CN106660350B - 复合材料片材以及包含其的货物集装箱 - Google Patents
复合材料片材以及包含其的货物集装箱 Download PDFInfo
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- CN106660350B CN106660350B CN201580027876.8A CN201580027876A CN106660350B CN 106660350 B CN106660350 B CN 106660350B CN 201580027876 A CN201580027876 A CN 201580027876A CN 106660350 B CN106660350 B CN 106660350B
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- paper wood
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Abstract
本发明涉及非刚性复合材料片材,其依次包括:(i)具有88至678gsm的面积重量的第一组件,其包括具有至少11g/分特韧度的长丝纱线的第一织物和紫外线和气候不渗透的第一聚合物层,(ii)具有120至430gsm的面积重量的第二组件,其包括耐火纸材,并且(iii)具有88至678gsm的面积重量的第三组件,其包括具有至少11g/分特的韧度的长丝纱线的第二织物以及耐冲击和耐刮擦第二聚合物层,所述第三组件的第二织物邻近所述第二组件的纸材。
Description
背景技术
技术领域
本发明涉及具有阻燃特性的非刚性复合材料片材。所述片材可用作货 物集装箱,具体地飞机里使用的集装箱中的壁。
相关领域的描述
货物集装箱或集装设备(ULD)用于飞机、船舶、公路车辆和有轨车 辆中以运载货物。出于经济原因,期望减小空集装箱的重量,同时使其操 作成本最小化。在空运货物集装箱中运输易燃材料对航空公司和航空货运 公司造成严重的安全问题。越来越关注当点火源为货物本身时,现有集装 箱克制火势蔓延的能力。此类点火源的示例为锂离子电池。因此,为预防 可能的人员伤亡和货物设备损失,航空公司和航空货运公司正在寻找阻燃 货物集装箱以克制可源于集装箱内的火灾。预计在未来几年内将加强监管 要求。因此需要提供轻质货物集装箱,其具有克制集装箱内火势蔓延的增 强能力,满足严格的耐用性标准,同时提供延长的寿命与最小的维护。
授予Richardson等人的美国专利8,292,027描述了复合材料层合体,其 依次包括:(a)阻燃聚合物防潮层(b)无机薄片层和(c)阻燃热塑性膜 层。
授予Mormont和Jacques的美国专利申请公布2003/0170418公开了防 护产品,其具有隔热和隔音特性,使得其满足由联邦航空局发布的标准14 CFR,第25部分的要求。所述产品被设计成沿金属和复合材料结构(诸如 飞机驾驶舱、船体或火车或其它运输工具的外部结构)施用。所述产品基 本上呈“垫”的形式,所述垫由包封在外壳中的一个或多个纤维层,优选 地玻璃纤维组成。所述外壳一般包括至少一个第一支撑体,其优选地由具 有密封和防凝特性的有机材料制成,以及浸渍的云母纸。云母纸优选具有 小于50gsm的重量/单位面积并且包含具有大于1000的形状因子的云母 片。
在2004年11月18日在Lisbon的火灾和客舱安全研究会议上,在题目 为“Development of a Thermal/Acoustic Insulating Blanket Responding to the FAR25.856 by the Integration of Mica Flame Barrier”的展示中,Jacques和 Orance描述了开发了用于飞机机身的构造中的云母纸。
发明内容
本发明涉及非刚性复合材料片材,其依次包括:
(i)具有88至678gsm的面积重量的第一组件,其包括具有至少11g/ 分特韧度的长丝纱线的第一织物和第一聚合物层,
(ii)具有120至430gsm的面积重量的第二组件,其包括邻近第一组 件的第一织物和第三组件的第二织物定位的纸材,所述纸材进一 步包含芳族聚酰胺纤维、聚合物粘结剂和云母,以及
(iii)具有88至678gsm的面积重量的第三组件,其包括具有至少11g/ 分特的韧度的长丝纱线的第二织物和第二聚合物层,所述第三组 件的第二织物邻近所述第二组件的纸材,
其中
(a)所述第一织物和第二织物的纱线包含芳族聚酰胺、芳族共聚 酰胺、玻璃纤维或碳纤维,并且
(b)所述第一组件的第一聚合物层和所述第三组件的第二聚合物 层的聚合物为聚氨酯、聚乙烯、聚丙烯、聚萘二甲酸乙二醇 酯、聚丙烯腈、含氟聚合物、聚酰亚胺、聚酮、聚酰亚胺、 聚砜、聚芳硫醚、液晶聚合物、聚碳酸酯或离聚物。
附图说明
图1A和1B示出货物集装箱的透视图。
图2A至2C示出穿过本发明的非刚性复合材料片材的实施方案的横截 面。
具体实施方式
图1A以标记10示出适用于航空、海运容器等的阻燃货物集装箱,其 克制货物集装箱内火灾的影响。图1示出机架组装件11、侧壁12a和 12b、以及顶部13。图2B示出容器,所述容器包括机架组装件11、多个侧 壁12a至12e、顶部13和底部14。侧壁和顶板包括非刚性阻燃复合材料片 材。
非刚性阻燃复合材料片材。
图2A以标记20整体示出通过非刚性阻燃复合材料片材的一个实施方 案的横截面,其依次包括第一组件21、第二组件22和第三组件23。所述 片材布置在货物集装箱的机架之间使得第三组件是面向货物31的最内组件 并且第一组件是远离货物30的最外组件。
优选地,当根据ASTM D3039/D3039M-08测试时,复合材料片材具 有至少350N/cm(200lb.per in.)的断裂强度。在一些实施方案中,复合材 料片材具有至少525N/cm(300lb.per in.)或甚至至少700N/cm(400lb.per in.)的断裂强度。
复合材料片材的一些实施方案提供对具有927℃,+/-38℃(1700°F, +/-100°F)的直接火焰的耐穿透性。一些规格还要求在施用火焰源之后五 分钟内没有火焰穿透样本,并且其中当根据火焰穿透FAA测试法14CFR 25.855附录F第III部分-测定货物隔室衬里(顶板位置)的耐火焰穿透性的 测试方法测试时,在水平测试样本的上表面上方101.6mm(4英寸)处测量 的峰值温度不超过204℃(400°F)。
优选地,复合材料片材可承受对-50℃至+80℃的温度范围的暴露而不 损害其在最终产品的寿命跨度内的可靠性和耐久性。
在一些实施方案中,第一组件、第二组件和第三组件可任选地通过诸 如粘合剂或热层压的方式彼此粘结。
第一组件
第一组件21具有88至678gsm(2.6至20oz./sq.yd.)的面积重量并且 包括具有至少11克/分特(10克/旦尼尔)的韧度的连续长丝纱线的第一织 物25和第一聚合物层24,所述聚合物层为复合材料片材的最外层。聚合物 层提供对物理和化学攻击和液体渗透的化学和环境(即,气候和紫外线) 抵抗性。
所谓化学和环境/气候抵抗性是指聚合物层承受(但不过度降解)风、 雨、污染物诸如存在于典型的工业区域中的酸性和/或油性残余物的影响, 和阳光暴露的能力。优选地,聚合物层具有抵抗由化学反应性、或溶剂作 用、烃、化学品、臭氧、细菌、真菌和湿气、以及皮肤油造成的,典型地 与商用飞机相关联的操作和维护相关联的损坏的增强的能力。
所谓防紫外线是指,当暴露于紫外线辐射时,聚合物层保留其外观和 物理完整性,但不过度降低其柔韧性和机械特性(即,脆性)。优选地, 聚合物层阻隔至少95%的紫外线,更优选地至少98%且最优选地100%的紫 外线。第一聚合物膜的紫外线不可渗透性可通过在聚合物材料中包含添加 剂进一步减轻。此类添加剂的示例包括填料、颜料、稳定剂和润滑剂。不 与第一织物接触的第一聚合物层的外表面可任选地利用紫外线阻隔材料进行涂覆或处理。
紫外线(UV)是在可见光谱的上限处的不可见辐射带。在10至 400nm范围内的波长处,紫外线(UV)在可见光的末端处开始并且在X射 线的开始处结束。因为复合材料片材对紫外线的主要暴露是阳光,所以最 重要的防紫外线性是对于较低频率、较长波长的射线。
优选地,第一聚合物层具有软的、非塑性感觉,其对于与人类皮肤进 行接触的产品而言是理想的并且在产品寿命跨度范围内,在宽温度范围 内,甚至在低至-50℃(-60°F)的温度下,维持其韧度和柔韧性。
在一些实施方案中,第一织物层25可通过化学、热或机械方式粘结到 第一聚合物层24。在一些实施方案中,第一聚合物层可浸渍到第一织物 中。
在一些实施方案中,第一织物和第一聚合物层之间的粘结强度为至少 263N/m(1.5lb./in)。在另一个实施方案中,第一织物和第一聚合物层之间 的粘结强度为至少438N/m(2.5lb./in)、或甚至至少876N/m(5lb./in)。
当将粘合剂用于化学粘合时,优选粘合剂的面积重量介于2至40gsm 之间。粘合剂层可以为热塑性树脂或热固性树脂。热固性树脂包括环氧树 脂、环氧酚醛树脂、酚醛树脂和聚酰亚胺。热塑性树脂包括聚酯、聚氨 酯、聚醚酮、聚醚醚酮、聚醚酮酮、聚醚砜和聚烯烃。优选热塑性树脂。
优选地,所述粘合剂层可任选地包含最多40重量百分比的阻燃剂成 分。适宜的阻燃成分包括三氧化锑,卤化阻燃剂包括四溴双酚A、多溴联 苯、五溴二苯醚(氧化物)、八溴二苯醚(氧化物)、十溴二苯醚(氧化 物)和六溴环十二烷。含磷阻燃剂诸如基于有机磷酸盐的那些也是适宜 的。
在一些实施方案中,粘合剂层阻隔至少95%的紫外线,更优选至少 98%且最优选100%的紫外线。粘合剂可进一步包含填料、颜料、稳定剂、 和其它性能增强添加剂。
粘合剂必须能够在75至200℃范围内的温度下活化,即形成键。在一 些实施方案中,活化范围为120至140℃。所谓活化,是指就热固性树脂而 言,树脂必须在规定温度范围内固化并粘结到聚合物层和织物。就热塑性 树脂而言,活化是指树脂充分地软化并流动以粘结到聚合物层和织物。
第二组件
在一些实施方案中,第二组件22具有120至430gsm的面积重量并且 包括阻燃纸材26。在一些实施方案中,如图2A所示,第二组件的纸材26 邻近第一组件的第一织物25和第三组件的第二织物28。
在一个实施方案中,基于芳族聚酰胺纤维加粘合剂的合并重量计,所 述纸材包含40至70重量百分比的芳族聚酰胺纤维和30至60重量百分比的 聚合物粘合剂。在另一个实施方案中,纸材包含40至55重量百分比的芳 族聚酰胺纤维和45至60重量百分比的粘合剂。在一些其它实施方案中, 纸材包含40至90重量百分比的芳族聚酰胺纤维和10至60重量百分比的粘 合剂。在另一个实施方案中,纸材包含40至60重量百分比的芳族聚酰胺 纤维和40至60重量百分比的粘合剂。优选的粘合剂为优选地呈沉析纤维 形式的间位芳族聚酰胺。
所述纸材进一步包含添加剂、无机材料诸如云母、蛭石、陶瓷纤维、 玻璃纤维以及它们的共混物。
优选地,基于纸材总重量计,阻燃纸材包含25至60,优选地35至35 重量百分比的间位芳族聚酰胺沉析纤维,0至20,优选地10至15重量百 分比的间位芳族聚酰胺絮状物,以及40至90或40至70,优选地45至55 重量百分比的添加剂。具有小于25重量百分比间位芳族聚酰胺沉析纤维的 组合物缺乏所需的柔韧性和强度,然而具有大于60重量百分比间位芳族聚 酰胺沉析纤维的组合物在火焰中太弱而不能防止崩解。具有一些间位芳族 聚酰胺絮状物的组合物表现出改善的强度和柔韧性但具有大于20重量百分 比的絮状物的组合物表现出减小的强度和组合物粘结性。具有小于40重量 百分比添加剂的组合物缺乏承受火焰穿透所需的耐热性,然而具有大于90 重量百分比添加剂的纸材组合物太硬且脆。
如本文所用,术语“沉析纤维”是指基本上为二维薄膜状小颗粒的细 分聚合物产品,其具有100至1000微米的长度和宽度和0.1至1微米的厚 度。通常通过使聚合物溶液流动至与该溶液的溶剂不混溶的液体凝固浴中 来制备沉析纤维。聚合物溶液流在聚合物凝聚时受到剧烈剪切力和紊流的 影响。
纤维可以呈絮状物的形式。絮状物一般包含通过将连续长丝纤维切割 成较短长度但不显著原纤化而制成的短纤维;并且短纤维的长度可以为几 乎任何长度。适宜范围的示例为1mm至12mm(对于强化纤维)和5mm 至800mm(对于纺制成纱的短纤维)。适用于本发明的短纤维为授予 Hoinesss的美国专利5,474,842所公开的强化纤维。
云母是优选的添加剂材料。云母是呈多种单斜形式的结晶矿物质硅酸 盐,其易于分离成非常薄的叶或片。云母的示例为花岗岩钾和辉石云母。 在一些实施方案中,云母具有100至500微米的薄片粒度和0.05至0.15微 米的厚度。
蛭石为水合的硅铝酸镁云母状的矿物质,以多层结晶天然存在。蛭石 通常包含按重量(干重)计以理论氧化物计约38%-46%的SiO2、约16%- 24%的MgO、约11%-16%的Al2O3、约8%-13%的Fe2O3,并且其余的一般 为钾、钙、钛、锰、铬、钠以及钡的氧化物。“片状脱落的”蛭石指的是 已经过化学处理或热处理而使晶体层膨胀并且分离,从而产生高纵横比的 蛭石片状物的蛭石。
氧化铝-硅酸盐纤维是陶瓷纤维的示例。
适宜的纸材包括购自DuPont的418和419,其包含间 位芳族聚酰胺纤维和云母的共混物,所述云母以约50重量百分比的量存 在。添加这些性能增强添加剂是为了赋予纸材和复合材料片材诸如改善的 防火性、导热性、尺寸稳定性等的特性。在一些实施方案中,将纸材压 延。
用于本发明的纸材厚度取决于层合体的最终用途或所需性质,但是为 了提供整体高柔韧度和最低可用重量,其通常为0.100至0.375mm或甚至 0.125至0.250mm厚。纸材厚度可甚至为0.150至0.200mm。低于0.100mm 的纸材厚度可导致不可取的特征结构诸如较弱和较少尺寸稳定的第二组 件,与不令人满意的阻燃性。具有大于0.375mm厚度的纸材可增加不可取 的重量和硬度。
在一些实施方案中,纸材的基重为135至315gsm或195至255gsm。在一些实施方案中,所述纸材具有不大于10%的含水量。
纸材具有沿第一方向至少2625N/m(15lb/in)的干拉伸强度和沿第二 方向至少1750N/m(10lb/in)的干拉伸强度,该第二方向横向于该第一方 向。所谓干拉伸强度意指已在环境温度和湿度下,通常在48%-52%的相对 湿度和22℃-24℃下适应的纸材的拉伸强度。TAPPI T-402 sp-08是限定了用 于纸材、板以及纸浆产品的环境条件的示例性规范。需要沿第一方向的干 拉伸强度为至少1225N/m(7lb/in)以确保通过后续的工艺步骤对纸材进行 适当的处理,特别是确保在卷绕期间形成紧密的卷筒,从而防止卷筒松垂 和伸缩式套叠。
在一些实施方案中,纸材具有沿第一方向至少5000N/m的干拉伸强度 和沿第二方向至少3500N/m的干拉伸强度。纸材可甚至具有沿第一方向至 少6500N/m的干拉伸强度和沿第二方向至少4500N/m的干拉伸强度。
纸材的芳族聚酰胺纤维可以为间位芳族聚酰胺、对位芳族聚酰胺或两 者的组合。
芳族聚酰胺纤维的高温特性确保了当纸材可暴露于150℃的温度至少 10分钟时纸材在加工步骤期间的热稳定性和机械稳定性,也就是说,当经 历150℃的温度至少10分钟时,纸材将不改变尺寸。
纸材的芳族聚酰胺纤维可以为絮状物形式、纸浆形式、或它们的组 合。本文所用,术语“芳族聚酰胺”是指聚酰胺,其中至少85%的酰胺(- CONH-)连接基直接连接到两个芳族环。添加剂可与芳族聚酰胺一起使 用。实际上已发现,可将多达10重量%的其它聚合材料与芳族聚酰胺共 混,或者可使用共聚物,所述共聚物具有多达10%的替代芳族聚酰胺的二 胺的其它二胺,或多达10%的替代芳族聚酰胺的二酰氯的其它二酰氯。
一般通过将连续的卷绕丝切割成具体长度的段来制备絮状物。如果絮 凝物的长度小于2毫米,其一般太短而无法为纸材提供足够的强度。如果 絮凝物的长度大于25毫米,其将非常难以形成均匀的湿法成网的纤维网。 制备的具有小于5微米,尤其是小于3微米的直径的絮状物难以具有足够 的剖视均匀性和再现性;如果絮状物的直径大于20微米,其将非常难以形 成均匀的纸张重量由轻至中等的纸材。
如本文所用,术语“纸浆”是指具有纤柄和通常从纤柄延伸的原纤的 纤维材料颗粒,其中纤柄通常为柱形并且直径为10至50微米,并且原纤 为通常与纤柄连接的细毛发状构件,经测量其直径仅为一微米的若干分之 一或几微米,并且长度为约10至100微米。芳族聚酰胺纤维絮状物具有与 碳纤维絮状物类似的长度。间位芳族聚酰胺和对位芳族聚酰胺纤维均是适 宜的,并且以商品名知购自E.I.Du Pont de Nemours,Wilmington,DE(DuPont),和以商品名购自Teijin Aramid, Conyers,GA。
优选的纸浆材料为对位芳族聚酰胺。然而,也可利用对位芳族聚酰胺 与其它合成纤维或天然纤维诸如液晶聚酯、聚芳唑、间位芳族聚酰胺和纤 维素的共混物。用于制备芳族聚酰胺纸浆的一种例证性方法公开于授予 Haines等人的美国专利5,084,136中。
可将不同的热固性和热塑性树脂用作本发明的纸材中的聚合物粘结 剂。这些树脂可按纤条体、薄片、粉末和絮状物的形式来提供。如本文所 用,术语“纤条体”是指基本上为二维薄膜状小颗粒的极细分的聚合物产 品,已知其具有100至1000微米的长度和宽度以及0.1至1微米的厚度。 优选的粘合剂树脂类型为芳族聚酰胺、聚酰亚胺、酚醛树脂和环氧树脂。 然而,也可使用其它类型的树脂。
通常通过使聚合物溶液流动至与该溶液的溶剂不混溶的液体凝固浴中 来制备沉析纤维。聚合物溶液流在聚合物凝聚时受到剧烈剪切力和紊流的 影响。本发明的纤条体材料可选自间位或对位芳族聚酰胺或它们的共混 物。更优选地,纤条体为间位芳族聚酰胺。
沉析纤维和絮状物的示例性组合包括间位芳族聚酰胺沉析纤维和间位 芳族聚酰胺絮状物;间位芳族聚酰胺沉析纤维和对位芳族聚酰胺絮状物; 间位芳族聚酰胺沉析纤维和对位芳族聚酰胺絮状物和聚对苯二甲酸乙二酯 (PET)絮状物的共混物;对位芳族聚酰胺沉析纤维和对位芳族聚酰胺絮状 物;以及具有对位芳族聚酰胺纸浆的对位芳族聚酰胺沉析纤维和对位芳族 聚酰胺絮状物。
在一个优选的实施方案中,纤条体形式的纤维和聚合物粘合剂可一起 制浆以形成混合物,所述混合物在网筛或带上转化为纸材。现将参考授予 Tokarsky的美国专利4,698,267和4,729,921;授予Hesler等人的 5,026,456;授予Kirayoglu等人的5,223,094和5,314,742中的用于由芳族聚 酰胺纤维和芳族聚酰胺沉析纤维形成纸材的例证性方法。
一旦形成纸材,就可将其压延至所期望的空隙率/表观密度。
任选地,如图2B和2C所示,第二组件可包括与纸材26接触的保护 性聚合物层32。此类保护性聚合物层在制造、安装和使用期间向纸材提供 机械增强和保护。保护性聚合物层可以在纸材的一个侧面或两个侧面上。 在优选的实施方案中,保护性聚合物层呈自承膜的形式。
在一些实施方案中,保护性聚合物层32可通过诸如粘合剂或热粘结的 方式粘结到纸材26。在一些实施方案中,保护性聚合物层和纸材之间的粘 结强度为至少140N/m(0.8lb./in)。在另一个实施方案中,保护性聚合物 层和纸材之间的粘结强度为至少262N/m(1.5lb./in.)。
保护性聚合物层32必须能够承受至少200℃的温度至少10min。聚合 物层可以为热固性材料或热塑性材料。优选热塑性层。
优选地,所述保护性层32应具有V-0的UL 94火焰分级。UL 94火焰 分级为Underwriters Laboratory测试,The Standard for Flammability of PlasticMaterials for Parts in Devices and Appliances(用于设备和器具部件的塑 性材料的可燃性标准),所述测试测量一旦所述样品被点燃时火焰要么熄灭 要么蔓延的趋势。V-0表示所述材料在竖直位置被测试,并且在点火源被移 除后十秒之内自熄灭。
优选地,所述保护性层具有在4至30微米范围内的厚度。更优选地, 所述厚度范围应在5至15微米且最优选在5至7微米范围内。所述层进一 步向层合体提供机械强度和硬度。
适用于保护性层的材料包括聚酮、聚酰亚胺、聚砜、聚芳硫醚、含氟 聚合物、液晶聚合物和聚碳酸酯。聚酮的示例为聚醚醚酮(PEEK)和聚醚 酮酮(PEKK)。聚醚砜和聚苯砜为聚砜的示例。聚对亚苯基硫化物是可用 于本发明的适宜的聚芳硫醚。聚氟乙烯(PVF)和聚偏氟乙烯(PVDF)为 含氟聚合物的示例。适宜的含氟聚合物以商品名Tedlar购自DuPont。聚芳 酯为适宜的液晶聚合物的示例。这些膜中的一些还可涂覆有第二种聚合物 材料。例如,聚酰亚胺膜可涂覆有氟化的乙烯丙烯、FEP并且用于 本发明。
保护性层32的表面可任选地处理(诸如利用粘合剂)以改善与纸材的 粘附性。适宜的表面处理方法包括但不限于电晕蚀刻和用偶联剂如铵、鏻 或锍盐进行洗涤。在保护层粘结到纸材26和织物层25和/或28的情况下, 粘合剂可以为热塑性树脂或热固性树脂。热固性树脂包括环氧树脂、环氧 酚醛树脂、酚醛树脂、聚氨酯和聚酰亚胺。热塑性树脂包括聚酯、聚醚 酮、聚醚醚酮、聚醚酮酮、聚醚砜和聚烯烃。优选热塑性树脂。
为了防止由火焰蔓延事件期间纸材上的保护性聚合物层收缩或熔融或 崩解施加的机械应力造成的可能损坏,优选复合材料层合体的层间粘结可 在火焰暴露的较早阶段中失效(即剥离或熔融或软化),因此导致复合材 料层合体的内部脱粘。也就是说,纸材与保护性膜的分层将在保护性膜开 始崩解之前发生。由于它们的相对低活化温度,热塑性粘合剂是比热固性 粘合剂优选的选择,因为它们将有利于有效分层。
用于将保护性层粘结到纸材的粘合剂层可任选地包含最多40重量百分 比的阻燃剂成分。适宜的阻燃成分包括三氧化锑,卤化阻燃剂包括四溴双 酚A、多溴联苯、五溴二苯醚(氧化物)、八溴二苯醚(氧化物)、十溴 二苯醚(氧化物)和六溴环十二烷。含磷阻燃剂也可广泛使用。
优选地,粘合剂应当能够在75至200℃范围内的温度下活化。在一些 实施方案中,活化范围为120℃至140℃。所谓活化,是指就热固性树脂而 言,树脂必须在规定温度范围内粘结到聚合物层和织物。就热塑性树脂而 言,活化是指树脂充分地软化并流动以粘结到聚合物层和织物。
作为对作为纸材组分的云母的替代物,轻质开口编织织物稀松布可嵌 入云母片的层中或铺设在云母片的层上。所述稀松布可由天然的、有机或 无机纤维制成,其中玻璃、棉、尼龙或聚酯是典型的示例。玻璃纤维稀松 布尤其优选用于嵌入到所述片层中。所述稀松布可为织造或针织结构并具 有不超过40克/平方米的典型单位面积重量。
在另一个实施方案中,所述云母层包含100%的片,即,没有诸如树 脂、粘合剂、布料或纸材的载体材料。然而,可存在一些残余的由形成云 母片层期间云母的不完全干燥而产生的分散剂。
第三组件
第三组件23具有88至678gsm(2.6至20oz./sq.yd.)的面积重量并且 包括具有至少11克/分特(10克/旦尼尔)的韧度的长丝纱线的第二织物28 和第二聚合物层29,所述第三组件的第二织物邻近第二组件的纸材。第二 聚合物层为复合材料片材的最内层。第二聚合物层提供增强的耐磨性/耐擦 伤性和耐刺穿性,改善的抗冲击韧性以及对物理苛待、化学接触攻击和液 体渗透的增强的抵抗性。
优选地,第二聚合物层在最终产品的寿命跨度内,在宽温度范围内, 甚至在低至(-50℃(-60°F))的温度下,维持其韧度和柔韧性。
在一些实施方案中,可通过诸如粘合剂、热粘结的方式或通过紧固 件,将第二织物层粘结到第二聚合物层。
当使用粘合剂时,粘合剂层可以为热塑性树脂或热固性树脂。热固性 树脂包括环氧树脂、环氧酚醛树脂、酚醛树脂、聚氨酯和聚酰亚胺。热塑 性树脂包括聚酯、聚醚酮、聚醚醚酮、聚醚酮酮、聚醚砜和聚烯烃。优选 热塑性树脂。所述粘合剂可任选地包含最多40重量百分比的阻燃剂成分。 适宜的阻燃成分包括三氧化锑、卤化阻燃剂,包括四溴双酚A、多溴联 苯、五溴二苯醚(氧化物)、八溴二苯醚(氧化物)、十溴二苯醚(氧化 物)和六溴环十二烷。含磷阻燃剂也可广泛使用。
所述粘合剂必须能够在75至200℃范围内的温度下活化。在一些实施 方案中,活化范围为120至140℃。所谓活化,是指就热固性树脂而言,树 脂必须在规定温度范围内粘结到聚合物层和织物。就热塑性树脂而言,活 化是指树脂充分地软化并流动以粘结到聚合物层和织物。第二聚合物层和 第二织物之间的粘结强度为至少263N/m(1.5lb./in)。在一些实施方案 中,第二聚合物层和第二织物之间的粘结强度为至少315N/m (1.8lb./in)、或甚至876N/m(5lb./in)。
在一些实施方案中,第二织物28和第二聚合物层29之间的粘结强度 为至少263N/m(1.5lb./in)。在另一个实施方案中,第二织物和第二聚合 物层之间的粘结强度为至少315N/m(1.8lb./in)。
在一些实施方案中,第二织物可任选地在一个或两个侧面上利用无机 涂层诸如陶瓷处理。
第一织物和第二织物
在一些实施方案中,第一织物25或第二织物28分别具有70至 508gsm(2.1至15oz./sq.yd.)的面积重量。在一些其它实施方案中,织物面 积重量为101至373gsm(3至11oz./sq.yd.)。在一些实施方案中,第一织 物具有101至170gsm(3至5oz./sq.yd.)的面积重量。在一些实施方案中, 第二织物具有170至270gsm(5至8oz./sq.yd.)的面积重量。
第一织物或第二织物可以为织造或非织造的。典型的织造织物样式为 平纹编织、方平编织、纱罗斜纹编织或缎纹编织。在一个实施方案中,第 一织物为平织织物,其包括在经向和纬向方向上含量为11经密/cm(28经 密/英寸)的555分特(500旦尼尔)KM2+对位芳族聚酰胺纱。在另一个实 施方案中,第二织物为平织织物,其包括在经向和纬向方向上含量为9.4经 纱/cm(24经密/英寸)的1111分特(1000旦尼尔)KM2对位芳族聚酰胺 纱。
与韧性聚合物膜组合的织物的细旦纱导致非刚性复合片材的耐刺穿性 的显著增强,并且因此导致整体耐久性的显著增强。
非织造织物包括其中长丝以无规取向布置的织物,或者包括仅以一个 方向对齐的长丝的织物。该后一类型的织物也被称为非卷曲的或单向织 物。
在一些实施方案中,在编织之后,将第一织物和/或第二织物擦洗或热 清洁。此类工艺在纺织物工业中为人们所熟知来除去污染物,诸如来自编 织过程的油。
优选地,第一织物和第二织物的长丝纱线包含芳族聚酰胺或芳族共聚 酰胺。还可使用玻璃纤维和碳纤维,尤其是基于聚丙烯腈的碳纤维。
织物25和28由具有多个长丝的复丝纱线制成。纱线可被缠结和/或合 股。为了本文的目的,术语“长丝”被定义为相对柔韧的、宏观上均匀的 并且在其垂直于其长度的横截面积上具有高的长宽比的主体。长丝横截面 可以是任何形状,但是通常是圆形的或豆形的。在本文中,术语“纤维” 与术语“长丝”互换使用,并且术语“经纱”(end)与术语“纱线”互换 使用。
长丝可以具有任何长度。优选地长丝是连续的。在卷装中旋绕到线轴 上的复丝包含多根连续长丝。复丝可被切割成短纤维并制成适用于本发明 的短纤纱。短纤维可以具有约1.5至约5英寸(约3.8cm至约12.7cm)的长 度。短纤维可以是直的(即不卷曲)或者卷曲以沿它的长度具有锯齿形褶 皱,具有约3.5至约18个褶皱/英寸(约1.4至约7.1个褶皱/厘米)的褶皱 (或重复弯曲)频率。
在一些实施方案中,纱线具有至少11克/分特的纱线韧度,以及至少 100克/分特的模量。在一些实施方案中,纱线具有333至2222分特(300 至2000旦尼尔)或甚至555至1111分特(500至1000旦尼尔)的线密 度。在一些实施方案中,所述第一织物或第二织物的纱线具有555分特或 1111分特的线密度。
当聚合物为聚酰胺时,优选芳族聚酰胺。术语“芳族聚酰胺”是指其 中至少85%的酰胺(-CONH-)键直接连接到两个芳族环的聚酰胺。适宜的 芳族聚酰胺纤维在Man-MadeFibres-Science and Technology第2卷 (Interscience Publishers,1968年)的标题为“Fibre-Forming Aromatic聚酰 胺”的章节中(第297页,W.Black等人)有所描述。芳族聚酰胺纤维以 及它们的生产在美国专利3,767,756、4,172,938、3,869,429、3,869,430、 3,819,587、3,673,143、3,354,127和3,094,511中也有所公开。
优选的芳族聚酰胺为对位芳族聚酰胺。优选的对位芳族聚酰胺是被称 为PPD-T的聚(对苯二甲酰对苯二胺)。所谓PPD-T,是指由对苯二胺和 对苯二甲酰氯的等摩尔比聚合反应产生的均聚物,以及由少量其它二胺与 对苯二胺结合、少量其它二甲酰氯与对苯二甲酰氯结合所得的共聚物。作 为一般原则,其它二胺和其它二酰氯可以至多多达对苯二胺或对苯二甲酰 氯的约10摩尔%,或者可能略高的量使用,前提条件是仅其它二胺和二酰 氯不具有干扰聚合反应的反应性基团。PPD-T也指其它芳族二胺和其它芳 族二甲酰氯结合所得的共聚物,诸如例如2,6-萘亚甲基酰氯或氯代对苯二 甲酰氯或二氯对苯二甲酰氯或3,4′-二氨基二苯醚。
添加剂可与芳族聚酰胺一起使用,并且已发现,至多多达10重量%或 更多的其它聚合物材料可与芳族聚酰胺共混。可使用共聚物,所述共聚物 具有多达10%或更多的其它二胺(替代了芳族聚酰胺的二胺)或者多达 10%或更多的其它二酰氯(替代了芳族聚酰胺的二酰氯)。
另一种适宜的纤维为基于芳族共聚酰胺的纤维,其是通过对苯二甲酰 氯(TPA)与50/50摩尔比的对亚苯基二胺(PPD)和3,4′-二氨基二苯醚 (DPE)的反应制备的。另一种适宜的纤维为通过如下方式形成的纤维: 两种二胺即对苯二胺和5-氨基-2-(对氨基苯基)苯并咪唑与这些单体的对苯 二酸或衍生物或酸酐衍生物或酰氯衍生物发生缩聚反应。
玻璃纤维包括“E”玻璃和“S”玻璃。E-玻璃是可商购获得的低碱玻 璃。一种典型的组合物由54重量%SiO2、14重量%AI2O3、22重 量%CaO/MgO、10重量%B2O3和小于2重量%Na2O/K2O组成。一些其它材 料也可以杂质含量存在。S-玻璃是可商购获得的氧化镁-氧化铝-硅酸盐玻 璃。该组合物比E-玻璃更硬、更坚固、并且更贵,其通常用于聚合物基体 复合材料中。
在一些实施方案中,碳纤维是标准或中等模量的纤维,诸如可以商品 名Torayca购自Toray Industries或以商品名HexTow购自Hexcel Corporation的那些。通常,此类纤维具有3,000或6,000或12,000或24,000 长丝/丝束。
在一些实施方案中,第一织物和/或第二织物可任选地利用阻燃剂成分 处理以有助于非刚性阻燃复合材料的火焰传播特性。适宜的阻燃成分包括 三氧化锑,卤化阻燃剂,其包括四溴双酚A,多溴联苯、五溴二苯醚(氧 化物)、八溴二苯醚(氧化物)、十溴二苯醚(氧化物)和六溴环十二 烷。含磷阻燃剂也可广泛使用。
第一聚合物层和第二聚合物层
第一聚合物层24或第二聚合物层29,或第一聚合物层和第二聚合物 层两者的聚合物可分别为热塑性聚合物或热固性聚合物。优选热塑性聚合 物。
在优选的实施方案中,第一聚合物层和第二聚合物层呈自承膜的形 式。
适宜的聚合物包括聚氨酯、聚乙烯、聚丙烯、聚对苯二甲酸乙二醇 酯、聚丙烯腈、含氟聚合物、聚酰亚胺、聚酮、聚酰亚胺聚 砜、聚芳硫醚、液晶聚合物、聚碳酸酯、和离聚物如乙烯甲基丙烯酸共聚 物(E/MAA)。
示例性含氟聚合物包括聚氟乙烯乙烯氯三氟乙烯共聚物和聚四氟乙烯示例性聚酮包括聚醚醚酮(PEEK) 和聚醚酮酮(PEKK)。
在一个实施方案中,第一聚合物层为聚氨酯。在另一个实施方案中, 第二聚合物层为离聚物树脂诸如乙烯甲基丙烯酸共聚物。在另一个实施方 案中,第一聚合物层是不透明的和对紫外线不可透过的。所谓不透明和对 紫外线不可透过是指第一聚合物层阻断至少95%的紫外线,更优选地至少 98%和最优选地100%的紫外线,尤其是在紫外光谱的上限处的那些射线。
在一些实施方案中,第一聚合物层和/或第二聚合物层具有17至 170gsm(0.5至5oz./sq.yd.)或34至136gsm(1至4oz./sq.yd.)或甚至67 至102gsm(2至3oz./sq.yd.)的面积重量。
在一些实施方案中,第一聚合物层和/或第二聚合物层中的至少一个表 面可以金属化。优选地,在复合材料片材中,金属化表面在邻近第一织物 或第二织物的聚合物层的侧面上。
使用
如本文所述的复合材料片材可用于需要防火和防着火的许多应用中。 示例包括货物集装箱的侧壁和顶板、耐火覆盖件、隔板,诸如用于可用于 飞机、火车或建筑中的电池和毯或衬里中。
测试方法
可使复合材料片材经历火焰穿透测试,所述测试重复测试方法14CFR 25.855附录F第III部分-测定货物隔室衬里的耐火焰穿透性的测试方法 (Test Method To DetermineFlame Penetration Resistance of Cargo Compartment Liner)的温度和空气质量通量测试条件。偏低的热通量由较 高的空气质量通量补偿以重复待在烧穿测试期间施加在阻燃复合材料上的 所需热-机械应力水平。
复合材料片材的拉伸特性通过ASTM D3039/D3039M-08聚合物基体 复合材料的拉伸特性的标准测试方法(Standard Test Method for Tensile Properties of PolymerMatrix Composite Materials)来测定。
纸材的干拉伸强度根据TAPPI D-828纸材和纸板的拉伸特性(TensileProperties of Paper and Paperboard)(使用恒定伸长速率的设备)来测量。
纸材的厚度通过TAPPI T411 om-10纸材、纸板和组合板的厚度 (Thickness ofPaper,Paperboard,and Combined Board)(厚度)来测量。
纸材的面积干重根据ISO 536(1995)纸材和纸板的克重和TAPPI T 410克重的测定(Determination of Grammage and TAPPI T 410 Grammage of Paper andPaperboard)(重量每单位面积)来测量。
纸材的含水量根据ISO 287(1985)含水量的测定-烘箱干燥法 (Determinationof Moisture Content-Oven Drying Method)来测量。
实施例
实施例1
制备非刚性复合材料片材。
第一组件
第一组件包括热粘结至具有1.05g/cm3的面积重量的不透明0.075mm (3密耳)吹塑聚酰胺膜(第一聚合物层)的织造织物(第一织物),从而 产生85gsm的面积重量。织物具有125gsm(3.7oz./sq.yd.)的面积重量。织 物为在经向和纬向中均具有28经密/英寸的平纹织物,并且由556分特 (500旦尼尔)对位芳族聚酰胺KM2+纱线,并入1W034织造成。 所述纱线具有31g/dtex的标称韧度。介于第一聚合物膜和第一织物之间的 粘结强度测试为至少437N/m(2.5lb./in)。
第二组件
第二组件包括0.200mm(8密耳)等级T418纸材,其具有 237gsm的标称基重。当根据ASTM D-828测量的,所述纸材具有在第一方 向(纵向)上8700N/m,和在第二方向(横向)上6000N/m的标称拉伸强 度。
第三组件
第三组件包括热粘结至具有0.94g/cm3的面积重量的0.075mm(3密 耳)离聚物膜(第二聚合物层)的织造织物(第二织物),从而产 生76gsm的面积重量。织物具有220gsm(6.5oz./sq.yd.)的面积重量。织物 为在经向和纬向中均具有24经密/英寸(9.4经密/cm)的平纹织物,并且由 1111分特(1000旦尼尔)对位芳族聚酰胺KM2纱线,并入1W041 织造成。所述纱线具有30g/dtex的标称韧度。介于第一聚合物膜和第一织 物之间的粘结强度测试为至少262N/m(1.5lb./in)。
如图2A所示,将第一组件、第二组件和第三组件组装在一起。第二 组件不粘结到第一组件或第三组件。
使加工成形的复合材料片材经历两次火焰穿透测试。在第一测试中, 测试样品处于顶板位置,其中复合材料的膜侧面向火焰。所述样品 示出良好的耐火焰穿透性,其中纸材用作对927℃,+/-38℃(1700°F,+/- 100°F)火焰的有效隔板,其中在施用火焰源之后5分钟内没有火焰穿透样 本。在水平测试样本的上表面上方4英寸处测量的峰值温度不超过204℃ (400°F)。
在第二测试中,测试样品处于竖直位置,其中复合材料的膜侧 面向火焰。所述样品示出良好的耐火焰穿透性,其中纸材用作对927℃,+/- 38℃(1700°F,+/-100°F)火焰的有效隔板,其中在施用火焰源之后5分钟 内没有火焰穿透样本。在水平测试样本的上表面上方4英寸处测量的峰值 温度不超过204℃(400°F)。
复合材料片材的机械强度也被测试为符合由国家航空标准NAS 3610 对用于空运货物集装设备的材料所设定的耐久性标准。复合材料片材的 101.6mm(4英寸)宽条的轴向拉伸强度为1,700+/-50lbs或771+/-22kg (425+/-12.5lb/in或74228+/-2189N/m)。
比较例A
加工形成复合材料片材,其包括热粘结在实施例1的0.075mm(3密 耳)聚氨酯(第一聚合物层)和0.075mm(3密耳)(第二聚合物 层)膜之间的322gsm(9.5oz./sq.yd.)织造织物。介于PU膜和织物之间的 粘结强度为至少437N/m(2.5lb./in)。织物为在经向和纬向中均具有24经 密/英寸(94经密/cm)的平纹织物,并且由1667分特(1500旦尼尔)对 位芳族聚酰胺29纱线,并入1F211织造成。单层复合材料的 101.6mm(4英寸)宽条的轴向拉伸强度不大于900lbs或408kg(225lb/in 或39403N/m)。
比较例A测试为符合垂直和水平火焰传播的TSO C90a货物货盘、网 和集装箱(集装设备)规格的易燃性要求。然而,当暴露于火焰时,缺乏 任何有效的阻燃特性,样品在施加火焰源之后30秒内在火焰穿透中损坏。
实施例2
该实施例按照实施例1制备,不同的是组件2热粘结至具有0.025mm (1密耳)浇注聚氨酯膜层的组件1和3,所述聚氨酯膜包含最多达50重 量百分比的阻燃剂成分。
使实施例2在顶板位置处经历火焰穿透测试。将火焰施用于复合材料 的膜侧上。所述样品示出良好的耐火焰穿透性,其中纸材用作对 927℃,+/-38℃(1700°F,+/-100°F)火焰的有效隔板,其中在施用火焰源 之后5分钟内没有火焰穿透样本。在水平测试样本的上表面上方4英寸处 测量的峰值温度不超过204℃(400°F)。
实施例3
该实施例按照实施例1制备,不同的是第二组件为0.125mm(5密 耳)等级T418纸材,其具有148gsm的标称基重。当根据ASTM D-828测量时,所述纸材具有在第一方向(纵向)上5200N/m,和第二方向 (横向)上3500N/m的标称拉伸强度。
使实施例3的复合材料片材在顶板位置上经历火焰穿透测试。将火焰 施用于复合材料的膜侧上。所述样品示出良好的耐火焰穿透性,其 中纸材用作对927℃,+/-38℃(1700°F,+/-100°F)火焰的有效隔板,其中 在施用火焰源之后5分钟内没有火焰穿透样本。在水平测试样本的上表面 上方4英寸处测量的峰值温度不超过204℃(400°F)。
复合材料片材还经历火焰穿透测试,其中片材处于竖直位置。将火焰 施用于复合材料的膜侧上。所述样品示出不一致的耐火焰穿透性, 其中在施用火焰源之后5分钟内,火焰穿透至少30%的样本。
认为样本在顶板位置处的火焰穿透测试是可接受的,然而认为样本在 竖直位置处的测试仅是勉强可接受的。
比较例B
该实施例按照实施例1制备,不同的是使用0.075mm(3密耳) 等级T418纸材,其具有89gsm的标称基重。当根据ASTM D-828 测量时,所述纸材具有在第一方向(纵向)上2900N/m,和第二方向(横 向)上1900N/m的标称拉伸强度。
使该实施例的复合材料片材在顶板位置上经历火焰穿透测试。将火焰 施用于复合材料的膜侧上。所述样品示出不一致的耐火焰穿透性, 其中在施用火焰源之后5分钟内,火焰穿透大部分样本。该测试结果被认 为是不可接受的。
Claims (13)
1.一种非刚性复合材料片材,其依次包括:
(i) 具有88至678gsm的面积重量的第一组件,其包括具有至少11g/分特的韧度的连续长丝纱线的第一织物和第一聚合物层,所述第一织物是织造的,
(ii) 具有120至430gsm的面积重量的第二组件,其包括邻近第一组件的第一织物和第三组件的第二织物定位的纸材,所述纸材包含芳族聚酰胺纤维、聚合物粘合剂和云母,以及
(iii) 具有88至678gsm的面积重量的第三组件,其包括具有至少11g/分特的韧度的连续长丝纱线的第二织物和第二聚合物层,所述第三组件的第二织物邻近所述第二组件的纸材,所述第二织物是织造的,其中
(a) 所述第一织物和第二织物的纱线包含芳族聚酰胺、芳族共聚酰胺、玻璃纤维或碳纤维,并且
(b) 所述第一组件的第一聚合物层和所述第三组件的第二聚合物层的聚合物为聚氨酯、聚乙烯、聚丙烯、聚萘二甲酸乙二醇酯、聚丙烯腈、含氟聚合物、聚酰亚胺、聚酮、聚砜、聚芳硫醚、液晶聚合物、聚碳酸酯或离聚物,
其中所述纸材的聚合物粘合剂以基于纸材中存在的芳族聚酰胺纤维加聚合物粘合剂的合并重量计45至60重量百分比的量存在。
2.根据权利要求1所述的非刚性复合材料片材,其中所述复合材料具有至少350N/cm的断裂强度。
3.根据权利要求1所述的非刚性复合材料片材,其中当根据FAA测试方法14 CFR25.855附录F第III部分测试时,所述复合材料片材能够承受927℃的火焰温度5分钟,而不烧穿。
4.根据权利要求1所述的非刚性复合材料片材,其中当根据FAA测试方法14 CFR25.855附录F第III部分测试时,所述复合材料片材能够承受927℃的火焰温度5分钟,而不烧穿,并且距离远离火焰的片材侧101mm的温度不超过204℃。
5.根据权利要求1所述的非刚性复合材料片材,其中所述第一织物或第二织物具有70至508gsm的面积重量。
6.根据权利要求1所述的非刚性复合材料片材,其中所述第一织物具有101至170gsm的面积重量。
7.根据权利要求1所述的非刚性复合材料片材,其中所述第二织物具有170至270gsm的面积重量。
8.根据权利要求1所述的非刚性复合材料片材,其中所述第一织物和/或第二织物的长丝纱线具有333至2222分特的线密度。
9.根据权利要求1所述的非刚性复合材料片材,其中所述纸材具有195至255gsm的基重。
10.根据权利要求1所述的非刚性复合材料片材,其中所述纸材具有不大于10%的含水量。
11.根据权利要求1所述的非刚性复合材料片材,其中所述离聚物为乙烯甲基丙烯酸共聚物。
12.一种货物集装箱,其包括机架组装件、多个侧壁、顶板和底板,其中所述侧壁和顶板包括权利要求1所述的非刚性复合材料片材。
13.一种耐火覆盖件、隔板、毯或衬里,其包括权利要求1所述的非刚性复合材料片材。
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