CN1671544A - 碳蜂窝体 - Google Patents

碳蜂窝体 Download PDF

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CN1671544A
CN1671544A CNA038134187A CN03813418A CN1671544A CN 1671544 A CN1671544 A CN 1671544A CN A038134187 A CNA038134187 A CN A038134187A CN 03813418 A CN03813418 A CN 03813418A CN 1671544 A CN1671544 A CN 1671544A
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matrix
pyrolysis
honeycomb
stabilisation
fiber
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CN1307045C (zh
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T·谢贝尔
R·维斯
M·亨里希
M·埃伯特
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Schunk Kohlenstofftechnik GmbH
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Abstract

本发明涉及一种制备具有蜂窝结构的碳材料体的方法。为了能以简便的方法制得相应的碳材料体，推荐对由纸张或纤维网制成的、具有蜂窝结构的预成型体进行热解和稳定化处理。

Description

碳蜂窝体
本发明涉及一种制备具有蜂窝结构的碳材料体的方法。
具有蜂窝结构的相应材料体在重量很小的情况下能显示出高刚性的优点。为了能用碳材料制得相应的蜂窝结构，根据US5567500推荐的方法，要使用多层纤维材料层并使其处于相互偏转的纤维方向，同时在相应层之间还要设置一个预设有蜂窝结构的型芯，用以随后通过加热作用硬化这些层，同时实现层间连接。为此要用树脂浸渍这些层。其中所说的层特别是指织物或预浸渍片。
为了能得到特别适用于飞机中的、且兼具重量轻和稳定性好这一特性的夹层结构体或是板材，不得不采用成本昂贵的这种制备方法来构造蜂窝结构。
还存在一种由芳族聚酰胺纸(NOMEX)或铝组成的蜂窝体。
US4518704中记载了一种具有蜂窝状结构的并由活性炭制成的材料体。其中，先要将一种含活性炭的混合物挤出，然后干燥成形体，最后进行热解。
在根据DE4301396C2制备多孔纤维结构体的过程中，首先制备连续纤维的纤维束，然后相互叠加放置成至少两层，最后进行相互连结。
JP57027130A或JP11217278A是用活性炭制得多孔材料体或蜂窝体。其中，在将它们成型后再将这些材料体干燥并热解。
本发明的任务在于提供一种具有蜂窝结构的碳材料体，其能简便地制得且具有高机械强度，并且在保持所需的材料性质的同时还能对其进行调节。
为解决该难题，推荐使用一种预成型的具有蜂窝结构且由树脂浸渍过的纸张或纤维网制成的基体，其中首先对基体进行热解，然后使其稳定化和/或使其致密化。
与已知的现有技术不同，这里使用了一种具有蜂窝结构的预成型基体来制备碳材料体，并且该基体在很大程度上含有一种能转变为碳的材料，由此使得不再需要如现有技术中所需的那种碳织物或预浸渍片的层式结构了。
换句话说，使用可用于商业目的且本身也能商购得的蜂窝体，就能用碳通过热解和稳定化作用制得如下所述的一种蜂窝体，即其能例如被板材所覆盖，用以构成航天航空技术中所需的夹层结构。但是也特别优选可将如此制得的一种具有蜂窝结构的碳材料体用于化学工业中，例如作为催化剂或过滤器。
特别优选将一种由经树脂浸渍过的芳族聚酰胺构成的蜂窝体用作基体。不受此限制地，能通过材料从气相中沉积而使热解后的基体稳定化或致密化。这里优选用C、SiC、B4C和/或Si特别是通过CVI(化学气相渗透)和/或CVD(化学气相沉积)沉淀而使经热解后的基体稳定化或致密化。
此外，还推荐在850℃≤T1≤1100℃、特别优选900℃≤T1≤1000℃的温度T1下碳化该预成型的基体。还可以在1700℃≤T2≤3100℃、特别是1800℃≤T2≤2450℃的温度T2下石墨化该基体。
预成型的基体至少由一种树脂以及一种预设有蜂巢结构的增强介质组成。所谓的树脂指的是如具有高C产率的环氧化物，热塑性塑料如PEEK，PI，酚树脂，呋喃树脂，环氧化的酚醛树脂或其他粘结体系等一类在热解之时和之后能具有或保证粘结或成型稳定性的材料。
预成型的、具有蜂窝结构且由纸张或纤维网制成的基体应该具有耐高温的纤维如C纤维或SiC纤维，或者是具有足够高碳残留量的可热解纤维。属于这些纤维的例子有酚树脂纤维、芳族聚酰胺纤维、亚麻纤维、大麻纤维或其他天然纤维。
但是，在上述的这些物质中优选使用例如由用树脂如酚树脂浸渍过的芳族聚酰胺纸制成的预成型蜂窝体。相应的蜂窝体可从Dupont de Nemours公司购得，且其商品名为NOMEX。
此外，本发明还设计对经热解的且具有蜂窝结构的碳材料体和稳定化体进行后处理或对其进行调质。这同样可通过表面技术如CVI技术(化学气相渗透)、CVD法(化学气相沉积)、沥青涂覆进行或利用含碳的溶液如树脂、环氧树脂、酚树脂进行处理，然后将它们转化成碳而进行。还可以利用能转换成陶瓷如SiC的陶瓷浆进行后处理。
特别优选通过硅化作用构造SiC表面层。为此目的，可使用CVD或CVI法来处理碳材料体，用以形成SiC或PyC(高温石墨层)。还可以用液态沥青或聚合物进行涂层。接着，使经如此涂层的碳材料体碳化或石墨化。
虽然确定具有蜂窝结构的相应碳材料体特别适用于诸如航空航天领域内的夹层结构或面板，但是其也能用于耐高温的领域内，比如作为催化剂和过滤器的载体结构，反应器和化学装置的填料体，在使用有腐蚀性介质的情况下用作高温环境下的高透过性载体结构，化学装置的物质交换部件，解吸塔中用于水处理的填料体，吸收塔中用于净化废气的填料体，液体和气体分配器，热绝缘材料，或诸如加热工艺气体的电阻加热元件。
一般而言，蜂窝结构本身是六边形的，但也可以是其他几何形状，如圆形或矩形。
本发明制备的具有蜂窝结构的碳材料体典型地具有如下尺寸：
板材大小900mm×600mm，蜂窝高度40mm。蜂窝可以具有7mm×4mm和0.2mm的典型壁厚的典型六边形结构。
以下将结合实施例来进一步详细地阐释本发明。从权利要求(其本身和/或相互的结合)中可以得到本发明的其他一些细节、优点和特征。
为将由碳构成的且呈六面体结构的蜂窝体用于承重的夹层板，首先就要将ECA4.8-48型的NOMEX蜂窝体在保护气氛下进行热解。热解在800℃到1050℃的温度范围内进行。然后借助CVI法，利用PyC(高温石墨)沉积使所得到的脆性很高的碳蜂窝结构体稳定化。这个过程要在约1250℃的温度下进行并持续约60小时。
如此制得的碳蜂窝片显示出了良好的耐压值。为进一步提高机械性能，就要利用酚树脂对碳蜂窝片进行树脂浸渍，接着在950℃至1050℃的温度下进行再碳化。为了更进一步提高机械性能，就要将浸渍和再碳化过程重复两次。然后，借助酚树脂粘贴膜，并且在一定的压力(约2bar)和温度(约140℃)下在表面，也就是蜂窝体的端面上施以热压，从而将已预成型的CFC片(碳纤维增强的碳材料片，约2mm厚)粘贴到如此制得的碳蜂窝体材料上。最后在约1000℃的温度下对如此形成的CFC夹层板进行再碳化处理，用以将形成粘结介质的酚树脂膜转变成碳。
按上述方法就制得了高刚性的且能用在高温炉部件中作为承载结构的CFC夹层板。

Claims (12)

1.由树脂浸渍过的纸张或纤维网构成的、具有蜂窝结构的预成型基体用于制备碳蜂窝体的用途，其中先将该基体热解，然后至少使其稳定化和/或致密化。
2.如权利要求1的制备碳蜂窝体的方法，其特征在于，将一种由树脂浸渍过的芳族聚酰胺纸构成的蜂窝体用作基体。
3.如权利要求1的方法，其特征在于，通过气相材料沉积使经热解的基体稳定化或致密化。
4.如权利要求3的方法，其特征在于，特别是通过CVI沉积和/或CVD沉积，利用C、SiC、B4C和/或Si而使所述热解的基体稳定化或致密化。
5.如权利要求1的方法，其特征在于，在经热解后的基体上形成一层SiC或PyC层。
6.如权利要求1的方法，其特征在于，用含碳的溶液如树脂涂覆所述经热解和致密化或稳定化处理过的基体，然后再次进行热解。
7.如权利要求1的方法，其特征在于，用能转化为陶瓷如SiC的陶瓷浆涂覆经热解和稳定化或致密化处理的基体。
8.如权利要求1的方法，其特征在于，在850℃≤T1≤1100℃、特别是900℃≤T1≤1000℃的温度T1下碳化所述具有蜂窝结构的基体。
9.如权利要求1或8的方法，其特征在于，在1700℃≤T2≤3100℃、特别是1800℃≤T2≤2450℃的温度T2下石墨化所述基体。
10.如权利要求1的方法，其特征在于，使用具有耐高温的纤维如碳纤维或SiC纤维，或者是具有足够高碳残留量的可热解的纤维如酚树脂纤维、芳族聚酰胺纤维、亚麻纤维、大麻纤维或其他纤维素纤维作为增强材料的这样一类基体。
11.至少如上述权利要求之一的方法，其特征在于，接着使经热解和稳定化或致密化处理的基体进行进一步的增强或调质处理。
12.至少如上述权利要求之一的方法，其特征在于，对经热解和稳定化或致密化处理过的基体进行硅化处理。
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