CN102046367B - 改进的复合材料 - Google Patents
改进的复合材料 Download PDFInfo
- Publication number
- CN102046367B CN102046367B CN200980119875.0A CN200980119875A CN102046367B CN 102046367 B CN102046367 B CN 102046367B CN 200980119875 A CN200980119875 A CN 200980119875A CN 102046367 B CN102046367 B CN 102046367B
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- composite
- resin
- conductive particle
- metal
- prepreg
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Abstract
本发明公开了一种复合材料,该复合材料包括:预浸渍体,所述预浸渍体包含至少一种聚合物树脂和至少一种导电性纤维补强材料;分散于聚合物树脂中的导电性颗粒;和包含其它树脂组分的涂布金属的碳纤维顶层,其中金属包含一种或多种选自镍、铜、金、铂、钯、铟和银中的金属。
Description
本发明涉及复合材料,特别涉及涂布的纤维补强的复合材料,其具有增强的导电性。
复合材料由于它们有吸引力的机械性质和比金属更低的重量而日益应用于很多领域中的结构应用中。复合物由材料层构成以提供结构上有利的层压型材料。不过,虽然导电性是金属最显著属性之一,但是基于纤维补强材料的复合材料(如粘性膜,表面膜,和预浸渍(预浸渍体)材料)一般具有低得多的导电性。
传统复合材料通常由补强相和基质相构成,补强相一般包含连续或不连续纤维,基质相一般为热固性或热塑性聚合物。用于制造复合物的最早的第一代基质聚合物天然是脆的,因此有必要开发更加韧性的变体。用作航天应用中初级结构的复合材料趋于是所谓的第二代或第三代增韧的材料。
特别需要对若干应用显示出导电性的复合材料。这些应用包括用于防雷击保护、静电消除(ESD)、和电磁干扰(EMI)的用途。现有的复合材料,如基于碳纤维的那些复合材料,具有通常与碳丝(carbon filament)的石墨性质有关的一定程度的导电性。不过,导电性水平不足以防护复合材料免受强放电如雷击的破坏作用。
第二代增韧的复合材料由于基质材料内的增韧相引入而表现出比早先的第一代材料的改进。通过各种方式向这些材料中引入改进的导电性。这包括通过膨胀箔、金属网、或交织的金属丝将金属引入组装中。用于该目的的典型金属包括铝、青铜和铜。这些复合材料能提供更好的导电性。不过,它们通常重并且具有明显劣化的机械性质和美学性质。这些复合物通常位于材料的第一层(ply)或顶部二层,因此经常导致差的总体表面抛光。
当雷击于第二代复合物时,破坏一般限于表面保护层。雷击的能量典型地足以蒸发一些金属并在网或其它保护层中灼烧出小孔。对底层复合物的破坏可以最小化,破坏限于顶部一层或两层。然而,这样的雷击后,有必要切除受损区域并用新鲜的金属防护和如果需要的新鲜的复合物来修复。
如前所述,含碳纤维的材料具有一定的导电性。不过,导电通道仅沿着纤维方向,在与纤维补强材料的平面垂直的方向(z-方向)具有有限的电流耗散能力。碳补强的材料经常包含夹层(interleaf)结构,夹层结构经常包含一些树脂层,其由于夹层的电绝缘性质导致沿z-方向固有的低的导电性。当被雷击时,该布置的结果可能导致灾难性的后果,因为放电能进入夹层,使其中的树脂挥发,并引发物质分层和穿透复合材料。
其它导电性颗粒如炭黑、聚吡咯、碳纳米纤维、及其混合物单独用作复合材料中的添加剂,而且显示出改进的耐受由例如雷击引起的破坏性。
添加涂布金属的颗粒至夹层型预浸渍体显示出降低由雷击引起的对复合物的损坏水平,而且能进一步降低对表面和下部层的损坏。
所谓第三代增韧的复合材料基于夹层技术,其中树脂层与纤维补强的层交替,并提供冲击防护。不过,这些树脂层起到电绝缘体的作用,因此沿材料z-方向(即,与纤维方向垂直)的电导率差。对复合材料的雷击能导致具有贯穿多层层压品的孔的组件的灾难性故障。
因此,本发明寻求提供复合材料,其具有较此处所述的先前尝试改进的导电性,并且与标准复合材料相比具有极少或者不具有额外的重量。本发明还寻求提供复合材料,其具有改进的导电性,而不损害材料的机械性能。本发明进一步寻求提供制备具有改进的导电性的复合材料的方法。
再一目的是提供耐雷击复合材料,其便于制造、使用和修复。
根据本发明的第一方面,提供复合材料,其包含:
i)预浸渍体,由至少一种聚合物树脂和至少一种导电纤维补强材料构成;
ii)分散于聚合物树脂中的导电性颗粒;和
iii)包含其它树脂组分的涂布金属的碳纤维顶层,其中所述金属包含一种或多种选自镍、铜、金、铂、钯、铟和银中的金属。
根据本发明的第二方面,提供制备复合材料的方法,包括以下步骤:
i)提供预浸渍体,该预浸渍体包含至少一种聚合物树脂和至少一种导电性纤维补强材料;
ii)将导电性颗粒分散于聚合物树脂中;和
iii)添加包含其它树脂组分的涂布金属的碳纤维顶层,其中所述金属包括选自镍、铜、金、铂、钯、铟和银中的一种或多种金属。
顶层能在制造预浸渍体期间或之后添加,并可使用通过预浸渍体中包含的树脂所提供的粘合性来就地固结(consolidated in place)。
已发现:在预浸渍体的聚合物树脂中使用导电性颗粒并使用包含其它树脂组分的涂布金属的碳纤维层作为预浸渍体的顶层,在整个复合材料中提供降低的体积电阻率、表面电阻率和改进的z-方向电导率,其中所述金属包含一种或多种选自镍、铜、金、铂、钯、铟和银中的金属。此外,还发现分散于树脂配方中和随后被预浸渍的导电性颗粒得到的预浸渍体具有与相当的未改性预浸渍体基本类似的加工特性。
使用包含其它树脂组分的涂布金属的碳纤维层作为含有涂布金属的颗粒的预浸渍体复合材料的顶层,增加预浸渍体复合材料的导电性,其中所述金属包含一种或多种选自镍、铜、金、铂、钯、铟和银中的金属。这使得复合材料甚至更耐损坏,其可以承受强放电如雷击。
术语复合材料包括包含纤维补强材料的材料,其中聚合物树脂与纤维接触,而非浸含于纤维中。术语复合材料还包括本领域中通常称为预浸渍体的替换性布置,其中树脂部分地包埋于或部分地浸含于纤维中。预浸渍体还可以具有完全浸渍的纤维补强材料层。复合材料还可以包括具有多层纤维-树脂-纤维层的多层材料。
术语″夹层结构(interleaf structure)″是指具有纤维-树脂-纤维结构的多层材料。术语″夹层″是指存在并夹于纤维层之间的聚合物树脂。术语″夹层厚度″是从下部纤维层的最高表面到上部纤维层的最下表面测量的跨越夹层的平均距离。因此,夹层厚度等于插入的聚合物树脂层的厚度,术语夹层厚度和聚合物树脂厚度是可互换的。
文中所用的术语中间层、夹层树脂层、中间层树脂层、和不含纤维的层都是可互换的,是指聚合物树脂层。
本文所用的术语聚合物树脂是指聚合物体系。
术语″聚合物树脂″和″聚合物体系″在本申请中可互换使用,是指具有不同链长度的树脂的混合物。因此,术语聚合物包括以下实施方案,其中存在的树脂为包含任意单体、二聚体、三聚体或具有链长度大于3的树脂的树脂混合物形式。当固化时,所得聚合物树脂形成树脂的交联基质。
体积电阻率是指半导体材料的″体电阻率″或″体积电阻率″。可以看出,术语″初始的体积电阻率″是指添加导电性颗粒之前聚合物树脂的体积电阻率的大小。以Ohms-m为单位的值是所给材料的内阻。Ohms-m(Ωm)用于计量三维材料的电阻率。材料的体积电阻率ρ通常通过下式定义:
ρ=RA/l
其中:
ρ为静电阻率(以欧姆米计),
R为均匀材料样品的电阻(以欧姆计),
l为样品长度(以米计)
A为样品的横截面积(以平方米计)。
在本发明中,仅沿z-方向测量体积电阻率(贯穿复合材料厚度)。在任何情况下都称为″体积″电阻率,因为在计算中总是考虑到跨越厚度。
本发明的目的通过下面方法实现:除了将低体积分数的导电性颗粒以完全不足以赋予聚合物树脂(由该聚合物树脂制备预浸渍体)本身以导电性的水平(即,在缺乏碳纤维的情况下)引入至预浸渍体的夹层区域之外,还将包含其它树脂组分的涂布金属的碳纤维顶层引入至预浸渍体上,其中所述金属包含一种或多种选自镍、铜、金、铂、钯、铟和银的金属。
此外,已发现添加导电性颗粒如碳颗粒和涂布银的玻璃球至复合材料中,以及添加包含其它树脂组分的涂布金属的碳纤维顶层,会降低体积电阻率,并因此提供超过可合理预期的导电水平,其中所述金属包含一种或多种选自镍、铜、金、铂、钯、铟和银的金属。
典型地,金属涂层总量为纤维的约10至约65重量%。
任何金属镍、铜、金、铂、钯、铟和银可以单独或组合地用于涂布碳纤维,但是典型地,镍与选自铜、金、铂、钯、铟和银中的一种或多种金属的组合用于涂布碳纤维。更典型地,铜-镍涂层用于涂布碳纤维。
涂布金属的碳纤维层的效率如此,使得用于复合组装中的导电性层的总数可以降低,由此能使得导电性层限于雷击防护最为关键的外部。此外,由于本发明复合材料增强的导电性,任何由雷击引起的损坏基本上限于外层。
本发明的复合材料便于制造,这是因为现有的依附性(parasitic)材料难于加工。在本发明中,碳纤维层能被容易地引入至预浸渍体,根据需要,能容易地作为整体产品供给。
此外,表面抛光良好,本发明的复合材料能与预浸渍体类似地加工。
本发明的再一益处是预浸渍体的改进的导热性,其导致更快的变热时间和在固化放热期间产生的热的更好消散。再一益处是复合材料电阻基本上不会因温度变化而变化。
体积电阻率的降低和电导率的改进产生改进的雷击性能。因此,鉴于使用了低水平的导电性颗粒和由夹层树脂本身正常显示出的高电阻率,通过本发明实现的上述改进是出人意料的。
本文所用术语″阻抗性(resistivity)″和″导电性(conductivity)″分别是指电阻率(electrical resistivity)和电导率(electrical conductivity)。
本文所用术语″颗粒″是指离散的三维形状添加剂,其是不同的,被当作单个单元,与其它单个添加剂是可分离的,但这并不排除添加剂彼此相互接触。该术语涵盖本文所描述和定义的导电性颗粒的形状和粒度。
本文所用术语″长径比″被理解为是指三维体的最长尺寸与最短尺寸之比。该术语可应用于本文中所用的任何形状和尺寸的添加剂。如果该术语用于表述球形或基本上球形体,则相关比例是指球形体的最大横截面直径与最小横截面直径之比。因此,应当理解理想球形的长径比为1。此处限定的导电性颗粒的长径比基于施涂任意金属涂层后的颗粒的尺寸。
涂布金属的碳纤维层典型地包含非织造碳纤维,这是因为其具有优良的表面抛光,但是也可以代之以包含机织布或针织布。替换性地,切短(chopped)的涂布金属的碳纤维可以直接施涂于预浸渍体表面上。重要的是,碳纤维是轻质的。
碳纤维的面积重量范围可以为约5gsm至约100gsm范围。添加34gsm碳纤维层能在面积和深度方面降低由雷击导致的损害的约30-40%。
术语导电性颗粒的粒度(size)是颗粒最大横截面直径。
范例性导电性颗粒可以包括但不限于球形、微球形、树枝形(dendrite)、珠状、粉末状、和任何其它适当三维添加剂,或它们的任意组合。
本发明中所用的导电性颗粒可以包含任何能降低体积电阻率因而有助于复合材料导电性的导电性颗粒。
导电性颗粒可以选自涂布金属的导电性颗粒、非金属性导电性颗粒、或者它们的组合。
导电性颗粒分散于聚合物树脂中。拟定术语″分散″可以包括导电性颗粒基本上遍及于整个聚合物树脂中,而在聚合物树脂的任何部分中导电性颗粒都不存在显著更高的浓度。此外,术语″分散″还包括如果只在复合材料的特定区域中要求降低的体积电阻率,导电性颗粒存在于聚合物树脂的局部区域中。
涂布金属的导电性颗粒可以包含基本上被适当金属涂敷的核心颗粒(core particle)。
核心颗粒可以是任何适当的颗粒。适当的颗粒包括但不限于由聚合物、橡胶、陶瓷、玻璃、矿物、或耐火产品(如飞灰)形成的那些颗粒。
聚合物可以是任何热塑性或热固性聚合物。术语″热塑性聚合物″和″热固性聚合物″如本文中所表征的。
由玻璃形成的核心颗粒可以是用于制造实心或空心玻璃微球的任何种类。
适当的含有二氧化硅的玻璃颗粒的非限定性实例包括钠玻璃、硼硅酸盐、和石英。替换性地,玻璃可以基本上不含二氧化硅。适当的不含二氧化硅的玻璃包括只是例举的硫属玻璃。
核心颗粒可以是多孔的或空心的,或本身可以是核-壳结构,例如核-壳聚合物颗粒。核心颗粒可以在涂布金属前首先涂布有活化层、粘合促进层、底层(primer layer)、半导电性层或其它层。
核心颗粒典型地为由玻璃形成的空心颗粒。使用由玻璃形成的空心核心颗粒可以在重量减轻是特别重要的应用中是有利的。
核心颗粒的混合物可以用于获得例如较低密度或其它有用的性质,例如一部分空心的涂布金属的玻璃颗粒可以与一部分涂布金属的橡胶颗粒一起使用,以获得具有较低比重的增韧层。
适用于涂布核心颗粒的金属包括但不限于银、金、镍、铜、锡、铝、铂、钯、和任何其它已知具有高导电性的金属,或其中任何两种或更多种的组合。典型地,银由于其高电导率而被使用。
多层金属涂层可以用于涂布核心颗粒,例如涂布有金的铜和涂布有银的铜。金属的同时沉积也是可行的,由此产生混合的金属涂层。
涂布金属可以通过任何已知用于涂布颗粒的方法来进行。适当的涂布方法的实例包括化学气相沉积、溅射、电镀、或非电解沉积。
金属可以作为成块金属、多孔金属、柱形、微晶、纤丝、树枝状、或任何已知金属涂层形式存在。金属涂层可以是光滑的,或可以包含表面不规则度如原纤维(fibril)、或凸起以增加比表面积并改进界面粘合。
金属涂层可以随后用任何本领域已知试剂处理以改进与聚合物树脂的界面粘合,所述试剂例如硅烷、钛酸盐(酯)、和锆酸盐(酯)。
金属涂层的电阻率应当优选小于3×10-5Ωm,更优选小于1×10-7Ωm,最优选小于3×10-8Ωm。
涂布金属的导电性颗粒可以是任何适当的形状,如球形、椭球形、扁球形(spheroidal)、盘形、树枝形、棒状、圆盘形、针状、立方形或多面体。还可以使用精细切短或研磨纤维,如涂布金属的研磨玻璃纤维。颗粒可以具有边界分明的几何结构或者可以为不规则形状。
涂布金属的导电性颗粒典型地具有长径比<100,优选<10,最优选<2。
涂布金属的导电性颗粒的粒度(size)分布可以是单分散的或多分散的。优选地,至少约90%的涂布金属的颗粒的粒度在约0.3μm至约100μm范围内,更优选约1μm至约50μm范围内,最优选在约5μm至约40μm范围内。
导电性颗粒可以是非金属性导电性颗粒。应当理解这包括任何适当的非金属性颗粒,其不具有金属涂层,并能降低体积电阻率,由此有助于复合材料的导电性。
适当的非金属性导电性颗粒包括但不限于石墨片、石墨粉、石墨颗粒、石墨烯片、富勒烯、炭黑、本征导电性聚合物(ICPs,包括聚吡咯、聚噻吩、和聚苯胺)、电荷转移复合物(charge transfer complex)、或它们的任意组合。
适当的非金属性导电性颗粒组合包括ICPs与炭黑和石墨颗粒的组合。
非金属性导电性颗粒粒度分布可以是单分散的或多分散的。优选地,至少约90%的非金属性导电性颗粒的粒度在约0.3μm至约100μm范围内,更优选约1μm至约50μm范围内,最优选约5μm至约40μm范围内。
导电性颗粒具有这样的粒度,存在于聚合物树脂中的至少约50%的颗粒的粒度在聚合物树脂层厚度约10μm内。换言之,树脂层厚度与导电性颗粒粒度之差小于约10μm。典型地,导电性颗粒具有以下粒度,存在于聚合物树脂中的至少约50%的颗粒的粒度在聚合物树脂层厚度5μm内。
因此,至少约50%导电性颗粒的粒度使得它们跨越夹层厚度(聚合物树脂层),颗粒与在聚合物树脂层附近设置的上部纤维补强材料层和下部纤维补强材料层接触。
导电性颗粒可以占复合材料的约0.2vol.%至约20vol.%。优选地,导电性颗粒占约0.4vol.%至约15vol.%。更优选地,导电性颗粒占约0.8vol.%至约10vol.%。
在替换性实施方案中,导电性颗粒的量可以为聚合物树脂层的小于约10vol.%。
可看出导电性颗粒的优选范围以vol.%表示,这是因为颗粒重量可能由于密度变化而表现出大的变化。
导电性颗粒可以单独使用或以任何适当组合使用。
不希望被任何理论所束缚,已发现:由于导电性颗粒(涂布金属的或非金属性的)起到跨越夹层厚度(即,跨越聚合物树脂层并介于纤维补强材料层之间)的导电性桥的作用,由此连接纤维补强材料并改进z-方向电导率,因此可带来本发明的益处。包含其它树脂组分的涂布金属的碳纤维顶层再进一步改进z-方向电导率,其中所述金属包含一种或多种选自镍、铜、金、铂、钯、铟和银中的金属。
还发现,使用粒度基本上等于夹层厚度的导电性颗粒能有利地以相对低载量水平提供贯穿复合材料(在z-平面中)的导电性。导电性颗粒的这些低载量水平低于制备本身导电的聚合物树脂通常所要求的水平。
因此,导电性颗粒通过降低复合材料的体积电阻率而有助于导电性。
复合材料还可以包含碳纳米材料。碳纳米材料可以选自任何适当的碳纳米管和碳纳米纤维。
碳纳米材料可以具有直径在约10至约500nm范围内,优选在约100至约150nm范围内。
碳纳米材料可以优选具有长度在约1至约10μm范围内。
碳纳米材料可以通过跨越夹层的进一步桥接而提供贯穿复合材料(在z-平面中)的附加的导电性通道。纤维补强材料典型地以包含很多纤维束(fibrestrand)的层形式设置。复合材料典型地包含至少两层设置于聚合物树脂层各一侧的纤维补强材料层。除了在材料的x-和y-平面中提供导电性之外,所述层还起到材料结构的支撑层的作用,且基本上含有聚合物树脂。
预浸渍体的纤维补强材料可以选自混杂或混合纤维体系,其包含合成或天然纤维,或者它们的组合。纤维补强材料由导电性的纤维形成,因此纤维补强材料是导电性的。
纤维补强材料典型地可以选自任何适当材料如金属化玻璃、碳、石墨、金属化聚合物纤维(具有连续或不连续的金属层),该聚合物可溶于或不溶于聚合物树脂。可以选择这些纤维的任意组合。可以使用这些纤维与非导电性纤维(如纤维玻璃)的混合物。
纤维补强材料最优选地基本上由碳纤维形成。
纤维补强材料可以包含破裂的(即拉伸中断的)或选择性不连续纤维、或者连续纤维。预计使用破裂的或选择性不连续纤维可以有助于在根据本发明的完全固化之前固化复合材料铺置(lay-up),以及改进其成型的能力。
纤维补强材料可以为织物、非轧花、无纺布、单向、或多向织物带或丝束(tow)形式。
织物形式优选选自平纹编织、缎纹编织、或斜纹编织风格。非轧花和多向形式具有很多层和纤维取向。
纤维补强材料的这些风格和形式在复合补强材料领域是公知的,可商购自很多公司,包括法国Villeurbanne的Hexcel Reinforcements。
预浸渍体的聚合物树脂和其它树脂组分均优选独立地包含至少一种热固性或热塑性树脂。
术语′热固性树脂′包括任何在固化之前为塑性的且通常为液体、粉末、或可延展的并且设计为模塑成最终形式的适当材料。本发明中使用的热固性树脂可以是任何适当的热固性树脂。一旦固化,热固性树脂就不适于熔融和再成型。适当于本发明的热固性树脂材料包括但不限于以下的树脂:酚醛树脂(phenol formaldehyde),脲醛树脂,1,3,5-三嗪-2,4,6-三胺(密胺)树脂,双马来酰亚胺树脂,环氧树脂,乙烯基酯树脂,苯并噁嗪树脂,酚醛树脂(phenolicresin),聚酯,不饱和聚酯,氰酸酯树脂,或其中任意两种或更多种的组合。
热固性树脂优选选自环氧树脂,氰酸酯树脂,双马来酰亚胺树脂,乙烯基酯,苯并噁嗪树脂,和酚醛树脂。
术语“热塑性树脂”包括任何以下材料,其为塑性的或可变形的,当加热时熔融为液体,当充分冷却时凝固为脆性固体并形成玻璃态。一旦形成和固化,热塑性树脂适用于熔融和再成型。适用于本发明的热塑性聚合物可以包括任意的聚醚砜(PES),聚醚醚砜(PEES),聚苯砜,聚砜,聚酯,可聚合的大环(例如环状对苯二酸丁二酯),液晶聚合物,聚酰亚胺,聚醚酰亚胺,芳族聚酰胺,聚酰胺,聚酯,聚酮,聚醚醚酮(PEEK),聚氨酯,聚脲,聚芳醚,聚芳硫醚(polyarylsulphide),聚碳酸酯,聚苯醚(PPO)和改性PPO,或其中任何两种或更多种的组合。
高分子环氧树脂优选包含以下中的至少一种:双酚-A(BPA)二缩水甘油醚和双酚-F(BPF)二缩水甘油醚及其衍生物;4,4′-二氨基二苯基甲烷(TGDDM)的四缩水甘油基衍生物;氨基酚的三缩水甘油基衍生物,以及本领域公知的其它缩水甘油醚和缩水甘油基胺。
聚合物树脂施用于纤维补强材料上。纤维补强材料可以全部或部分地被聚合物树脂浸渍。在替换性实施方案中,聚合物树脂可以为最接近纤维补强材料且与纤维补强材料接触、但基本上不浸渍所述纤维补强材料的分离层。
用于浸渍碳纤维层的其它树脂组分可以是导电性或非导电性的,可以包含至少一种热固性或热塑性树脂。范例性树脂包括但不限于所有上述列举用于聚合物树脂的树脂化合物。其它树脂组分可以是与聚合物树脂相同或不同的树脂。其它树脂组分还可以任选有益地含有导电性颗粒(涂布金属的或非金属性的)。
复合材料可以包括至少一种固化剂。固化剂可以实质上存在于聚合物树脂中。规定术语″实质上存在″意思是指至少约90wt.%的固化剂,典型地约95wt.%的固化剂。
对于环氧树脂,本发明的固化剂是有助于本发明的环氧官能性化合物固化,特别是有助于该环氧化合物开环聚合的那些。在特别优选的实施方案中,该固化剂包括在环氧官能性化合物开环聚合中与其聚合的那些化合物。固化剂典型地包括氰基胍,芳族和脂族胺,酸酐,路易斯酸,取代的脲,咪唑和肼。
可以组合使用两种或更多种该固化剂。
适当的固化剂包括酐,特别是多元羧酸酐如桥亚甲基四氢化邻苯二甲酸酐(nadic anhydride)(NA)、甲基纳迪克酸酐(methylnadic anhydride)、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、内次甲基四氢邻苯二甲酸酐、或偏苯三酸酐。
其它适当的固化剂是胺,包括芳族胺如1,3-二氨基苯、1,4-二氨基苯、4,4′-二氨基二苯基甲烷,和多氨基砜如4,4′-二氨基二苯基砜(4,4′-DDS)、和3,3′-二氨基二苯基砜(3,3′-DDS)。
此外,适当的固化剂可以包括酚醛树脂,如具有平均分子量约550-650的酚醛树脂、具有平均分子量约600-700的对-叔丁基酚醛树脂、和具有平均分子量约1200-1400的对-正辛基酚醛树脂。
还可使用其它适当的含有酚基的树脂如间苯二酚类树脂,和通过阳离子聚合形成的树脂如二环戊二烯-酚共聚物。其它适当的树脂还有三聚氰胺甲醛树脂和脲醛树脂。
不同的商购可得的组合物可用作本发明中的固化剂。一种该组合物是AH-154,双氰胺类型配方,可得自Ajinomoto USA Inc。其它适当的包括Ancamide 1284(其为4,4′-亚甲基二苯胺和1,3-苯二胺的混合物),可得自Pacific Anchor Chemical,Performance Chemical Division,Air Products andChemicals,Inc.,Allentown,USA。
如此选择固化剂,使得当与其在适当温度组合时,其提供复合材料的树脂组分固化。提供树脂组分的足够固化所需的固化剂量将根据包括固化的树脂种类、期望的固化温度、和固化时间等很多因素而变化。固化剂典型地包括氰基胍,芳族和脂族胺,酸酐,路易斯酸,取代尿素,咪唑和肼。各具体情形所需的固化剂的具体量可以通过公认的常规试验来确定。
范例性优选的固化剂包括4,4′-二氨基二苯基砜(4,4′-DDS)和3,3′-二氨基二苯基砜(3,3′-DDS)。
如果存在固化剂,则固化剂可以为复合材料的约45wt.%至约2wt.%。更典型地,固化剂可以以约30wt.%至约5wt.%的范围存在。最典型地,固化剂可以以约25wt.%至约5wt.%的范围存在。
如果存在促进剂,促进剂典型地为urones。可以单独或组合使用的适当的促进剂包括N,N-二甲基-N′-3,4-二氯苯基脲(Diuron)、N,N-二甲基-N′-3-氯苯基脲(Monuron),优选N,N-(4-甲基-间-亚苯基双[N′,N′-二甲基脲](TDIurone)。
复合材料和/或碳纤维层还可以包括另外的成分如性能增强或改性剂。仅仅列举的性能增强或改性剂可以选自柔韧剂(flexibilise),增韧剂(toughening agent)/颗粒,另外的促进剂,核壳橡胶,阻燃剂,湿润剂,颜料/染料,阻燃剂,增塑剂,UV吸收剂,抗真菌(anti-fungal)化合物,填料,粘度改进剂/流动调节剂,增粘剂,稳定剂,抑制剂,或其中两种或更多种的任意组合。
增韧剂/颗粒可以包括仅列举的任意下列单独或组合的物质:聚酰胺,共聚酰胺,聚酰亚胺,芳族聚酰胺,聚酮,聚醚醚酮,聚亚芳基醚(polyaryleneether),聚酯,聚氨酯,聚砜,高性能烃聚合物,液晶聚合物,PTFE,弹性体,和嵌段弹性体(segmented elastomer)。
如果存在增韧剂/颗粒,增韧剂/颗粒可以占复合材料的约45wt.%至约0wt.%。更典型地,它们可以占约25wt.%至约5wt.%。最典型地,它们可以占约15wt.%至约10wt.%。
适当的增韧剂/颗粒可以仅列举Sumikaexcel 5003P,其可商购自Sumitomo Chemicals of Tokyo,Japan。5003P的替换物是Solvay polysulphone105P和Solvay 104P,其可商购自Solvay of Brussels,Belgium。
适当的填料可以包括(只是列举)任何下列单独或组合物质:二氧化硅,氧化铝,氧化钛,玻璃,碳酸钙,和氧化钙。
适当的颜料可以包括只是列举的二氧化钛。这降低对底漆(primer)和涂料(paint)的需求,由此进一步改进本发明复合材料作为用于最小损害地抵御雷击的材料的益处。
复合材料可以包含另外的聚合物树脂,其为至少一种如之前所定义的热固性或热塑性树脂。
尽管期望大多数导电性颗粒位于复合材料的聚合物树脂内部,但是如果小百分数的该颗粒分布于纤维补强材料内部,这一般不是有害的。导电性颗粒可以通过常规的混合或共混操作而适当分散于预浸渍体的聚合物树脂内部。
含有所有必需的添加剂和导电性颗粒的混合树脂可以通过任何已知方法被引入至预浸渍体中,例如所谓的涂漆法(lacquer process)、树脂膜法、挤出法、喷雾法、印刷法或其它已知方法。
在涂漆法中,所有树脂组分都溶解或分散于溶剂中,将纤维补强材料浸于溶剂中,然后通过加热去除溶剂。在树脂膜法中,聚合物树脂作为连续膜从涂漆(lacquer)或热熔融树脂流延于已用剥离剂处理的基质上,然后使涂布的膜与纤维补强材料在热和压力作用下相接触,树脂膜熔融并流入纤维中。可以使用很多膜,纤维层的一面或两面可以以此方式浸渍。
如果预浸渍体是通过膜或涂漆法制造的,则大多数导电性颗粒将被补强纤维″过滤″,由此会基本上阻止进入纤维补强材料,这是因为粒度大于补强纤维之间的距离。其它方法如喷雾法或印刷法能够使导电性颗粒被直接置于纤维补强材料上,所述颗粒在纤维间具有非常低的渗透性。
当使用涂布金属的空心颗粒,也许有必要利用较低剪切力的混合设备,以降低混合可能在导电性颗粒上产生的变形效果。
预浸渍体可以是连续带、丝束浸渍料(towpreg)、织物、网的形式,或者切短长度的带、丝束浸渍料、织物、或网的形式。预浸渍体还可以起到粘合剂或表面膜的作用,此外可以具有包埋的呈纺织、编织和非纺织形式的载体。
根据本发明配制的预浸渍体可以使用任何已知方法被制成最终组件,所述已知方法例如手工铺置、自动带铺置(ATL)、自动纤维布置、真空装袋、高压釜固化、高压釜外固化(out of autoclave cure)、流体协助加工、压力协助加工、合模加工(matched mould process)、简单压制固化、压制-粘着固化(press-clave cure)、或连续带压制。
根据本发明的一个实施方案,复合材料可以包含单层导电性纤维补强材料,其被施用于包含导电性颗粒的聚合物树脂层的一面上。复合材料可以以简单的层实施方案(ply embodiment)来制造,随后通过铺置来形成多层,以提供夹层结构。因此,在形成纤维-树脂-纤维构造的情况下,在铺置期间形成夹层结构。
因此,复合材料可以包含单个预浸渍体。替换性地,复合材料可以包含多个预浸渍体。
预浸渍体的聚合物树脂层厚度优选在约1μm至约100μm范围内,更优选在约1μm至约50μm范围内,最优选在约5μm至约50μm范围内。
可以施用多层导电性复合材料。因此,只是列举,组装可以使用12层标准复合材料和4层包含本发明导电性颗粒的复合材料来制备,由此提高最终组装的导电性。作为进一步的实例,层压体组装能由12层标准复合材料和包含导电性颗粒且不具有碳纤维补强材料的复合材料制备。任选地,在使用本发明的复合材料情况下,电绝缘层可以置于碳纤维层和树脂表面之间。例如,玻璃补强的纤维层能用作绝缘层。应当理解,存在很多可以使用的组装,此处描述的那些只是列举。
进一步益处是在完全固化之前本发明的复合材料是完全挠性的,适用于自动带铺置加工,该加工日益用于制造航空工业中的大型复合结构。
本发明的复合材料可以使用本领域已知的任何适当的温度、压力和时间条件来全部或部分地固化。
复合材料可以使用选自以下的方法来固化:UV-可见光照射,微波照射,电子束,γ照射,或其它适当的热或非热照射。
由此,根据本发明的第四方面,提供制备固化复合材料的方法,该方法包括第二方面的步骤和随后使复合材料固化的步骤。
第四方面的固化步骤可以使用任何已知方法。特别优选的方法是本文所述的固化方法。
由此提供固化复合材料,其包含根据本发明第一方面的复合材料,其中该复合材料是固化的。
当复合材料固化时,涂布金属的碳纤维层中其它树脂组分也同时固化。
尽管以下讨论的研究大多关于雷击防护,也容易地看出显示出降低的体积电阻率和高电导率的复合材料具有很多潜在应用。由此,通过本发明实现的电导率水平会使得形成的复合材料适用于电磁屏蔽、静电防护、电流回路、和其它需要提高的电导率的应用。
此外,尽管很多讨论集中在航空组件上,也还可以将本发明应用于雷击和其它在风轮机、建筑物、航海器、火车、机动车和其它有关方面中的电管理问题。
设想当本发明用于航空组件时,能用于初次结构应用(即对于维持航空器完整性是关键的那些结构元件),以及二次结构应用。
由此,提供用于制备由固化复合材料形成的航空制品的方法,该方法包括以下步骤:
-根据第四方面的方法制备固化复合材料;
-通过任何方法使用固化复合材料来生产航空制品。
根据本发明的再一方面,提供包含本发明固化复合材料的航空制品。
此处所述的所有特征可以与任何上述方面以任意组合进行组合。
为了可以更容易地理解本发明,现在仅通过列举和说明引用以下描述和附图,其中;
图1是模拟雷击之后,夹层体系(比较例1)的损坏面板的上表面照片。
图2是模拟雷击之后,夹层体系(比较例1)的损坏面板的下表面照片。
图3是模拟雷击之后,含有涂布银的空心玻璃球(比较例2)的夹层体系的损坏面板的上表面照片。
图4是模拟雷击之后,根据本发明的、含有涂布银的空心玻璃球的、具有涂布铜-镍的碳罩34gsm的夹层体系(实施例3)的损坏面板的上表面照片。
图5是模拟雷击之后,夹层体系(比较例1)的损坏面板的超声C-扫描;损害深度1-6层,损坏面积56,000mm2。
图6是含有涂布银的空心玻璃球(比较例2)的夹层体系的损坏面板的超声C-扫描;损害深度1-3层,损坏面积34,000mm2。
图7是根据本发明的、含有涂布银的空心玻璃球的、具有涂布铜-镍的碳罩的夹层体系的(实施例3)损坏面板的超声C-扫描;损害深度1-2层,损坏面积21,000mm2。
图8示出具有整体连接至导电性预浸渍体的涂布金属的纤维表面层并具有涂布金属的颗粒的预浸渍体组装。未示出其它颗粒状材料(例如在预浸渍体树脂中的热塑性颗粒)。
图9示出具有多层导电性预浸渍体和含有涂布金属的纤维层的表面层的预浸渍体组装。树脂I可以与树脂II相同或不同。
在图8中,能看到具有树脂表面层4并具有涂布金属的导电性颗粒8的浸渍体组装2,所述树脂表面层4包含整体连接至导电性预浸渍体的涂布金属的纤维6。在该图中未示出其它颗粒状材料,如预浸渍体树脂中的热塑性颗粒。
图9示出另一种具有多层导电性预浸渍体和表面层的预浸渍体组装10,该导电性预浸渍体具有聚合物树脂12(树脂I)和导电性碳纤维补强材料14,该表面层包含树脂4(树脂II)和涂布金属的纤维层6。树脂I可以与树脂II相同,或它们可以为不同树脂。
试验
在以下实施例中,″碳复合物″是指在补强碳纤维存在下用于制造预浸渍体的基础树脂(basic matrix resin)。HexPly M21是夹层的(interleaved)环氧树脂预浸渍体材料,可得自Hexcel Composites,Duxford,Cambridge,UnitedKingdom。
比较例1(碳复合物)
使用Winkworth混合机(Z-桨叶混合机)生产M21树脂,然后在硅酮剥离纸上成膜。然后使用中试规模UD预浸渍机将该树脂膜浸注于单向中间模碳纤维(intermediate modulus carbon fibre)上,这生产在35wt.%的树脂时具有面积重量190g/m2的预浸渍体。生产约为60cm×60cm的两个六层预浸渍体(铺置(lay up)0/90),这些在真空平台(vacuum table)上在7巴压力下在177℃下固化2小时。
面板测试区域1A:具有高可能性的初始雷击附着(initial lightning flashattachment)(进入或离开)并具有低可能性的闪电持续(flash hang on)的航空器表面(诸如雷达罩或前缘)。区域1A还包括扫掠引导附着(swept leaderattachment)区域。区域1A测试具有三个波形分量,高电流分量A(2x106A,<500μs),中电流分量B(平均2kA,<5ms)和持续电流分量C(200C,<1s)。面板的两个表面沿边缘附近打磨,以确保与外部框架的良好接触。区域IA是指所有的这样的航空器表面区域,在该区域中在具有低可能性的闪电持续的闪电通道附着期间,首次回击是预期的。
电极经由细铜线连接至面板。铜线提供测试时电流和蒸发的通道。有必要的是产生的电压不足以击穿空气。
如从表1和图1、2和5中可见,未闪电防护的夹层体系明显遭到区域1A模拟雷击的损坏。损坏遍及该体系,如果在实际雷击期间发生这会是灾难性的。
比较例2(碳复合物)
使用Winkworth混合机(Z-桨叶混合机)生产用涂布银的玻璃球(树脂的2vol.%,3.5wt.%)改性的M21树脂,然后在硅酮剥离纸上成膜。然后,使用中试规模的UD预浸渍机将该树脂膜浸注于单向的中间模件碳纤维上,这产生在35wt.%的树脂时具有面积重量190g/m2的预浸渍体。生产约为60cm×60cm的两个六层预浸渍体(铺置0/90),这些在真空平台上在7巴压力下在177℃下固化2小时。
面板测试区域1A如比较例1。
添加导电性颗粒至夹层体系已明显减小由区域1A雷击造成的损坏面积。表1以及图3和6示出损害深度降低一半,至顶部三层,损坏面积降低39%,这表明添加桥接树脂富集夹层的导电性颗粒的益处。
实施例3(碳复合物)
使用Winkworth混合机(Z-桨叶混合机)生产用涂布银的玻璃球(树脂的2vol.%,3.5wt.%)改性的M21树脂,然后在硅酮剥离纸上成膜。然后,使用中试规模的UD预浸渍机将该树脂膜浸注于单向的中间模件碳纤维上,这产生在35wt.%的树脂时具有面积重量190g/m2的预浸渍体。生产约为60cm×60cm的两个六层预浸渍体(铺置0/90)。向该铺置的外层添加Cu-Ni-C罩(34gsm)(由Technical Fibre Products提供),其用M21树脂膜(25gsm)浸渍。这些面板在真空平台上在7巴压力下在177℃下固化2小时。
面板测试区域1A如比较例1。
表1以及图4和7示出在区域IA模拟雷击后,添加Cu-Ni-C罩的层并且使用涂布银的空心玻璃珠进一步降低损坏面积和损害深度(至顶部二层)。
表1
除非文中另有说明,或者除非在参考测试方法和步骤中另有说明,否则所有列出的测试和物理性质都是在大气压和室温(即20℃)下测量的。
表面电阻率是具有均一厚度的薄膜的电阻率的度量。表面电阻率以欧姆/平方米(Ω/sq.)计,其相当于二维体系的电阻率。该术语因此是流经表面的电流的电阻率的度量,而不是穿过材料的电流的电阻率(表示为体积电阻率)的度量。表面电阻率也称为薄层电阻。
应当理解,本发明不限于上述仅作为范例的实施方案的细节。很多变体是可行的。
Claims (33)
1.复合材料,包括
i)预浸渍体,其包含至少一种聚合物树脂和至少一种导电性纤维补强材料;
ii)分散于所述聚合物树脂中的导电性颗粒;和
iii)包含树脂组分的面积重量为5gsm至100gsm的轻质涂布金属的碳罩顶层,所述树脂组分可以与所述预浸渍体中包含的所述至少一种聚合物树脂相同或不同,其中所述金属包含一种或多种选自镍、铜、金、铂、钯、铟和银中的金属。
2.根据权利要求1所述的复合材料,其中所述轻质涂布金属的碳罩包括涂布有镍与一种或多种选自铜、金、铂、钯、铟和银中的金属的组合的轻质碳罩。
3.根据权利要求2所述的复合材料,其中所述轻质碳罩涂布有镍和铜的组合。
4.根据权利要求1至3中任一项所述的复合材料,其中所述预浸渍体中包含的所述至少一种聚合物树脂和/或所述顶层中包含的所述树脂组分各自独立地包含至少一种热固性或热塑性树脂。
5.根据权利要求1至3中任一项所述的复合材料,其中所述导电性颗粒包括涂布金属的导电性颗粒或非金属性导电性颗粒。
6.根据权利要求5所述的复合材料,其中所述涂布金属的导电性颗粒包括基本上被金属包覆的核心颗粒。
7.根据权利要求6所述的复合材料,其中适用于涂布核心颗粒的金属包括银、金、镍、铜、锡、铝、铂或钯,或其任意两种或更多种的组合。
8.根据权利要求6所述的复合材料,其中使用多层金属涂层涂布核心颗粒。
9.根据权利要求5所述的复合材料,其中涂布金属的导电性颗粒的长径比<100。
10.根据权利要求5所述的复合材料,其中至少约90%的涂布金属的导电性颗粒和/或非金属性导电性颗粒的粒度在约0.3μm至约100μm范围内。
11.根据权利要求6所述的复合材料,其中所述核心颗粒选自聚合物、橡胶、陶瓷、玻璃、矿物、或耐火产品。
12.根据权利要求6所述的复合材料,其中所述核心颗粒是多孔的、空心的、或具有核-壳结构。
13.根据权利要求5所述的复合材料,其中金属涂层的电阻率小于3×10-5Ωm。
14.根据权利要求5所述的复合材料,其中非金属性导电性颗粒选自石墨片、石墨粉、石墨颗粒、石墨烯片、富勒烯、炭黑、本征导电性聚合物、电荷转移复合物、或它们的任意组合。
15.根据权利要求1至3中任一项所述的复合材料,其中所述复合材料进一步包含碳纳米材料。
16.根据权利要求15所述的复合材料,其中所述碳纳米材料选自碳纳米纤维、碳纳米管或它们的组合。
17.根据权利要求1至3中任一项所述的复合材料,其中所述导电性颗粒占该复合材料的约0.4vol.%至约15vol.%。
18.根据权利要求1至3中任一项所述的复合材料,其中纤维补强材料选自混杂或混合纤维体系,其包括合成纤维或天然纤维、或者它们的组合。
19.根据权利要求18所述的复合材料,其中所述纤维补强材料选自金属化玻璃、炭、石墨、或金属化聚合物纤维。
20.根据权利要求1至3中任一项所述的复合材料,其中所述复合材料包含至少一种固化剂。
21.根据权利要求20所述的复合材料,其中所述固化剂是4,4'-二氨基二苯基砜(4,4'-DDS)或3,3'-二氨基二苯基砜(3,3'-DDS)。
22.根据权利要求1至3中任一项所述的复合材料,其中所述复合材料包括另外的选自柔韧剂、增韧剂、促进剂、核壳橡胶、阻燃剂、湿润剂、颜料/染料、增塑剂、UV吸收剂、抗真菌化合物、填料、粘度改进剂/流动调节剂、增粘剂、稳定剂、抑制剂、或其中两种或更多种的任意组合的成分。
23.根据权利要求22所述的复合材料,其中所述增韧剂包括任意单独或组合的下列物质:聚酰胺,聚酰亚胺,聚酮,聚亚芳基醚,聚酯,聚砜,高性能烃聚合物,液晶聚合物,PTFE,和弹性体。
24.根据权利要求23所述的复合材料,其中聚酰胺选自共聚酰胺或芳族聚酰胺。
25.根据权利要求23所述的复合材料,其中聚酮选自聚醚醚酮。
26.根据权利要求23所述的复合材料,其中聚酯选自聚氨酯。
27.根据权利要求23所述的复合材料,其中弹性体选自嵌段弹性体。
28.制造复合材料的方法,包括:
i)提供预浸渍体,该预浸渍体包含至少一种聚合物树脂和至少一种导电性纤维补强材料;
ii)将导电性颗粒分散于所述聚合物树脂中;和
iii)添加包含树脂组分的面积重量为5gsm至100gsm的轻质涂布金属的碳罩顶层,所述树脂组分可以与所述预浸渍体中包含的所述至少一种聚合物树脂相同或不同,其中所述金属包括选自镍、铜、金、铂、钯、铟和银中的一种或多种金属。
29.根据权利要求28所述的方法,其中所述至少一种聚合物树脂具有初始的体积电阻率,并且其中将导电性颗粒分散于树脂中的步骤使聚合物树脂的体积电阻率降低至低于初始的体积电阻率。
30.用于制造固化的复合材料的方法,包括权利要求28的步骤(i)-(iii)以及随后使复合材料固化的步骤。
31.固化的复合材料,包括根据权利要求1-27中任一项所述的复合材料,其中所述复合材料是固化的。
32.航空制品,包括权利要求31的固化的复合材料。
33.用于制造由固化复合材料形成的航空制品的方法,包括以下步骤:
根据权利要求30所述的方法,制造固化的复合材料;和
使用固化的复合材料制造航空制品。
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GB0805640A GB0805640D0 (en) | 2008-03-28 | 2008-03-28 | Improved composite materials |
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PCT/GB2009/000616 WO2009118509A1 (en) | 2008-03-28 | 2009-03-06 | Improved composite materials |
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CN200980119875.0A Active CN102046367B (zh) | 2008-03-28 | 2009-03-06 | 改进的复合材料 |
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EP (1) | EP2271486B2 (zh) |
JP (2) | JP5730753B2 (zh) |
CN (1) | CN102046367B (zh) |
BR (1) | BRPI0909075A2 (zh) |
ES (1) | ES2446946T3 (zh) |
GB (1) | GB0805640D0 (zh) |
RU (1) | RU2496645C2 (zh) |
WO (1) | WO2009118509A1 (zh) |
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WO2009118509A1 (en) | 2009-10-01 |
JP2015091669A (ja) | 2015-05-14 |
JP5730753B2 (ja) | 2015-06-10 |
EP2271486A1 (en) | 2011-01-12 |
ES2446946T3 (es) | 2014-03-10 |
RU2010144034A (ru) | 2012-05-10 |
CN102046367A (zh) | 2011-05-04 |
EP2271486B2 (en) | 2021-01-27 |
US8517300B2 (en) | 2013-08-27 |
GB0805640D0 (en) | 2008-04-30 |
US20110017867A1 (en) | 2011-01-27 |
BRPI0909075A2 (pt) | 2020-06-23 |
JP2011519749A (ja) | 2011-07-14 |
RU2496645C2 (ru) | 2013-10-27 |
EP2271486B1 (en) | 2013-12-25 |
US20140047710A1 (en) | 2014-02-20 |
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