CN101460301A - 碳泡沫结构绝缘板 - Google Patents

碳泡沫结构绝缘板 Download PDF

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CN101460301A
CN101460301A CNA2006800512681A CN200680051268A CN101460301A CN 101460301 A CN101460301 A CN 101460301A CN A2006800512681 A CNA2006800512681 A CN A2006800512681A CN 200680051268 A CN200680051268 A CN 200680051268A CN 101460301 A CN101460301 A CN 101460301A
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carbon foam
insulation board
foam core
structural
sip
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D·J·米勒
Y·格里芬
M·塞格尔
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Advanced Energy Technology Inc
Graftech International Holdings Inc
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Graftech International Holdings Inc
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Abstract

结构绝缘板，该结构绝缘板包括碳泡沫芯(12)，该碳泡沫芯具有高压缩强度与密度比、期望的阻燃性质和环境应力抗性。该碳泡沫结构绝缘板(10)也包括与碳泡沫芯(12)的第一表面和第二表面结合的第一层(14)和第二层(16)。碳泡沫结构绝缘板(10)的应用包括住宅和商业建筑、飞行器以及船舶的结构元件和阻燃元件。

Description

碳泡沫结构绝缘板
技术领域
[0001]本发明涉及可用于以下应用的高强度结构板，该应用包括屋顶、地板、墙、门和其它结构的建筑构造，其中高的强度与密度比和改善的阻燃特性是有用的。更详细地讲，本发明涉及碳泡沫在结构绝缘板中的用途，该结构绝缘板高度耐热、湿和其它环境应力，同时维持极高的压缩强度。
背景技术
[0002]许多住宅单元的结构由木材材料和金属钉的组合建造。在结构框架的建造之后，安装绝缘材料如玻璃纤维绝缘层以控制从住宅外部至内部的热传导。也使用经常包含石膏板的内部嵌板，以维持外墙和内表面之间的玻璃纤维绝缘层的放置。虽然该类型的建筑结构可较好地理解和具有足够的强度，但该方法既缓慢又是劳动密集的。此外，这些结构对环境应力如湿气或昆虫维持差的绝缘性和抗性。因此，结构绝缘板(SIPs)用作结构建筑材料已经获得普及。外部的高强度层基本上附接至绝缘内层，产生具有强度和绝缘性两者的夹层。例如，Smith的美国专利第4,163,349号公开了绝缘建筑物，但该绝缘建筑物没有足够的绝热性。
[0003]Hardcastle等(美国专利第4,425,396号)公开了包含合成有机聚合物泡沫的绝缘板，该合成有机聚合物泡沫包含由多个热塑性塑料片组成的保护性风化层。
[0004]Cahi1l(美国专利第6,656,858号)描述了由约0.5-3磅/立方英尺的低密度层和聚合物结构的第二、增强层组成的轻质层压墙。这些结构为轻质的，具有低的抗湿性，满足建筑规范关于横向风载荷的要求。
[0005]Porter(美国专利第6,599,621号)描述了具有高强度和防火和特别防水和湿度变化的SIP。该公开的结构包含内部绝缘芯，该内部绝缘芯在一个表面上具有石膏纤维板，在第二表面上具有定向结构刨花板。优选，该绝缘芯包含塑料泡沫如发泡聚苯乙烯或氨酯，该塑料泡沫与石膏纤维板和定向结构刨花板两者粘合。
[0006]Porter(美国专利第6,588,172号)描述了将塑料浸渍纸的层压层掺入到SIP以增加板的拉伸强度，同时使它防潮。典型地该层置于石膏板和塑料泡沫芯之间，通过常规的粘合剂粘附。
[0007]Parker(美国专利第4,628,650号)描述了包含泡沫芯的SIP，该泡沫芯包含具有从泡沫芯边缘突出的突出部分的层。设置该突出部分以促进相邻SIPs之间的有效密封，提供更好的热绝缘。另外，该板的芯具有穿过用于放置托梁、大头钉或椽的结构的通道。
[0008]Clear(美国专利第6,079,175号)描述了用于建筑结构的粘结材料SIP。将轻质填充材料如底灰、水泥和水倒入两个最外层肋状物的空间之间，据称这为板和因此板包含的结构提供绝缘、强度以及刚度。该SIP的优点为可在偏远地区或更贫瘠的地区构建，因为它构建起来相当便宜。
[0009]Pease(美国专利第6,725,616号)制备绝缘混凝土墙体，该绝缘混凝土墙体用附接至增强绝缘条的块铸造或构建。该专利权人指出，使用专利权人的将增强的硬质泡沫固定至混凝土墙体表面的方法制备绝缘墙体时，使用者将需要较少的时间和劳动。
[0010]Pease(美国专利第6,892,507号)描述用硬质泡沫片制备SIP的方法和装置。硬质泡沫片具有放置增强条的多个凹槽。然后用增强片材将条和硬质泡沫覆盖和粘合，该片材提供结构支撑和保湿性两者。
[0011]不幸地是，先有技术制备的SIPs对于许多要求高强度包括高压缩强度值的结构应用无效。此外，所有先有技术要求保护的大多数SIPs不能有效抗燃烧或经历显著炭化的高温或明火。另外，先有技术SIPs通常缺乏高的强度与密度比，使得这样的SIPs不适于其中建筑结构需要的轻质、绝缘并且坚固的板的应用。
[0012]因此，希望具有低密度和期望的隔热性质的结构板，其中该板具有高强度和高强度与密度比，该高强度和高强度与密度比使碳泡沫结构绝缘板可用于以下的结构应用：包括屋顶、地板、门和墙。的确已经发现，对于不限于住宅建筑物、商业建筑物、飞行器或船舶的结构应用，包括高于先有技术考虑的强度与密度比和压缩强度，以及高于先有技术考虑的阻燃性的特性组合为必需的。
发明内容
[0013]本发明提供独特地能够用于要求高强度与密度比和/或高燃烧或炭化抗性的应用中的SIP。本发明的碳泡沫结构绝缘板显示提供迄今未见到的强度和相对轻质特征的组合的密度、压缩强度和压缩强度与密度比。另外，在从高湿度到严重低温的其它环境条件下，碳泡沫的碳素晶格产品在维持结构完整性的同时抗炭化和燃烧两者。此外，可以期望的尺寸和构型制备碳泡沫，对于结构绝缘板的特定尺寸来讲可容易地机械加工。
[0014]更详细地讲，本发明的结构碳泡沫板具有密度为约0.05-约0.6克/厘米3(g/cc)、压缩强度为至少约2000磅/英寸2(psi)(例如用ASTMC695测定)的碳泡沫芯。当预定用于构造应用时，碳泡沫芯的重要特征为可获得高于7000psi/g/cc的强度与密度比的强度与密度比。
[0015]为了在整个板上一致的热绝缘和强度特征，在纵向和横向上，本发明的结构碳泡沫板都应具有相对均匀密度的碳泡沫芯。特别是，为了提供要求的高压缩强度该碳泡沫应具有相对均匀的孔隙分布，孔隙为相对各向同性的。此外，碳泡沫芯应具有约65％-约95％，更优选约70％-约95％的总孔隙率，以形成碳泡沫结构绝缘板的最佳强度与密度比。
[0016]为制备碳泡沫芯，最好在范围可为约500℃，更优选至少约800℃至约3200℃的温度下，在惰性或空气排除的气氛下将聚合物泡沫块特别是酚醛泡沫块碳化，制备用于结构碳泡沫板的碳泡沫。
[0017]在加入外层之前，可用各种涂料处理碳泡沫芯以改善碳泡沫SIP的总性能。例如，可将抗氧化涂料涂覆至碳泡沫以增加高氧化性条件下的SIP寿命。另外，当暴露于极端温度时，也可将阻燃涂料涂覆至碳泡沫芯以进一步增加碳泡沫芯和因此SIP的完整性。
[0018]因为整体碳泡沫SIP通常设计为平面，因此碳泡沫芯的第一外侧面和第二外侧面覆盖有层。任选，外层之一层可由定向结构刨花板(strand board)(OSB)组成，而其他外层由各种石膏板组成。存在其它外层，该其它外层包括但不限于各种热塑性塑料、有机片材、纤维浸渍物和复合板。
[0019]应将碳泡沫芯粘合至外层以构造SIP。可通过使用材料如在外层和碳泡沫芯之间产生化学相互作用的粘合剂或粘固剂进行粘合。这些材料包括碳泡沫应用专用粘合剂和一般的粘固剂、胶粘剂或高温胶。任选可使用机械材料。
[0020]因此，本发明的一个目的为结构碳泡沫板，该结构碳泡沫板具有确保它用作要求高强度与密度比的结构应用的特征。
[0021]本发明的另一个目的为结构板，其具有碳泡沫芯结构，该结构具有高足以用于高应力结构应用的压缩强度。
[0022]本发明的还另一个目的为结构碳泡沫板，其中碳泡沫芯提供阻燃屏障，该阻燃屏障非常抗燃烧和炭化。
[0023]本发明的还另一个目的为可以期望尺寸和构型制备的结构绝缘板泡沫，其中碳泡沫芯可由机械加工或与其它类似的碳泡沫片结合提供更大的结构碳泡沫板。
[0024]本发明的另一个目的为提供抗环境应力的结构绝缘板，该环境应力包括高湿度和严重的温度波动。
[0025]本发明的还另一个目的为提供结构碳绝缘板，其中碳泡沫芯提供足够的热绝缘以在板的外部和板的内部之间维持温差。
[0026]阅读以下描述后，这些方面和其它方面对技术人员来讲将是显而易见的，通过提供含有碳泡沫芯的结构碳泡沫板，可实现这些方面和其它方面，所述碳泡沫芯的压缩强度与密度比率为至少约7000psi/g/cc，压缩强度与密度比率尤其为至少约8000psi/g/cc。本发明的SIP具有碳泡沫芯，该碳泡沫芯的密度为约0.03g/cc-约0.6g/cc、更优选为约0.05g/cc-约0.15g/cc，压缩强度为至少约2000psi，孔隙率为约65％-约95％。此外，碳泡沫芯的热传导率为约0.06W/mK-约0.3W/mK。
[0027]此外，可通过在惰性或空气排除的气氛下将聚合物泡沫制品，尤其是酚醛泡沫碳化来制备碳泡沫芯。用于碳泡沫芯的酚醛泡沫前体的压缩强度应优选为至少约100psi。
[0028]应理解，上述一般描述和以下详细描述提供本发明的实施方案，并将提供对要求保护的本发明的性质和特征理解的概观或框架。
附图简述
[0029]图1为依照本发明实施方案的碳泡沫结构绝缘板的视图。
实现本发明的最佳方式
[0030]从聚合物泡沫，如聚氨酯泡沫或酚醛泡沫，优选酚醛泡沫制备依照本发明的碳泡沫芯的碳泡沫。酚醛树脂为聚合物和低聚物的大家族，其由基于苯酚和甲醛的反应产物的各种结构组成。当存在酸性或碱性催化剂时，通过苯酚或取代苯酚与醛、尤其是甲醛的反应制备酚醛树脂。酚醛树脂泡沫为由开孔(cell)和闭孔组成的固化***。该树脂通常为氢氧化钠催化的水性甲阶酚醛树脂，其甲醛：苯酚比率可变化，但优选为约2:1。游离苯酚和甲醛含量应为低含量，虽然尿素可用作甲醛清除剂。
[0031]通过调节树脂的水含量和加入表面活性剂(例如乙氧基化非离子型表面活性剂)、发泡剂(例如戊烷、二氯甲烷或氯氟烃)和催化剂(例如甲苯磺酸或苯酚磺酸)制备泡沫。磺酸催化反应，而放热引起发泡剂在树脂中乳化，以使泡沫蒸发和膨胀。表面活性剂控制孔尺寸和开孔单元与闭孔单元的比率。采用间歇过程和连续过程两者。在连续过程中，机器类似于连续聚氨酯泡沫使用的机器。泡沫的性质主要取决于密度和孔结构。
[0032]优选的苯酚为间苯二酚，然而，也可使用能够与醛形成缩合产物的其它类苯酚。这样的苯酚包括一元酚和多元酚、邻苯二酚、对苯二酚、烷基取代的苯酚例如甲酚或二甲苯酚；多环一元酚或多元酚，例如萘酚、对，对′-二羟基联苯(p，p′-dihydrexydiphenyl)二甲基甲烷或羟基蒽。
[0033]用于制备泡沫起始原料的苯酚也可用于与能够以如苯酚一样的方式与醛反应的非酚类化合物混合。
[0034]优选的用于溶液的醛为甲醛。其它合适的醛包括将以同样的方式与苯酚反应的那些醛。这些醛包括例如乙醛和苯甲醛。
[0035]一般而言，可用于本发明的方法的苯酚和醛为美国专利第3,960,761和5,047,225号中描述的那些，其公开内容通过引用结合到本文中。
[0036]任选为增加抗氧化性，可通过只用于改善碳泡沫抗氧化性的化合物特定包含物产生本发明的SIP的碳泡沫芯。这样的固体氧化抑制添加剂包括磷酸铵、磷酸铝、磷酸锌或硼酸。氧化抑制添加剂的另外的特征为可在碳泡沫制备的树脂制备阶段或酚醛泡沫形成阶段期间加入该添加剂。使用任一方法，最后的酚醛泡沫碳化引起磷或硼保留在碳泡沫结构内部，降低碳泡沫的氧化率。特别是，最后的碳泡沫产品中保留的约0.01％-约0.5％重量的磷或硼降低氧化率超过50％。
[0037]或者，在碳化过程完成之后但在SIP中集成之前，可用氧化-抑制剂处理碳泡沫产品。优选的方法为用含磷材料如磷酸铵、磷酸、磷酸铝或磷酸锌的水溶液浸渍碳泡沫，然后热处理至约500℃以同时去除水和将磷固定至碳。另外，可将水溶性硼化合物如硼酸引入上述方法以产生抗氧化性碳泡沫产物。
[0038]在碳泡沫芯的制备中用作起始原料的聚合物泡沫应具有反映待形成的碳泡沫期望的最终密度的初始密度。换句话说，聚合物泡沫的密度应为约0.03g/cc-约0.6g/cc，更优选约0.05g/cc-约0.4g/cc，最优选约0.05g/cc-约0.15g/cc。聚合物泡沫的孔结构应接近约65％-约95％的孔隙率和相对高的压缩强度，即大约为至少约100psi，和高至约300psi或更高。
[0039]为了将聚合物泡沫转变为碳泡沫，在惰性或空气排除的气氛例如在氮气存在的情况下，通过加热至约500℃、更优选至少约800℃、最高达约3200℃的温度，将泡沫碳化。应控制加热速率，以便在几天的时间内使聚合物泡沫达到期望的温度，因为在碳化期间聚合物泡沫可收缩多达约50％或更多。为了有效的碳化，应小心以确保聚合物泡沫片的均匀加热。
[0040]通过使用在惰性或空气排除的气氛下加热的聚合物泡沫，获得非石墨化玻璃碳泡沫，其具有起始聚合物泡沫的近似密度，但压缩强度为至少约2000psi，且强度与密度比显著地为至少约7000psi/g/cc，更优选至少约8000psi/g/cc。碳泡沫具有相对均匀分布的各向同性孔隙，该孔隙的平均长宽比为约1.0-约1.5。
[0041]为了进一步阐述本发明的原则和操作，提供以下表格来阐述碳泡沫芯可具有的不同性质。然而，在任何方面都不应将该表格视为限制。
[0042]通过使用不同密度前体材料，制备用于本发明SIP的碳泡沫芯的一系列碳泡沫。该产品的性质列于下面。
[0043]现在参考图1，该图显示依照本发明的一个实施方案具有碳泡沫芯12的SIP 10局部侧视图。
[0044]碳泡沫芯12和SIP 10通常为平面的，虽然可构造满足各种规格。任选通过机械加工或模塑，碳泡沫芯12可为弯曲的或具有圆形边缘以最好地适合期望的结构应用。
[0045]SIP 10包括位于碳泡沫芯12的相对外表面的第一外层14和第二外层16。如同碳泡沫芯12和SIP 10一样，第一外层14和第二外层16都可具有用于期望应用的各种形状。第一外层14和第二外层16可包含相似的或完全不同的材料，取决于SIP的特定结构应用。这些材料包括典型的构造材料如夹板、定向结构刨花板、干墙、石膏、粘固剂复合材料、木材复合材料或各种其它刚性有机或无机构造板。此外，第一外层14和第二外层16也可为上述材料的浸渍物或包括热塑性塑料、树脂、碳复合材料、陶瓷复合材料或各种其它人工产生的材料。在要求显著刚性或耐磨性的特定结构应用中，可使用各种金属化合物以包含第一外层14和第二外层16两者。在飞行器制造的情况中，这些层可包括环绕碳泡沫芯12的薄金属皮，或在刚性船舶的情况中，外层14和外层16可包括硬化的金属复合材料。显然，第一外层14和第二外层16的选择将基于特定SIP 10的必要拉伸强度和阻燃性质。此外，第一外层14和第二外层16可为两种不同的材料，其中SIP 10的使用需要这样的性质。例如在住宅建筑物结构中，第一外层14可由相当不受环境应力影响的热塑性塑料组成，而第二外层16可为石膏板或住宅建筑物内部更常见的美观的嵌板。可包含外层14和16之一或两者的其它材料包括但不限于以下材料：纸、加强的纸复合材料、定向结构刨花板、纤维板、干墙、石膏、石膏复合材料、木材、木材复合材料、夹板、热塑性塑料、塑料复合材料、树脂、金属、金属合金、金属复合材料及其组合。
[0046]在另外的实施方案中，将膨胀石墨的压缩颗粒片掺入至SIP，处于与碳泡沫芯接触的位置。这些石墨片可位于碳泡沫芯的一个侧面或两个侧面上、位于外层和碳泡沫芯之间。可通过将包含例如硝酸和硫酸混合物的溶液***石墨片，通过暴露于热中使薄片膨胀或剥落，然后压缩剥落的薄片形成相干片来制备合适的膨胀石墨压缩颗粒片(在工业中经常称为＂柔性石墨＂)。在例如美国专利申请公布号US-2005-0079355-A1中描述了膨胀石墨压缩颗粒片的制备，其公开内容通过引用结合到本文中。
[0047]通过将膨胀石墨压缩颗粒片掺入碳泡沫芯，产生了优异的阻燃结构。在碳泡沫芯的一个或两个相对侧面上，压缩膨胀石墨片的各向异性热性质提供热管理的显著改善，允许SIP作为阻燃材料用于多种应用中。
[0048]第一外层14和第二外层16通过粘合或粘结材料18与碳泡沫芯12连接。该粘合或粘结材料18可包括适用于从高温条件至暴露于酸性环境的特定应用的化学粘合剂。不同的化学粘合材料包括粘合剂、胶、粘固剂和胶粘剂。任选可通过机械材料将第一外层14和第二外层16附接至碳泡沫芯12。虽然该方法的确影响碳泡沫芯12的完整性和均匀特性，机械连接可获得低成本，并且非常快的完成。将第一外层14和第二外层16附接至碳泡沫芯12的各种机械附接方法包括但不限于钉、大头钉、螺旋钉、支柱、压杆、扣件、钩环及其组合。另外，可通过外层14和16与碳泡沫芯的一系列高度压缩处理，将第一外层14和第二外层16压粘至碳泡沫芯。虽然比机械或化学附接选项持久差，但该附接类型没有如化学或机械附接方法那样引入额外的化合物或削弱碳泡沫芯12的结构完整性。
[0049]第一涂层20和第二涂层22都是任选的，并涂覆至碳泡沫芯12以改变碳泡沫芯12的性质。特别是，第一涂层20和第二涂层22可相同或不同，取决于碳泡沫芯12的条件和必需的性质。例如第一涂层20和第二涂层22都可为阻燃性改善涂层，以改善碳泡沫芯12的阻燃性。另外，在其中SIP 10的一个侧面更可能暴露于氧化环境，而SIP 10的其他侧面更可能暴露于火中时，第一涂层20可为抗氧化涂层，第二涂层22可为阻燃涂层。并且，任选采用第一涂层20和第二涂层22；对于SIP
10的许多应用，第一涂层20和第二涂层22都不是必需的。
[0050]用碳泡沫芯12作为SIP 10中的绝缘层，SIP 10具有固有的阻燃/抗燃性质。因为其它绝缘材料只从结构绝缘板的结构中排除氧，因此碳泡沫芯12对燃烧或炭化都非常有抗性。特别是，碳泡沫芯12主要将碳与它的泡沫构造内部存在的相对少的其它元件连接。因此，除了碳泡沫芯12的碳的简单氧化以外，几乎没有燃烧存在。为使该氧化发生，温度必须达到相当极端的温度，使得碳泡沫芯12非常适用于其中要求阻燃结构的商业结构和住宅结构中。
[0051]相似地，碳泡沫芯12对许多环境应力有抗性，该环境应力包括昆虫、湿度和热。碳泡沫为非常坚硬的物质，使得它本身不适于昆虫居住，而湿度变化几乎不改变它的化学和结构性质。此外，可选择第一外层14和第二外层16用于SIP 10将经历的特定环境应用。
[0052]最后，SIP 10和它的优异的强度与密度比和阻燃性使得SIP10适用于各种结构应用。在其中期望低密度但牢固的材料，其中也要求阻燃性的建筑物构造中，SIP 10相当特别地有用。此外，含有碳泡沫芯12的SIP 10具有期望的耐热性，因此在建筑物内帮助维持控制的气候。由于其高压缩强度与密度比，SIP 10对于要求轻质和坚固结构的船舶也是理想的。特别是，SIP 10可用于经历多种压缩但必须尽可能轻以维持船舶的机动性的***甲板。此外，SIP 10作为***甲板也将阻燃性元件直接灌注至甲板嵌板中。SIP 10的另外的用途可为飞行器的构建，其中刚性和坚固但轻质的材料是有用的。这些上述应用为本发明的碳泡沫结构绝缘板的可行用途，但绝不表示这些应用包括本发明实用的所有应用。
[0053]因此，通过本发明的实施，制备了具有迄今未被识别特征的包含碳泡沫芯的SIP。这些含有碳泡沫芯的SIP显示特别高的压缩强度与密度比、改善很多的阻燃性和环境稳定性，使得它们在从住宅建筑到飞行器和船舶结构单元的结构应用中独特地有效。
[0054]本申请中参考的所有引用专利和出版物的公开内容通过引用结合到本文中。
[0055]上述描述用于确保本领域技术人员能够实施本发明。不打算详述所有可能的变化和修改，在阅读本说明书后这些变化和修改对技术人员来讲是显而易见的。然而，所有这样的修改和变化将包括在权利要求定义的本发明范围内。权利要求将涵盖有效满足本发明预定目的的任何排列或顺序的指示元件和步骤，除非上下文中明确表明是相反的。

Claims (9)

1.一种结构绝缘板，所述板包含密度为约0.03g/cc-约0.6g/cc的碳泡沫材料。
2.权利要求1的结构绝缘板，所述板还包含：粘合至所述碳泡沫材料第一表面的第一外层；和粘合至所述碳泡沫材料第二表面的第二外层。
3.权利要求1的结构绝缘板，其中所述碳泡沫材料的压缩强度与密度比为约1000psi/g/cc-约20000psi/g/cc。
4.权利要求1的结构绝缘板，其中所述碳泡沫材料的热传导率为约0.06W/mK-约0.3W/mK。
5.权利要求1的结构绝缘板，其中所述碳泡沫材料包括在所述碳泡沫的外表面上的涂层。
6.权利要求5的结构绝缘板，其中所述涂层改善所述碳泡沫材料的阻燃性。
7.权利要求6的结构绝缘板，其中所述涂层改善所述碳泡沫材料的抗氧化性。
8.权利要求1的结构绝缘板，所述板在所述碳泡沫材料的至少一个表面上还包含膨胀石墨的压缩颗粒层。
9.权利要求2的结构绝缘板，其中所述外层选自纸、加强的纸复合材料、定向结构刨花板、纤维板、干墙、石膏、石膏复合材料、木材、木材复合材料、夹板、热塑性塑料、塑料复合材料、树脂、金属、金属合金、金属复合材料及其组合。
CNA2006800512681A 2005-12-21 2006-12-07 碳泡沫结构绝缘板 Pending CN101460301A (zh)

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