种高强度、高硬度、耐高温、耐腐蚀、低热膨胀系数的陶瓷材料。将碳化物制备成低体积密度、高孔隙率、高渗透率和高比表面积的陶瓷泡沫，可以广泛增加碳化物的应用范围，例如金属熔融过滤器、催化剂载体、耐火绝缘和太阳能接收器等领域。
常用的碳化物陶瓷泡沫制备方法主要有模板法、有机泡沫浸渍法、溶胶凝胶法、造孔剂造孔法、冷冻干燥法、气相渗透法、先驱体转化法和渗透法等。根据不同的方法制备的陶瓷泡沫的微观结构和形态学以及孔隙率以及碳化物含量皆不相同。
传统方法无法制备孔隙率超过98％的轻质碳化物泡沫，随着技术的发展，目前已有文献报道通过复杂条件可以制备出轻质碳化物泡沫或气凝胶。以碳化硅泡沫为例，例如石墨烯泡沫转化法，先在镍泡沫上通过化学气相沉积制备石墨烯，然后将镍泡沫刻蚀留下石墨烯泡沫，再通过石墨烯泡沫转化为超轻质碳化硅泡沫，该泡沫压缩强度极低，难以在实际中应用；也有以轻质碳泡沫为模板，利用化学气相沉积的方法在其表面沉积一层碳化硅，再空气中高温除碳，但是在气相沉积过程中会产生大量氯化氢腐蚀设备；利用静电纺丝的方法纺出碳化硅纳米纤维或者利用高温制备碳化硅纳米线，再通过冷冻干燥，交联，也可以得到碳化硅气凝胶，该类方法步骤繁琐。上述制备方法条件复杂苛刻，甚至对环境不友好，导致生产成本过高，不适合工业生产。
为了拓展高孔隙率碳化物泡沫陶瓷的商业使用，亟需开发一种适合量产的新型制备方法。
发明内容
本发明针对现有技术中的问题，目的在于提供一种新的制备超轻碳化物陶瓷泡沫的方法。本发明利用宏观上具有三维网状结构、微观上具有微纳米孔洞结构的超大比表面积的碳泡沫与反应物气体反应可以轻易得到孔隙率超过98％并且具有一定力学强度的碳化物陶瓷泡沫，此方法简单、成本低、对环境友好，适合轻质超高孔隙率碳化物泡沫的大规模生产。
所述制备超轻碳化物陶瓷泡沫的方法具体包括如下步骤：
步骤S1以清洁干燥的孔隙率超过95％的有机聚合物泡沫为模板，在高温惰性气氛下热解成同时具有三维网络结构和微纳米孔洞结构的碳泡沫；得到的碳泡沫中碳含量大于90％，孔隙率大于95％，比表面积大于300m2/g；
步骤S2硅源反应物或硼源反应物在惰性气体下加热至气态，并与所述碳泡沫发生碳热反应生成超轻碳化物陶瓷泡沫；得到的碳化物陶瓷泡沫孔隙率大于98％，体积密度5mg/cm3～60mg/cm3，压缩强度在0.05MPa～1.00MPa之间，导热率小于0.10W/m·K。
其中，步骤S1中，所述有机聚合物泡沫为密胺泡沫、聚氨酯泡沫、酚醛泡沫、聚乙烯泡沫、聚甲基丙烯酰亚胺或生物质衍生泡沫。这些所述有机聚合物泡沫为三维有机泡沫，具有三维网状结构。生成的
其中，步骤S2中，所述硅源反应物为一氧化硅、二氧化硅与硅粉混合物、二氧化硅与碳粉混合物、氧基硅烷与碳粉混合物、和、聚碳硅烷中的一种和多种。
其中，步骤S2；所述硼源反应物为三氧化二硼、硼酸、偏硼酸和/或四硼酸。
其中，在步骤S1之前，有机聚合物泡沫用无水乙醇洗涤，并于60℃干燥。
其中，在步骤S1中，热解升温速率为1℃/min～10℃/min，热解温度为400℃～800℃，热解时间为2h～4h。
其中，在步骤S2中，加热速率为1℃/min～10℃/min，碳热反应温度为1000℃～1600℃，碳热反应时间为2h～6h。
其中，所述惰性气体为氮气、氩气、氦气。
在本发明中，术语“三维网络结构”是指：由骨架相互连接组成的三维立体结构。
在本发明中，术语“微/纳米孔洞结构”是指：骨架并不是实心和表面平滑的，在微观上，骨架具有直径为纳米和微米尺度的孔洞和孔道。
本发明实现的技术原理如下：有机聚合物泡沫提供了碳源，硅源反应物或硼源反应物为在常温为固态或者液态，但是在高温下会变为气体状态且能与碳发生反应的物质。有机聚合物泡沫自身就有较小的体积密度和非常大的孔隙率，在惰性气体中逐渐升温，会分解转化为轻质碳泡沫，在这一过程中骨架中H、O和N会和C反应生成小分子逸出，并在骨架上留下了微/纳米级别的小孔。因此，有机聚合物泡沫热解转化的碳泡沫在宏观上为三维网络结构，微观上还具有纳米级的微/介孔结构，即微/纳米孔洞结构，这两种结构共同作用，不但为反应物气体提供了进入骨架内部的通道，也为后续反应提供了丰富的反应活性位点，使碳骨架可以和反应物气体充分接触反应，从而使碳完全转化为碳化物而不受固体扩散规律的影响。
本发明所选择的有聚合物泡沫原料400℃以上热解后能得到成形的碳泡沫，该碳泡沫碳元素含量大于90％，孔隙率大于95％，具有三维网络结构和微纳米孔洞结构，比表面积大于300m2/g。
本发明所选择的硅源反应物或硼源反应物在常温下为固态或者液态，在高温下能升华或者蒸发变为气态，且能与碳发生反应的单质或在高温下能生成并放出能与碳发生反应的气体的混合物以及有机化合物等。
本发明的积极进步效果在于：本发明的得到的碳化物陶瓷泡沫体积密度小，形状和三维网络结构保持完整，有一定的力学性能，有优异的隔热效果；其次制备方法相较其他方法更为简单环保，能够实现超高孔隙率轻质碳化物陶瓷泡沫大规模生产。
附图说明
图1a为实施例1的碳化硅陶瓷立于狗尾草上；
图1b为实施例1的碳化硅陶瓷的XRD谱图；
图1c为以密胺为模板、以一氧化硅为反应物得到的不同密度碳化硅泡沫的压缩强度和模量；
图1d为以密胺为模板、以一氧化硅为反应物得到的不同密度碳化硅泡沫的导热率；
图2a为实施例1得到的碳泡沫的电镜图；
图2b为实施例1得到的碳化硅陶瓷泡沫的电镜图；
图3为实施例1得到的碳化硅陶瓷泡沫结构图；
图4为实施例5得到的碳化硅陶瓷泡沫结构图。
具体实施方式
实施例1～7
步骤S0选用孔隙率超过95％有机聚合物泡沫为模板，用无水乙醇洗涤，60℃烘干。
步骤S1将清洗烘干后的有机聚合物泡沫放入高温炉中，置于刚玉坩埚中，将坩埚放入热解装置，按60ssm流量通入的惰性气体，以V1的升温速率加热到T1℃保温t1小时，然后自然冷却至室温，将碳泡沫用乙醇洗涤，除去吸附的有机小分子，60℃烘干，自然冷却。
步骤S2将步骤S1得到的碳泡沫置于刚玉坩埚中，在距离碳泡沫1cm处放入硅源反应物或硼源反应物，盖上坩埚盖防止升华或者蒸发得到的反应物气体过度逸出。将刚玉坩埚连同盖子放入高温炉，通入流量为60ssm的惰性气体，以V2的升温速率加热到T2℃保温t2小时，然后自然冷却至室温，得到超轻质碳化物陶瓷泡沫。各参数条件如表1所示。
表1实施例1～7反应参数条件
Figure BDA0002056769420000041
Figure BDA0002056769420000051
实施例1～7得到的碳化物陶瓷泡沫的特征参数
Figure BDA0002056769420000052
结论：本发明所制备出的碳化物陶瓷泡沫特征如下：孔隙率大于98％，体积密度5mg/cm3～60mg/cm3可调控，压缩强度在0.05MPa～1.00MPa之间，导热率小于0.10W/m·K。图2为以实施例1制备出的轻质碳化硅泡沫的相关数据。
孔隙率＝100％-轻质碳化硅泡沫的体积密度/碳化硅密度×100％。

Claims (7)

1.一种制备超轻碳化物陶瓷泡沫的方法，其特征在于所述方法具体包括如下步骤：
步骤S1以清洁干燥的孔隙率超过95％的有机聚合物泡沫为模板，在高温惰性气氛下热解成同时具有三维网络结构和微纳米孔洞结构的碳泡沫；
步骤S2硅源反应物或硼源反应物在氮气或惰性气体下加热至气态，并与所述碳泡沫发生碳热反应生成超轻碳化物陶瓷泡沫；
步骤S1中，所述有机聚合物泡沫为密胺泡沫、聚氨酯泡沫、酚醛泡沫、聚乙烯泡沫、聚甲基丙烯酰亚胺或生物质衍生泡沫；
步骤S2中，所述硅源反应物为一氧化硅、二氧化硅与硅粉混合物、二氧化硅与碳粉混合物、氧基硅烷与碳粉混合物、和聚碳硅烷中的一种和多种；
步骤S2中，所述硼源反应物为三氧化二硼、硼酸、偏硼酸和/或四硼酸；
步骤S2中，碳热反应温度为1000℃～1600℃。
2.根据权利要求1所述的方法，其特征在于：在步骤S1之前，有机聚合物泡沫用无水乙醇洗涤，并于60℃干燥。
3.根据权利要求1所述的方法，其特征在于：在步骤S1中，热解升温速率为1℃/min～10℃/min，热解温度为400℃～800℃，热解时间为2h～4h。
4.根据权利要求1所述的方法，其特征在于：在步骤S2中，加热速率为1℃/min～10℃/min，碳热反应时间为2h～6h。
5.根据权利要求1所述的方法，其特征在于：所述惰性气体为氩气、氦气。
6.根据权利要求1所述的方法，其特征在于：步骤S1得到的碳泡沫中碳含量大于90％，孔隙率大于95％，比表面积大于300m2/g。
7.根据权利要求1所述的方法，其特征在于：步骤S2得到的碳化物陶瓷泡沫孔隙率大于98％，体积密度5mg/cm3～60mg/cm3，压缩强度在0.05MPa～1.00MPa之间，导热率小于0.10W/m·K。
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