CN1778673A - 高强度整体碳泡沫体 - Google Patents

高强度整体碳泡沫体 Download PDF

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CN1778673A
CN1778673A CNA200510113865XA CN200510113865A CN1778673A CN 1778673 A CN1778673 A CN 1778673A CN A200510113865X A CNA200510113865X A CN A200510113865XA CN 200510113865 A CN200510113865 A CN 200510113865A CN 1778673 A CN1778673 A CN 1778673A
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D·J·米勒
I·C·勒维斯
R·A·默库里
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Graftech International Holdings Inc
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Abstract

一种碳泡沫体物品，该物品特别可用于复合材料工具或其它高温用途，该物品包括一种压缩强度/密度比为至少约7000psi/g/cc的碳泡沫体。

Description

高强度整体碳泡沫体
[0001]要告知的是，我们一居住在26553Sweetbriar Drive，North Olmstead，Ohio的美国公民Douglas J.Miller、居住在17100Valley Creek，Strongsville，Ohio的美国公民Irwin C.Lewis，和居住在1007 East Deeker Drive，Seven Hills，Ohio的美国公民Robert A.Mercuri-已经发明了一种新的和有用的“高强度整体碳泡沫体”。
技术领域
[0002]本发明涉及可用于多种用途，包括作为复合材料工具的高强度整体碳泡沫体。更具体地说，本发明涉及显示出改善的强度、重量和密度特征的碳泡沫体。本发明也包括这样的泡沫体的制造方法。
背景技术
[0003]碳泡沫体因其低密度加之要么非常高要么非常低的导热性等性能，最近吸引了颇多的活动。惯常，碳泡沫体是经由2条一般路线制备的。可高度石墨化的泡沫体是通过中间相沥青在高压下的热处理生产的。这些泡沫体倾向于有高热导率和电导率。例如，在Klett美国专利No.6,033,506中，中间相沥青在加热的同时施加1000psi的压力，产生一种含有孔度范围为90～200μm的互连孔的开孔泡沫体。按照Klett，在热处理到2800℃之后，该泡沫体的固体部分发展成一种层间间隔为0.366nm的高度结晶石墨结构。该泡沫体经确认有比先有泡沫体大的压力强度(对于0.53g/cc的密度来说，3.4MPa或500psi)。
[0004]在Hardcastle等(美国专利No.6,776,936)中，密度范围为0.678～1.5g/cc的碳泡沫体是通过在一个模型中以可高达800psi的压力加热沥青生产的。该泡沫体经证实是可高度石墨化的而且提供高热导率(250W/M°K)。
[0005]按照H.J.Anderson等在Proceedings of the 43dInternational SAMPE Meeting，P756(1998)中的论文，碳沫泡体是从中相沥青生产的，随后进行氧化热固并碳化到900℃。该泡沫体有开孔结构，其互连孔有不同的形状和范围为39～480μm以上的孔直径。
[0006]Rogers等在Proceedings of the 45th SAMPE Conference，P293(2000)中描述了碳泡沫体从煤系前体通过高压下的热处理的制备，给出密度为0.35～0.45g/cc、压缩强度为2000～3000psi(因而强度/密度比为约6000psi/g/cc)的材料。这些泡沫体有开孔结构，其互连孔的孔度范围可高达1000μm。与上述的中相沥青包沫体不同，它们并非可高度石墨化的。在一份最近的出版物中，描述了这种泡沫体类型的性能(High Performance Composites，September2004，P25)。该泡沫体在密度为0.27g/cc时压缩强度为800psi，或强度/密度比为3000psi/g/cc。
[0007]Stiller等(美国专利No.5,888,469)描述了通过加氢处理煤提取物的压力热处理的碳泡沫体制造。据主张，这些材料当密度为0.2～0.4g/cc时有600psi的高压缩强度(强度/密度比为1500～3000psi/g/cc)。这表明这些泡沫体与那些有不可石墨化的玻璃状碳或玻璃性质者相比是强度更大的。
[0008]碳泡沫体也可以通过聚合物或聚合物前体共混物的直接碳化来制造。Mitchell在美国专利No.3,302,999中讨论了通过使聚氨酯聚合物泡沫体在空气中于200～255℃加热，随后在惰性气氛中于900℃碳化来制备碳泡沫体。这些泡沫体的密度为0.085～0.387g/cc、压缩强度为130～2040psi(强度/密度比为1529～5271psi/g/cc)。
[0009]在美国专利No.5,945,084中，Droege描述了通过热处理从羟基化苯和醛(酚醛树脂前体)衍生的有机凝胶来制备开孔碳泡沫体。该泡沫体的密度为0.3～0.9g/cc、由孔度范围为2～50nm的小型中孔组成。
[0010]Mercuri等(Proceedings of the 9th CarbonConference，P206(1969))通过酚醛树脂热解制备了碳泡沫体。对于密度范围为0.1～0.4g/cc的泡沫体来说，压缩强度/密度比是2380～6611psi/g/cc。对于密度为0.25g/cc的碳泡沫体来说，孔是椭圆形的，孔直径为25～75μm。
[0011]Stankiewicz(美国专利No.6,103,149)以0.6～1.2的受控长宽比制备了碳泡沫体。该专利权人指出，用户往往要求完全各向同性的泡沫体以获得优异性能，理想的是长宽比为1.0。一种开孔碳泡沫体是通过用碳化性树脂浸渍聚氨酯泡沫体，随后热固化和碳化制造的。因此，原来聚氨酯泡沫体的泡孔长宽比从1.3～1.4变成0.6～1.2。
[0012]不幸的是，用先有技术方法制造的碳泡沫体对于很多高温应用例如复合材料工具来说不是有效的。一般市售的泡沫体并不是整体的，而且没有此类应用的强度和强度/密度比要求。此外，有高度互连孔的开孔泡沫体具有使其不适合于这样的应用的孔隙率。
[0013]因此，所希望的是一种整体性的而且有可控泡孔结构的碳泡沫体，其中，泡孔结构、强度和强度/密度比使该泡沫体适合于用来作为复合材料工具以及用于其它用途。的确，已经发现，包括高于先有技术上所期待的强度/密度比在内的特征的组合是碳泡沫体用于复合材料工具用途所必需的。也希望的是此类泡沫体的一种制备方法。
发明内容
[0014]本发明提供一种唯一能用于复合材料工具等用途的碳泡沫体。本发明泡沫体显示能提供此前未见到的强度和相对轻重量特征的组合的密度、压缩强度和压缩强度/密度比。此外，该泡沫体的整体性和相对球形的较大孔和较小孔的组合的双态泡孔结构提供了一种能以所希望尺寸和构型制造而且能容易地切削的碳泡沫体。
[0015]更具体地说，本发明碳泡沫体有约0.05～约0.4克/立方厘米(g/cc)的密度和至少约2000磅/平方英寸(psi)的压缩强度(用诸如ASTM C695测定)。该泡沫体当意在用于高温用途时的一个重要特征是强度与密度之比。对于这样的用途来说，要求强度与密度之比为至少7000psi/g/cc、更好至少约8000psi/g/cc。
[0016]本发明碳泡沫体应当有相对均匀的孔分布，以期提供所要求的高压缩强度。此外，该孔应当是相对各向同性的，这意味着该孔是相对球形的，即该孔有平均约1.0(这代表完美球形几何形状)与约1.5之间的长宽比。该长宽比是通过将任何孔的较长尺寸除以其较短尺寸确定的。
[0017]该泡沫体的总孔隙率应当为约65％～约95％、更好约70％～约95％。此外，已经发现高度有利的是有双态孔度分布，即两种平均孔度的组合，其主要部分是较大尺寸的孔和少部分较小尺寸的孔。较好，这些孔当中，孔体积的至少约90％，更好该孔体积的至少约95％应当是较大孔度部分，而该孔体积的至少约1％，更好该孔体积的约2％～约10％应当是较小孔度部分。
[0018]本发明碳泡沫体中双态孔度分布的较大孔部分应当是直径约10～约150μm、更好直径约15～约90μm，最好直径约25～约95μm。较小孔部分应当包含直径约0.8～约3.5μm，更好约1～约2μm的孔。本发明泡沫体的双态性质提供了一种介于开孔泡沫体与闭孔泡沫体之间的中间结构，从而限制了该泡沫体的液体渗透性而维持泡沫体结构。的确，有利的是，本发明碳泡沫体应当显示出不大于约3.0达西、更好不大于约2.0达西的渗透性(例如，按照ASTMC577测定)。
[0019]有利地是，为了制造本发明泡沫体，让一种聚合物泡沫块、尤其酚醛泡沫块在一种惰性的或不包括空气的气氛中，在范围可从约500℃，更好至少约800℃至可高达约3200℃的温度碳化，来制备可用于高温用途的碳泡沫体。
[0020]因此，本发明的一个目的是一种具有使其能用于高温用途例如复合材料工具用途的特征的整体碳泡沫体。
[0021]本发明的另一个目的是一种具有对高温用途充分的密度、压缩强度和压缩强度/密度比的碳泡沫体。
[0022]本发明的又另一个目的是一种具有能提供不希望有高度连接孔隙率的用途方面的效用的孔隙率和泡孔结构与分布的碳泡沫体。
[0023]本发明的还另一个目的是一种能以所希望尺寸和构型制造、而且能容易地切削或连接以提供更大碳泡沫体结构的碳泡沫体。
[0024]本发明的另一个目的是提供本发明碳泡沫体的一种制造方法。
[0025]这些方面和业内技术人员在审视以下描述时将变得显而易见的其它方面可以通过提供由压缩强度/密度比为至少约7000psi/g/cc、尤其压缩强度/密度比为至少约8000psi/g/cc的碳泡沫体形成的碳泡沫体物品来实现。本发明碳泡沫体有利地具有约0.05～约0.4的密度、至少约2000psi的压缩强度、和约65％与约95之间的孔隙率。该碳泡沫体的孔有平均约1.0～约1.5之间的长宽比。
[0026]较好，该孔的孔体积的至少约90％有约10～约150μm的直径；的确，最好，该孔的孔体积的至少约95％有约25～约95μm的直径。有利地是，该孔的孔体积的至少约1％有约0.8～约3.5μm之间的直径，更好，该孔的孔体积的约2％～约10％有约1～约2μm的直径。
[0027]本发明泡沫体可以通过使一种聚合物泡沫体物品、尤其酚醛泡沫体在一种惰性的或不包括空气的气氛中碳化来制造。该酚醛泡沫体应当较好有至少约100psi的压缩强度。
[0028]要理解的是，以上的一般描述和以下的详细描述都提供本发明的实施方案，且无意提供对权利要求书中所主张的本发明的本质和特征的综述或理解框架。
                    具体实施方式
[0029]按照本发明的碳泡沫体是从聚合物泡沫体例如聚氨酯泡沫体或酚醛泡沫体制备的，较好的是酚醛泡沫体。酚醛树脂是聚合物和低聚物一个大家族，由种类繁多的，以苯酚类与甲醛的反应产物为基础的结构组成。酚醛树脂是通过苯酚或有取代苯酚与醛、尤其甲醛在酸催化剂或碱催化剂的存在下反应制备的。酚醛树脂泡沫体是一种由开放泡孔和密闭泡沫组成的固化系统。该树脂一般是由氢氧化钠催化、甲醛/苯酚比可以改变但较好是约2∶1的水性可熔酚醛树脂。游离苯酚和甲醛含量应当是低的，尽管可以用脲作为甲醛清除剂。
[0030]该泡沫体是通过调整该树脂的水含量和添加表面活性剂(例如乙氧基化非离子型的)、发泡剂(例如戊烷、二氯甲烷、或氯氟碳)、和催化剂(例如甲苯磺酸或苯酚磺酸)来制备的。该磺酸催化反应，而放热引起乳化于该树脂中的发泡剂蒸发并使该泡沫体膨胀。该表面活性剂控制泡孔尺寸以及开孔泡孔与闭孔泡孔单元之比。间歇法和连续法两者都采用。在连续法中，机械类似于连续聚氨酯泡沫体使用的那种。该泡沫体的性能主要取决于孔隙率和泡孔结构。
[0031]较好的苯酚是间苯二酚，然而，能与醛生成缩合产物的这一类的其它苯酚也可以使用。这样的苯酚包括一元苯酚和多元苯酚、焦儿茶酚、氢醌、有烷基取代的苯酚例如间甲酚或二甲基苯酚；多核一元或多元苯酚，例如萘酚、p，p’-二羟基二苯基二甲基甲烷或羟基蒽。
[0032]用来制造泡沫体起始原料的苯酚类也可以以与非苯酚化合物的混合物使用，该非苯酚化合物能以与苯酚相同的方式与醛反应。
[0033]用于该溶液中的较好醛是甲醛。其它适用醛包括那些能以相同方式与苯酚反应者。这些包括，例如，乙醛和苯甲醛。
[0034]一般来说，能用于本发明方法的苯酚类和醛类是其公开文书列为本文参考文献的美国专利No.3,960,761和No.5,047,225中所述的那些。
[0035]用来作为制造本发明碳泡沫体的起始原料的聚合物泡沫体应当有能反映要形成的碳泡沫体的所希望最终密度的初始密度。换言之，该聚合物泡沫体的密度应当为约0.1～约0.6g/cc、更好约0.1～约0.4g/cc。该聚合物泡沫体的泡孔结构应当接近于约65％～约95％之间的孔隙率和相对高的压缩强度，即在至少约100psi和高达约300psi或更高的量级上。
[0036]为了使该聚合物泡沫体转化成碳泡沫体，该泡沫体是在一种惰性的或不包括空气的气氛中，例如在氮气的存在下加热到约500℃、更好至少约800℃至可高达约3200℃的温度碳化的。加热速度应当控制得使该聚合物泡沫体能用若干天的时间达到所希望的温度，因为该聚合物泡沫体在碳化期间会收缩多达约50％或更多。应当小心谨慎，以确保聚合物泡沫件的均匀加热以利于有效碳化。
[0037]通过使用在惰性或不包括空气的环境中加热的聚合物泡沫体，得到一种非石墨化玻璃状碳泡沫体，后者有起始聚合物泡沫体的近似密度、但至少约2000psi的压缩强度，而且重要的是，强度/密度比为至少约7000psi/g/cc、更好至少约8000psi/g/cc。该碳泡沫体有平均长宽比为约1.0～约1.5的各向同性孔的相对均匀分布。
[0038]所得到的碳泡沫体有约65％～约95％、更好约70％～约95％的总孔隙率和双态孔度分布；该孔的孔体积的至少约90％、较好至少约95％是直径约10～约150μm、更好直径约15～约95μm，最好直径约25～约95μm，而该孔的孔体积的至少约1％、更好约2％～约10％是直径约0.8～约3.5μm、更好直径约1～约2μm。本发明泡沫体的双态性质提供一种介于开孔泡沫体与闭孔泡沫体之间的中间结构，从在维持泡沫体结构的同时限制了该泡沫体的液体渗透性。小于3.0达西、甚至小于2.0达西的渗透性是较好的。
[0039]典型地说，孔隙率和单个孔度与形状等特征是用光学法测定的，例如，使用有亮场照明的环氧显微镜装置，而且是使用市售软件例如购自Media cybernetic公司(马里兰州银泉市)的Image-ProSoftware。
[0040]为了进一步说明本发明的原理和操作，提供了以下实施例。然而，这些实施例不应视为任何方面的限制。
                          实施例
[0041]一种尺寸为7.8英寸长、3.9英寸宽、2.9英寸厚的长方形酚醛泡沫块按照以下方式转化成碳泡沫体。该起始酚醛泡沫体的密度为0.32g/cc、压缩强度为约300psi。将该泡沫体装入一个钢罐中、隔绝空气、然后以2℃/小时加热到550℃的温度、以10℃/小时加热到900℃并在该温度保持约20小时。这样得到的碳泡沫体的密度为0.336g/cc、压缩强度为4206psi、强度/密度比为12,517psi/g/cc。该泡沫体的热导率在25℃实测为0.3W/m°K，渗透性实测为0.17达西。
[0042]该泡沫体用光学显微镜考察，该泡沫体的孔隙率实测为79.5％。观察了两组泡孔，这些泡孔外观是固的，直径相当均匀。使用影像分析程序确定两组不同泡孔的平均直径和长宽比。对于有25μm以上直径的大尺寸泡孔来说，计算的平均直径为35μm，标准偏差为24μm。泡孔长宽比计算为1.16，表明它们基本上是球形的。这些大孔占总孔隙率的孔体积的96％。占总孔隙率的孔体积的4％的小尺寸泡孔的平均直径为1.75μm、标准偏差为0.35。这些泡孔的长宽比实测为1.10。
[0043]与其它泡沫体比较，该泡沫体的泡孔结构的独特之处在于它显然介于闭孔构型与开孔构型之间。大泡孔显然只由小孔彼此弱连接，因而该泡沫体在水的存在下显示出渗透性但不容易吸收更粘的液体。
[0044]使用不同密度前体材料制造一系列碳泡沫体。这些产品的性能列于以下：
  泡沫体1   泡沫体2   泡沫体3
  密度g/cc   0.266   0.366   0.566
  压缩强度(psi)   2263   4206   8992
  压缩强度/密度   8.507   12.517   16.713
[0045]因此，通过本发明的实施，制备了有此前未认识到的特征的碳泡沫体。这些泡沫体显示出格外高的压缩强度/密度比，并有与众不同的双态泡孔结构，使其在复合材料工具用途等用途上变得独特地有效的。
[0046]本申请中引用的专利和所参照的出版物的公开内容全都列为本文参考文献。
[0047]以上描述意在使业内技术人员能实施本发明。无意详细说明所有可能的变异和修饰，这对于业内技术人员来说在阅读该描述时将变得显而易见。然而，意图是所有这样的修饰和变异都包括在随后权利要求书所界定的本发明范围内。该权利要求书意在涵盖能有效地达到本发明意向目标的任何安排或序列中所指出的要素和步骤，除非上下文具体指出矛盾之处。

Claims (22)

1.一种碳泡沫体物品，包含压缩强度/密度比为至少约7000psi/g/cc的碳泡沫体。
2.权利要求1的物品，其中该碳泡沫体的压缩强度/密度比为至少约8000psi/g/cc。
3.权利要求2的物品，其中该碳泡沫体的密度为约0.05～约0.4，压缩强度为至少约2000psi。
4.权利要求3的物品，其中该碳泡沫体的孔隙率为约65％～约95％。
5.权利要求4的物品，其中该碳泡沫体的泡孔有平均约1.0～约1.5的长宽比。
6.权利要求1的物品，其中该泡孔的孔体积的至少约90％有约10～约150μm的直径。
7.权利要求6的物品，其中该泡孔的孔体积的至少约95％有约25～约95μm的直径。
8.权利要求6的物品，其中该泡孔的孔体积的至少约1％有约0.8～约3.5μm的直径。
9.权利要求8的物品，其中该泡孔的孔体积的约2％～约10％有约1～约2μm的直径。
10.权利要求1的物品，其渗透性不大于约3.0达西。
11.一种碳泡沫体物品，包含一种有如下孔度分布的碳泡沫体：该泡孔的孔体积的至少约90％有约10～约150μm的直径，且该泡孔的孔体积的至少约1％有约0.8～约3.5μm的直径。
12.权利要求11的物品，其中该泡孔的孔体积的至少约95％有约25～约95μm的直径。
13.权利要求12的物品，其中该泡孔的孔体积的约2～约10％有约1～约2μm的直径。
14.权利要求11的物品，其中该碳泡沫体的压缩强度/密度比为至少约7000psi/g/cc。
15.权利要求14的物品，其中该碳泡沫体的压缩强度/密度比为至少约8000psi/g/cc。
16.权利要求15的物品，其中该碳泡沫体的密度为约0.05～约0.4，压缩强度为至少约2000psi。
17.权利要求16的物品，其中该碳泡沫体的孔隙率为约65％～约95％。
18.权利要求17的物品，其中该碳泡沫体的泡孔有平均约1.0～约1.5的长宽比。
19.权利要求11的物品，其渗透性不大于约3.0达西。
20.一种碳泡沫体物品的制造方法，包含使一种聚合物泡沫体物品在一种惰性或不包括空气的气氛中碳化。
21.权利要求20的方法，其中该聚合物泡沫体物品包含一种酚醛泡沫体。
22.权利要求21的方法，其中该酚醛泡沫体的压缩强度为至少约100psi。
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EP1805005A4 (en) 2011-08-24
WO2006047033A3 (en) 2006-10-12
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CN1778673B (zh) 2014-06-25
KR100934821B1 (ko) 2009-12-31
EP1805005B1 (en) 2013-01-02
KR20090082875A (ko) 2009-07-31
US20070029687A1 (en) 2007-02-08
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US20060086043A1 (en) 2006-04-27

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