CN101541432A - 纤维材料和组合物 - Google Patents
纤维材料和组合物 Download PDFInfo
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- CN101541432A CN101541432A CNA2007800289058A CN200780028905A CN101541432A CN 101541432 A CN101541432 A CN 101541432A CN A2007800289058 A CNA2007800289058 A CN A2007800289058A CN 200780028905 A CN200780028905 A CN 200780028905A CN 101541432 A CN101541432 A CN 101541432A
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Abstract
本发明涉及纤维材料,制造纤维材料的方法,包含纤维材料和树脂的组合物,或包含纤维材料以及细菌和/或酶的组合物。另外,本发明公开了纤维材料组合物的用途。例如,能够通过微生物对所述纤维材料发挥作用以制造燃料,所述燃料包括氢、醇如乙醇、有机酸和/或烃。
Description
相关申请的交叉引用
本申请要求于2006年6月15日提交的美国专利申请11/453951的优先权,因此其全部内容整体引入到本文中作为参考。
技术领域
本发明涉及纤维材料,并涉及组合物。
背景技术
在许多应用中大量制造、加工并使用纤维材料,例如纤维素材料和木质纤维材料。通常,这类纤维材料使用一次,然后作为废物抛弃。
在美国专利6,448,307、6,258,876、6,207,729、5,973,035和5,952,105中已经描述了各种纤维材料、它们的用途和应用。本段中的每篇专利的完整内容引入到本文中作为参考。
发明内容
一般,本发明涉及纤维材料、制造纤维材料的方法、包含纤维材料的组合物(例如,包含所述纤维材料和树脂的复合材料,或者包含纤维材料及细菌和/或酶的组合物),以及涉及所述物质的用途。例如,所述组合物可以用于制造乙醇或者副产品如蛋白质或木素,或者应用于作为绝缘的结构。
在本文中公开的任何纤维材料可以与在美国专利6,448,307、6,258,876、6,207,729、5,973,035和5,952,105中公开的任何纤维材料、树脂、添加剂或其它成分组合使用。反过来,这些纤维材料和/或成分可以用于这些专利的任何一篇或本申请中公开的任何应用、产品、步骤等中。
所述纤维材料或包含所述纤维材料的组合物可以例如与结构或载体(例如,网织品、膜、浮动装置(flotation device)、袋子、外壳(shell)或生物可降解物质)缔合、混合、相邻、被所述结构或载体环绕或者在其内部。任选地,所述结构或载体自身可由纤维材料制成,或者由包含纤维材料的组合物制成。在某些实施方案中,所述纤维材料与提高纤维材料生物降解速率的材料如质子酸相结合。在某些实施方案中,所述纤维材料与减缓纤维材料降解的材料如缓冲剂相结合。
组合物中纤维材料与其它成分的比例将取决于所述成分的性质,且可以方便地调节以用于具体的产品应用。
包括由在本文中所述的任何方法制成的任何纤维材料的在本文中所述的所有纤维材料例如可以用于与树脂形成复合材料,或者可以与细菌和/或一种或多种酶结合以制造有价值的产品如燃料(例如,乙醇、烃或氢)。
在一个方面,本发明的特征在于制造纤维材料的方法。所述方法包括:对纤维源进行剪切以提供第一纤维材料,及将所述第一纤维材料穿过具有1.59mm(1/16英寸、0.0625英寸)以下平均开孔尺寸的第一筛网以提供第二纤维材料。在剪切之前,可以将所述纤维源,例如切割成类似于五彩纸屑材料的片或带。
在某些实施方案中,第一筛网的平均开孔尺寸小于0.79mm(1/32英寸,0.03125英寸),例如,小于0.40mm(1/64英寸,0.015625英寸)、小于0.20mm(1/128英寸,0.0078125英寸)或者甚至小于0.10mm(1/256英寸、0.00390625英寸)。
在具体的实施方式中,用旋转切割机进行所述剪切。如果需要,当所述纤维源干燥(例如,吸收的水小于0.25wt%)、含水时,或者甚至当所述纤维源部分或完全浸没液体如水或异丙醇中时,也可以进行所述剪切。
第二纤维材料可以例如收集在具有的压力低于标准大气压(nominal atmospheric pressure),例如低于标准大气压至少10%、低于标准大气压至少50%或低于标准大气压至少75%的储存斗中。
所述第二纤维可以例如剪切一次或多次例如两次、三次,或更多次例如十次。剪切可以“打开”所述纤维材料和/或对所述纤维材料“加应力(stress)”,使得所述材料更易于分散在例如溶液或树脂中。
可以对所述第二纤维材料例如进行剪切,并将所得到的纤维材料穿过第一筛网。
可以对所述第二纤维材料进行剪切,并将所得到的纤维材料穿过第二筛网以提供第三纤维材料,所述第二筛网具有的平均开孔尺寸小于所述第一筛网的平均开孔尺寸。
所述第二纤维材料的平均长径比与所述第三纤维材料的平均长径比的比值可以例如小于1.5、小于1.4、小于1.25或者甚至小于1.1。
例如,可以将所述第二纤维穿过第二筛网,所述第二筛网具有的平均开孔尺寸小于第一筛网的平均开孔尺寸。
剪切和穿过(passing)可以例如同时进行。
第二纤维材料可以具有例如大于10/1、大于25/1或者甚至大于50/1的平均长径比。
例如,所述第二纤维材料的平均长度可以为0.5mm至2.5mm,例如为0.75mm至1.0mm。例如,所述第二纤维材料的平均宽度可以为5μm至50μm,例如为10μm至30μm。
所述第二纤维材料长度的标准偏差可以小于所述第二纤维材料平均长度的60%,例如小于所述第二纤维材料平均长度的50%。
在某些实施方案中,所述第二纤维材料的BET表面积大于0.5m2/g,例如大于1.0m2/g、大于1.5m2/g、大于1.75m2/g、大于2.5m2/g、大于10.0m2/g、大于25.0m2/g、大于50.0m2/g或者甚至大于100.0m2/g。
在某些实施方案中,所述第二纤维材料的孔隙率大于25%,例如大于50%、大于75%、大于85%、大于90%、大于92%、大于95%或者甚至大于99%。
在具体的实施方案中,通过交织单丝来形成所述筛网。
所述纤维源可以包括例如纤维素材料、木质纤维材料。
在某些实施方案中,所述纤维源包括纤维的共混物,纤维例如为源于纸张来源的纤维和源于纺织品来源例如棉花的纤维。
在另一方面中,本发明的特征在于制造纤维材料的方法,所述方法包括对纤维源进行剪切以提供第一纤维材料;及将所述纤维材料穿过第一筛网以提供第二纤维材料。所述第一纤维材料的平均长径比与所述第二纤维材料的平均长径比的比值小于1.5。
在另一方面中,本发明的特征在于制造纤维材料的方法,所述方法包括:对纤维源进行剪切以提供第一纤维材料;将所述纤维材料穿过第一筛网以提供第二纤维材料;然后,对第二纤维材料再次进行剪切以提供第三纤维材料。
在另一方面中,本发明的特征在于由在本文中描述的任何一种纤维材料制成的复合材料或组合物。例如,组合物可以包含在本文中描述的任何一种纤维材料及细菌和/或酶。包含在本文中描述的任何一种纤维材料及细菌和/或酶的组合物可以为干燥状态,或它们可以包含液体如水。
例如,所述复合材料可以为如下形式:梯凳(stepping stool)、管、面板、装饰材料、板材、外壳、薄片、块状体、砖、杆、栅栏、构件、门、百叶窗、遮蓬、遮光物、标志、框架、窗框、底板、地板、瓷砖、铁路枕木、塔板、工具手柄、货摊(stalls)、薄膜、包装物、带、箱子、篮子、架子、套、粘合剂、两脚规、墙、垫子、框架、书柜、雕刻品、椅子、桌子、书桌、玩具、游戏器具、托盘、锭盘、桥墩、艇、桅杆、化粪池、自动面板、计算机外壳、地上和地下电套管、家具、餐桌、工作台、护罩、塔板、吊杆、盆(servers)、匣子(caskets)、图书封面、手杖和腋杖。
在另一方面,本发明的特征在于平均长径比大于5且纤维长度的标准偏差小于平均纤维长度60%的纤维材料。
例如,平均长径比可以大于10/1,例如大于15/1、大于25/1、大于35/1、大于45/1或者甚至大于50/1。
例如,平均长度可以为0.5mm至2.5mm。
在另一方面,本发明的特征在于制备纤维材料的方法,所述方法包括:对纤维源进行剪切以提供第一纤维材料;收集所述第一纤维材料;然后对所述第一纤维材料进行剪切以提供第二纤维材料。
在另一方面,本发明的特征在于制造有用材料如燃料的方法。所述方法包括:对纤维源进行剪切以提供第一纤维材料;将所述第一纤维材料穿过平均开孔尺寸约1.59mm(1/16英寸,0.0625英寸)以下的第一筛网以提供第二纤维材料;及将所述第二纤维材料与细菌和/或酶结合,所述细菌和/或酶利用所述第二纤维材料制造燃料,所述燃料包括氢、醇、有机酸和/或烃。
所述醇可以为例如甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙二醇、1,4-丁二醇、丙三醇或这些醇的混合物;所述有机酸可以为例如丙二酸、丁二酸、戊二酸、油酸、亚油酸、羟基乙酸、乳酸、γ-羟基丁酸或这些酸的混合物;且所述烃可以为例如甲烷、乙烷、丙烷、异丁烯、戊烷、正己烷或这些烃的混合物。
在与细菌和/或酶结合以前,在本文中描述的任何一种纤维材料可以被水解以将较高分子量碳水化合物分解成较低分子量碳水化合物。
在另一方面,本发明的特征在于制造有用材料如燃料的方法,所述方法包括对纤维源或纤维材料进行剪切,然后将其与细菌和/或酶结合。例如,纤维源可以剪切一次以提供纤维材料,然后将所述纤维材料与细菌和/或酶结合以制备有用材料。
在另一方面,本发明的特征在于增加纤维组合物密度的方法。所述方法包括:对纤维源进行剪切以提供纤维材料;将所述纤维材料与细菌和/或酶结合以提供纤维材料组合物;将所述组合物封装在基本不透气的材料中;及从封装的组合物中除去夹带气体以增加组合物密度。例如,所述不透气材料可以为袋状,且通过从袋中排空空气,然后密封所述袋,能够增加所述组合物密度。
在另一方面,本发明的特征在于包含纤维材料、树脂和染料的复合材料。
例如,所述纤维材料可以具有大于5的平均长径比,及小于平均纤维长度60%的纤维长度的标准偏差。
在某些实施方案中,所述复合材料还包含颜料。
在某些实施方式中,染料浸透到纤维中或铺展在纤维表面上。
在另一方面,本发明的特征在于制造复合材料的方法,所述方法包括:对纤维材料染色;将所述纤维材料与树脂结合;及由所述组合形成复合材料。
在另一方面,本发明的特征在于制造复合材料的方法,所述方法包括:向树脂中添加染料以提供染料/树脂组合;将染料/树脂组合与纤维材料结合;并由染料/树脂组合和纤维材料形成复合材料。
在本文中使用的术语“纤维材料”为包含大量松散、不连续且可分离的纤维的材料。例如,可以由多涂层纸(polycoated paper)或漂白了的牛皮纸纤维源,通过例如使用旋转切割机进行剪切来制备纤维材料。
在本文中使用的术语“筛网”是指能够按照尺寸筛分材料的元件,例如,穿孔的板、圆筒等,或者金属丝网或布织物(cloth fabric)。
实施方案和/或方面可以具有如下优点的任何一种或其组合。纤维材料被打开和/或加应力,使得所述材料更易于分散在例如溶液或树脂中,并使得它们更易于受到化学药品、酶或生物攻击。所述纤维材料可以具有例如比较窄的长度和/或长径比分布,以便始终如一地限定它们的性能。例如,当纤维材料的纤维与熔融的树脂或溶液共混时,其可以以一致且可预测的方式改变熔融的树脂或溶液的流变性,例如结果产生例如更加易于模制和挤出的树脂/纤维材料组合。例如,所述纤维材料可以容易地穿过如那些在注塑模具中发现或与注塑模具相关的微小开孔或通道,例如浇口(gate)或热流道。由这类纤维材料模制的零件可以展示良好的表面光洁,例如大颗粒和/或团聚颗粒具有很少的可见斑点。
在本文中提及的所有公布、专利申请、专利和其它参考文献,关于它们所包含的所有内容整体引入到本文中作为参考。
本发明的其它特征和优点将通过下面的具体实施方式和权利要求书而变得显而易见。
附图说明
图1为显示将纤维源转化成第一和第二纤维材料的方块图。
图2为旋转切割机的剖视图。
图3-8为由单丝制成的各种筛网的俯视图。
图9为显示将纤维源转化成第一、第二和第三纤维材料的方块图。
图10A和10B为纤维源的照片;图10A为多涂层纸容器的照片;图10B为未漂白牛皮纸辊的照片。
图11和12分别为由多涂层纸制造的纤维材料25倍放大和1000倍放大的扫描电子显微照片。利用具有1/8英寸开孔的筛网在旋转切割机上制造所述纤维材料。
图13和14分别为由漂白了的牛皮纸板纸制造的纤维材料25倍放大和1000倍放大的扫描电子显微照片。利用具有1/8英寸开孔的筛网在旋转切割机上制造所述纤维材料。
图15和16分别为由漂白了的牛皮纸板纸制造的纤维材料25倍放大和1000倍放大的扫描电子显微照片。在每次剪切期间,利用具有1/16英寸开孔的筛网在旋转切割机上对所述纤维材料剪切两次。
图17和18分别为由漂白了的牛皮纸板纸制造的纤维材料25倍放大和1000倍放大的扫描电子显微照片。在旋转切割机上对所述纤维材料剪切三次。在第一次剪切期间,使用1/8英寸的筛网;在第二次剪切期间,使用1/16英寸的筛网;及在第三次剪切期间,使用1/32英寸的筛网。
图19为显示纤维材料组合物的可逆的堆密度增加的方块图。
具体实施方式
参考图1,例如在旋转切割机中剪切纤维源10以提供第一纤维材料12。将所述第一纤维材料12穿过平均开孔尺寸为1.59mm(1/16英寸,0.0625英寸)以下的第一筛网16以提供第二纤维材料14。如果需要,纤维源10在剪切之前,可以例如用切碎机进行切割。例如,当将纸用作纤维源10时,可以使用切碎机将纸首先切割成例如1/4至1/2英寸宽的条,所述切碎机例如为反向旋转螺杆切碎机,如由Munson(Utica,N.Y.)制造的切碎机。作为切碎的替代方法,使用闸刀式切纸机通过切割至所需的尺寸可以将纸的尺寸降低。例如,可以使用所述闸刀式切纸机将纸切割成例如10英寸宽×12英寸长的片。
在某些实施方案中,对纤维源10的剪切和将所得到的第一纤维材料12穿过第一筛网16同时进行。所述剪切和穿过还能以间歇式的方法进行。
例如,可以将旋转切割机同时用于剪切纤维源10和筛分所述第一纤维材料12。参考图2,旋转切割机20包括加料斗22,所述加料斗可以装载有通过对纤维源10进行切碎而制备的切碎的纤维源10′。将切碎的纤维源10′在静止刀片24和旋转刀片26之间进行剪切以提供第一纤维材料12。将第一纤维材料12穿过具有上述尺寸的筛网16,并将所得到的第二纤维材料14收集在储存斗30中。为了便于收集所述第二纤维材料14,储存斗30可以具有低于标准大气压的压力,例如低于标准大气压至少10%,例如低于标准大气压至少25%、低于标准大气压至少50%或者低于标准大气压至少75%。在某些实施方案中,利用真空源50(图2)保持储存斗低于标准大气压。
剪切可以有利于“打开”所述纤维材料和对所述纤维材料“加应力”,使得上述材料更易于分散在例如溶液或树脂中,并使得它们更易于被化学药品、酶或生物攻击。不希望受到任何具体理论束缚,至少在某些实施方案中相信剪切可以使得纤维表面具有官能团如羟基或羧酸基,所述官能团可以例如帮助将所述纤维分散在熔融的树脂中,或者提高化学药品或生物攻击。
所述纤维源可以在干燥状态、含水状态(例如,具有高达10wt%的吸收水)或湿状态(例如,具有约10wt%至约75wt%的水)下剪切。所述纤维源甚至可以在部分或全部浸没到液体如水、乙醇、异丙醇下时被剪切。
还可以在气体(如除空气以外的气体的气流或气氛),例如氧气或氮气或水蒸气中剪切所述纤维源。
制造纤维材料的其它方法包括石材研磨(stone grinding)、机械裂开或撕裂、针磨(pin grinding)或空气损耗研磨(air attrition milling)。
如果需要,根据所述纤维材料的长度、宽度、密度、材料类型或这些属性的一些组合,可以连续或间歇地将所述纤维材料分离复数份。例如,为了形成复合材料,通常需要具有较窄的纤维长度分布。另外,例如当制造包含细菌和/或酶的组合物时,通常希望使用基本上单一的材料作为进料。
例如,将包含铁质材料的纤维材料穿过磁铁例如电磁铁,然后将所得到的纤维材料穿过每种筛网具有不同尺寸开孔的一系列筛网,可以将铁质材料从任何纤维材料中分离出去。
所述纤维材料也可以例如通过使用高速气体例如空气分离。在这种方法中,通过抽取不同部分而将所述纤维材料进行分离,如果需要,可以对各部分进行光子学表征。在Lindsey等人的美国专利6,883,667中讨论了这类分离设备,其全部公开整体引入到本文中作为参考。
在它们制备好以后,可以立即使用所述纤维材料,或可以对它们进行干燥,例如在约105℃下干燥4至18小时,使得在使用之前水分含量例如低于约0.5%。
如果需要,可以从含木素的任何纤维材料如木质纤维材料中除去木素。另外,如果需要,可以对所述纤维材料进行杀菌以杀死可能存在于所述纤维材料上的任何微生物。例如,通过将纤维材料暴露于辐射如红外辐射、紫外辐射或电离辐射如伽马辐射,可以对纤维材料进行杀菌。通过调节温度例如在一定条件下对纤维材料进行加热或冷却足够时间以杀死任何微生物,或者通过使用化学杀菌剂如漂白粉(例如,次氯酸钠)、双氯苯双胍己烷或环氧乙烷,也可以对纤维材料进行杀菌。通过使用竞争性生物如抗细菌酵母(yeast against bacteria),也可以对纤维材料进行杀菌。
参考图3-8,在某些实施方案中,第一筛网16的平均开孔尺寸小于0.79mm(1/32英寸,0.03125英寸),例如小于0.51mm(1/50英寸,0.02000英寸)、小于0.40mm(1/64英寸,0.015625英寸)、小于0.23mm(0.009英寸)、小于0.20mm(1/128英寸,0.0078125英寸)、小于0.18mm(0.007英寸)、小于0.13mm(0.005英寸)或者甚至小于0.10mm(1/256英寸,0.00390625英寸)。通过交织具有适当直径的单丝52以提供所需的开孔尺寸来制备筛网16。例如,所述单丝可以由金属例如不锈钢制成。随着开孔尺寸越小,对单丝的结构性要求可能会越高。例如,对于小于0.40mm的开孔尺寸,由除了不锈钢以外的材料例如钛、钛合金、无定形金属、镍、钨、铑、铼、陶瓷或玻璃制成的单丝制造所述筛网可以是有利的。在某些实施方案中,所述筛网由具有使用激光插入所述板中的孔的板例如金属板制成。
在某些实施方案中,对第二纤维14进行剪切并将其穿过所述第一筛网16,或者不同尺寸的筛网。在某些实施方案中,将所述第二纤维材料14穿过平均开孔尺寸等于或小于第一筛网16的第二筛网。
参考图9,通过对所述第二纤维材料14进行剪切并将所得到的材料穿过平均开孔尺寸小于第一筛网16的第二筛网60,可以由所述第二纤维材料14制备第三纤维材料62。
纤维源包含纤维素纤维源,所述纤维素纤维源包括类似于图10A(多涂层纸)和10B(牛皮纸)中所示的那些的纸和纸产品;以及木质纤维的纤维源,所述木质纤维的纤维源包括木材和木材相关材料例如碎料板。其它合适的纤维源包括天然纤维源,例如草、稻壳、甘蔗渣、棉花、黄麻、大麻、亚麻、竹子、剑麻、蕉麻、稻草、玉米棒子、稻壳、椰子绒毛(coconut hair);α-纤维素含量高的纤维源,例如棉花;合成的纤维源,例如挤出纱线(定向纱线或未定向纱线)或碳纤维源;无机纤维源;及金属纤维源。天然或合成纤维源可以由原始废料织物材料例如残余物获得,或者它们可以为消费后废料例如碎布。当将纸产品用作纤维源时,它们可以为原始材料,例如废料原始材料,或者它们可以为消费后废料。除了原始原材料以外,消费后的、工业的(例如,废弃物)和生产废料(例如,来自纸张加工的流出物)也可以用作纤维源。同样,所述纤维源可以从人类(例如,污水)、动物或工厂废料获得或得到。另外的纤维源已经在美国专利6,448,307、6,258,876、6,207,729、5,973,035和5,952,105中进行了描述,上述每篇专利都整体引入到本文中作为参考。
可以使用任何上面纤维源的共混物。
通常,所述纤维材料的纤维可以具有比较大的平均长径比(例如,大于20比1),即使它们已经被剪切过多次。另外,在本文中描述的纤维材料的纤维可以具有比较窄的长度和/或长径比分布。不希望受到任何具体理论束缚,目前相信比较大的平均长径比及比较窄的长度和/或长径比分布至少部分地使得易于将所述纤维材料分散在树脂例如熔融的热塑性树脂中。还相信比较大的平均长径比及比较窄的长度和/或长径比分布至少部分地使得纤维材料的性能始终如一;纤维材料赋予树脂可预知的流变性调节;纤维材料和树脂的组合易于浇铸、挤出和注模;纤维材料易于穿过微小、通常曲折的通道和孔口;以及就模制的零件而言可能展示优异的表面光洁,例如光滑的光洁和/或基本不含可见斑点的光洁。
如在本文中使用的,平均纤维宽度(即,直径)为通过视觉随机选取大约5000根纤维测定的宽度。平均纤维长度为修正过的长度加权长度。BET(Brunauer、Emmet和Teller)表面积为多点表面积,且孔隙率为由水银孔隙度计测定的孔隙率。
第二纤维材料14的平均长径比可以为,例如大于8/1,例如大于10/1、大于15/1、大于20/1、大于25/1或者大于50/1。第二纤维材料14的平均长度可以为例如约0.5mm至2.5mm,例如约0.75mm至1.0mm,且第二纤维材料14的平均宽度(即,直径)可以为例如约5μm至50μm,例如约10μm至30μm。
在某些实施方案中,第二纤维材料14的长度的标准偏差小于第二纤维材料14的平均长度的60%,例如小于平均长度的50%、小于平均长度的40%、小于平均长度的25%、小于平均长度的10%、小于平均长度的5%或者甚至小于平均长度的1%。
在某些实施方案中,所述第二纤维材料14的BET表面积大于0.1m2/g,例如大于0.25m2/g、大于0.5m2/g、大于1.0m2/g、大于1.5m2/g、大于1.75m2/g、大于5.0m2/g、大于10m2/g、大于25m2/g、大于35m2/g、大于50m2/g、大于60m2/g、大于75m2/g、大于100m2/g、大于150m2/g、大于200m2/g或者甚至大于250m2/g。所述第二纤维材料14的孔隙率可以为例如大于20%、大于25%、大于35%、大于50%、大于60%、大于70%、例如大于80%、大于85%、大于90%、大于92%、大于94%、大于95%、大于97.5%、大于99%或者甚至大于99.5%。
在某些实施方案中,第一纤维材料12的平均长径比与第二纤维材料14的平均长径比的比值例如小于1.5,例如小于1.4、小于1.25、小于1.1、小于1.075、小于1.05、小于1.025或者甚至基本等于1。
在具体实施方案中,所述第二纤维材料14被再次剪切且将所得到的纤维材料穿过平均开孔尺寸小于第一筛网的第二筛网以提供第三纤维材料62。在此情况下,第二纤维材料14的平均长径比与第三纤维材料62的平均长径比的比值可以例如小于1.5,例如小于1.4、小于1.25或者甚至小于1.1。
在某些实施方案中,将所述第三纤维材料62穿过第三筛网以制造第四纤维材料。可以将所述第四纤维材料例如穿过第四筛网以制造第五材料。可以按需重复类似的筛分步骤许多次以制造所需的具有所需性能的纤维材料。
在某些实施方案中,所需的纤维材料包括平均长径比大于5且纤维长度的标准偏差小于平均长度60%的纤维。例如,所述平均长径比可以大于10/1,例如大于25/1或大于50/1,且平均长度可以为约0.5mm至2.5mm,例如约0.75mm至1.0mm。纤维材料的平均宽度可以为约5μm至50μm,例如约10μm至30μm。例如,所述标准偏差可以小于平均长度的50%,例如小于40%、小于30%、小于25%、小于20%、小于10%、小于5%或者甚至小于平均长度的1%。所需的纤维材料的BET表面积可以例如大于0.5m2/g,例如大于1.0m2/g、大于1.5m2/g、大于1.75m2/g、大于5m2/g、大于10m2/g、大于25.0m2/g、大于50.0m2/g、大于75.0m2/g或者甚至大于100.0m2/g。所需的材料的孔隙率可以例如大于70%,例如大于80%、大于87.5%、大于90%、大于92.5%、大于95%、大于97.5%或者甚至大于99%。特别优选的实施方案具有大于1.25m2/g的BET表面积和大于85%的孔隙率。
纤维材料/树脂复合材料
通过将所需的纤维材料和所需的树脂结合,可以制备包含在本文中描述的任何纤维材料或任何纤维材料的共混物(包含在美国专利6448307、6258876、6207729、5973035和5952105中公开的任何纤维材料)和树脂的复合材料,所述纤维材料例如为所述第一纤维材料12或第二纤维材料14,且所述树脂例如为热塑性树脂或热固性树脂。例如,通过将纤维材料和树脂在挤出机或其它混合器中进行混合,可以将所需的纤维材料与所需的树脂结合。为了形成复合材料,可以将纤维材料以纤维材料本身或者以可以在结合期间重新打开的密度增加的纤维材料的形式与树脂结合。在2006年3月23日提交的国际申请PCT/US2006/010648中讨论了这种密度增加的材料,其公开内容整体引入到本文中作为参考。
热塑性树脂的例子包括刚性和弹性热塑性塑料。刚性热塑性塑料包括聚烯烃(例如,聚乙烯、聚丙烯或聚烯烃共聚物)、聚酯(例如聚对苯二甲酸二乙酯)、聚酰胺(例如,尼龙6、6/12或6/10)以及聚乙烯亚胺。弹性热塑性树脂的例子包括弹性苯乙烯共聚物(例如,苯乙烯-乙烯-丁烯-苯乙烯共聚物)、聚酰胺弹性体(例如,聚醚-聚酰胺共聚物)和乙烯-乙酸乙烯酯共聚物。
在某些实施方案中,热塑性树脂的熔体流动速率为10g/10分钟至60g/10分钟,例如20g/10分钟至50g/10分钟或30g/10分钟至45g/10分钟,所述熔体流动速率使用ASTM 1238测得。
在某些实施方案中,可以使用上面任何热塑性树脂的相容性共混物。
在某些实施方案中,热塑性树脂的多分散指数(PDI),即重均分子量与数均分子量的比值大于1.5,例如大于2.0、大于2.5、大于5.0、大于7.5或者甚至大于10.0。
在具体实施方案中,可以将聚烯烃或聚烯烃的共混物用作热塑性树脂。
热固性树脂的例子包括天然橡胶、丁二烯橡胶和聚氨酯。
除了所需的纤维材料和树脂以外,还可以向纤维材料和树脂的组合中添加例如固体或液体形式的添加剂。例如,合适的添加剂包括填料如碳酸钙、石墨、硅灰石、云母、玻璃、玻璃纤维、二氧化硅和滑石;无机阻燃剂如三水合氧化铝或氢氧化镁;有机阻燃剂如氯代或溴代有机化合物;磨碎的建筑废料;磨碎的轮胎橡胶;碳纤维;或者金属纤维或粉末(例如,铝、不锈钢)。这些添加剂可以增强、扩展或改变电、机械或相容性性能。其它添加剂包括:香料;偶联剂;增容剂,例如马来酸聚丙烯(maleated polypropylene);加工助剂;润滑剂,例如氟化聚乙烯;增塑剂;抗氧化剂;遮光剂;热稳定剂;着色剂;发泡剂;抗冲改性剂;聚合物,例如可降解聚合物;光稳定剂;抗微生物剂;抗静电剂,例如硬脂酸酯或乙氧基化的脂肪酸胺。合适的抗静电化合物包括:导电炭黑;碳纤维;金属填料;阳离子化合物,例如季铵化合物例如氯化N-(3-氯-2-羟丙基)-三甲基铵、链烷醇酰胺和胺。代表性的可降解聚合物包括:多羟基酸,例如聚丙交酯、聚乙交酯及乳酸和羟基乙酸的共聚物、聚(羟基丁酸)、聚(羟基戊酸)、聚[丙交酯-共-(e-己内酯)]、聚[乙交酯-共-(e-己内酯)]、聚碳酸酯、聚(氨基酸)、聚(羟基链烷酸酯)、聚酸酐、聚原酸酯以及这些聚合物的共混物。
在某些实施方案中,在与树脂结合以前,先对纤维材料进行杀菌以杀死可能存在于纤维材料上的任何微生物。例如,通过将所述纤维材料暴露于辐射;通过在一定条件下对纤维材料进行加热足够时间以杀死任何微生物,例如在标准大气压下沸腾;或者通过使用化学杀菌剂,可以对纤维材料进行杀菌。
使得复合材料的气味和/或外观接近于天然木材例如杉木可以是有利的。例如,可以将香料如天然木材香料复合到用于制备复合材料的树脂中。在某些实施方式中,将香料以油的形式直接复合到树脂中。例如,使用辊式破碎机例如混合器或挤出机,例如具有反向旋转螺杆的双螺杆挤出机,可以将所述油复合到树脂中。混合器的一个例子为由Farrel制造的F-系列混合器。双螺杆挤出机的例子为由Krupp Werner & Pfleiderer制造的WP ZSK 50MEGAcompunderTM。在复合以后,可以将有香味的树脂添加至纤维材料中并挤出或模制。作为选择,填充香料的树脂的母料(master batches)可在商业上以商品名PolyIffTM得自于国际香料公司(InternationalFlavors and Fragrances)或得自于RTP公司。在某些实施方案中,复合材料中香料的量为约0.005wt%至约10wt%,例如约0.1%至约5%或者0.25%至约2.5%。
其它天然木材香料包括常青树或红杉。其它香料包括:薄荷、樱桃、草莓、桃子、酸橙、荷兰薄荷、肉桂、茴香、罗勒、香柠檬、黑胡椒、樟脑、甘菊、香茅、桉树、松树、冷杉、老鹳草、生姜、柚子、茉莉、刺柏子(juniperberry)、薰衣草、柠檬、中国柑桔、甘牛至草、麝香、myrhh、桔子、天竺薄荷、玫瑰、迷迭香、鼠尾草、檀香木、茶树、百里香、鹿蹄草、衣兰香精(ylang ylang)、香草、new car或这些香料的混合物。在某些实施方案中,纤维材料-香料组合中香料的量为约0.005wt%至约20wt%,例如约0.1%至约5%或者0.25%至约2.5%。于2005年6月7日提交的美国临时申请60/688,002号中描述的其它香料和方法,其全部公开引入到本文中作为参考。
可以使用上述任何纤维材料如第一纤维材料12或第二纤维材料14与树脂,形成制品如管、面板、装饰材料、板材、外壳、薄片、块状体、砖、杆、栅栏、构件、门、百叶窗、遮蓬、遮光物、标志、框架、窗框、底板、地板、瓷砖、铁路枕木、塔板、工具手柄、货摊、薄膜、包装物、带、箱子、篮子、架子、套、粘合剂、两脚规、墙、垫子、框架、书柜、雕刻品、椅子、桌子、书桌、玩具、游戏器具、托盘、锭盘、桥墩、艇、桅杆、化粪池、自动面板、计算机外壳、地上和地下电套管、家具、餐桌、工作台、护罩、塔板、吊杆、盆、匣子、图书封面、手杖、腋杖、绝缘体、丝线、布、新产品、家用品和房屋结构。
在与树脂结合且复合以形成上述复合材料以前,可以对纤维材料染色。在某些实施方案中,这种染色可以有助于掩蔽或隐藏纤维材料,尤其是在模制或挤出零件中大块的纤维材料。当这类大块存在的浓度比较高时,可以在模制或挤出零件中显示为斑点。
例如,可以使用酸性染料、直接染料或活性染料对所需要的纤维材料进行染色。这类染料得自于Spectra Dyes、Kearny、NJ或KeystoneAniline Corporation,Chicago,IL。染料的具体例子包括SPECTRATMLIGHT YELLOW 2G、SPECTRACIDTM YELLOW 4GL CONC 200、SPECTRANYLTM RHODAMINE 8、SPECTRANYLTM NEUTRAL REDB、SPECTRAMINETM BENZOPERPURINE、SPECTRADIAZOTMBLACK OB、SPECTRAMINETM TURQUOISE G、和SPECTRAMINETMGREY LVL 200%,每种染料均得自于Spectra Dyes。
在某些实施方案中,将包含颜料的树脂浓色母料(resin colorconcentrate)与染料共混。当这类共混物然后与所需要的纤维材料复合时,所述纤维材料可在复合期间被就地染色。浓色母料得自于Clariant。
实施例
在JEOL 65000场发射扫描电子显微镜上获得了扫描电子显微照片。通过Integrated Paper Services,Inc.,Appleton,WI使用自动分析仪(TAPPI T271)测定了纤维长度和宽度(即,直径)。通过微晶学分析设施(Micromeritics Analytical Service)测定了BET表面积,如孔隙率和堆密度一样。
实施例1-由多涂层纸制备纤维材料
从国际纸业(International Paper)获得1500磅运物车(skid)的由堆密度为20lb/ft3的未印刷多涂层白色牛皮纸板制成的原始、半加仑果汁硬纸盒。使用闸刀式切纸机将所述材料切割成8.25英寸×11英寸的片,并向Munson旋转切割机Model SC30进料。Model SC30装配有四个旋转刀片、四个固定刀片和具有1/8英寸开孔的排放筛网。将旋转刀片和固定刀片之间的缝隙设定为约0.020英寸。所述旋转切割机剪切经过刀口的类似于五彩纸屑的片,撕开所述片并以约每小时一磅的速率释放纤维材料。纤维材料的BET表面积为0.9748m2/g±0.0167m2/g,孔隙率为89.0437%且0.53磅/平方英寸下的堆密度为0.1260g/mL。纤维的平均长度为1.141mm,纤维的平均宽度为0.027mm,给出的平均L/D为42∶1。将纤维材料25倍放大和1000倍放大的扫描电子显微照片分别示于图11和12中。
实施例2-由漂白了的牛皮纸板制备纤维材料
从国际纸业获得1500磅运物车的堆密度为30lb/ft3的原始漂白的白色牛皮纸板板。使用闸刀式切纸机将所述材料切割成8.25英寸×11英寸的片并向Munson旋转切割机Model SC30进料。排放筛网具有1/8英寸的开孔。将旋转刀片和固定刀片之间的缝隙设定为约0.020英寸。所述旋转切割机剪切类似于五彩纸屑的片,以约每小时一磅的速率释放纤维材料。纤维材料的BET表面积为1.1316m2/g±0.0103m2/g,孔隙率为88.3285%且0.53磅/平方英寸下的堆密度为0.1497g/mL。纤维的平均长度为1.063mm,纤维的平均宽度为0.0245mm,给出的平均L/D为43∶1。将纤维材料25倍放大和1000倍放大的扫描电子显微照片分别示于图13和14中。
实施例3-由漂白了的牛皮纸板制备二次剪切的纤维材料
从国际纸业获得1500磅运物车的堆密度为30lb/ft3的原始漂白的白色牛皮纸板。使用闸刀式切纸机将所述材料切割成8.25英寸×11英寸的片并向Munson旋转切割机Model SC30进料。排放筛网具有1/16英寸的开孔。将旋转刀片和固定刀片之间的缝隙设定为约0.020英寸。所述旋转切割机剪切类似于五彩纸屑的片,以约每小时一磅的速率释放纤维材料。将由第一次剪切所得到的材料进料回到上述相同设备中并再次剪切。所得到的纤维材料的BET表面积为1.4408m2/g±0.0156m2/g,孔隙率为90.8998%且0.53磅/平方英寸下的堆密度为0.1298g/mL。纤维的平均长度为0.891mm,纤维的平均宽度为0.026mm,给出的平均L/D为34∶1。将纤维材料25倍放大和1000倍放大的扫描电子显微照片分别示于图15和16中。
实施例4-由漂白了的牛皮纸板制备三次剪切的纤维材料
从国际纸业获得1500磅运物车的堆密度为30lb/ft3的原始漂白的白色牛皮纸板。使用闸刀式切纸机将所述材料切割成8.25英寸×11英寸的片并向Munson旋转切割机Model SC30进料。排放筛网具有1/8英寸的开孔。将旋转刀片和固定刀片之间的缝隙设定为约0.020英寸。所述旋转切割机剪切经过刀口的类似于五彩纸屑的片。将由第一次剪切所得到的材料进料回到上述相同设备并将筛网更换为1/16英寸的筛网。对该材料进行剪切。将由第二次剪切所得到的材料进料回到上述相同设备并将筛网更换为1/32英寸的筛网。对该材料进行剪切。所得到的纤维材料的BET表面积为1.6897m2/g±0.0155m2/g,孔隙率为87.7163%且0.53磅/平方英寸下的堆密度为0.1448g/mL。纤维的平均长度为0.824mm,纤维的平均宽度为0.0262mm,给出的平均L/D为32∶1。将纤维材料25倍放大和1000倍放大的扫描电子显微照片分别示于图17和18中。
其它组合物和所述纤维材料的用途
可以制备这样的组合物,所述组合物包含在本文中描述的任何纤维材料,所述纤维材料包括美国专利6448307、6258876、6207729、5973035和5952105中公开的任何纤维材料、树脂、添加剂或其它成分。例如,在本文中描述的任何纤维材料可以与固体、液体或气体,例如,化学药品或化学制剂(固态或液态)如药物(例如,抗生素)、农业材料(例如,植物种子、肥料、除草剂或杀虫剂)或者酶或包含酶的制剂结合。另外可以制备包含一种或多种细菌或者与一种或多种酶组合的细菌的组合物。
这类组合物可以利用纤维材料的期望性能。例如,可以使用任何纤维材料来吸收化学药品,可能吸收它们自身重量的许多倍。例如,可以将纤维材料用于吸收溢出的油或其它化学药品。将这些纤维材料与可以代谢油或化学药品的微生物如细菌结合可以有助于清洁。例如,可以将所述纤维材料与酶溶液结合、干燥、然后用于宠物寝具中,或者将其与药物结合并用于传递治疗剂如药品。如果需要,可以将所述纤维材料与可降解聚合物,例如聚羟基乙酸、聚乳酸、以及羟基乙酸和乳酸的共聚物结合。其它可以使用的可降解材料已经在上面讨论过了。
可以在例如各种浸渍、喷雾或共混设备中制备包含纤维材料如纤维素或木质纤维材料与例如固态、液态或气态的化学药品或化学制剂的组合物。例如,使用带式混合机、锥形混合机、双锥体混合机和Patterson-Kelly“V”式混合机,可以制备所述组合物。
如果需要,可以将木素从含木素的任何纤维材料如木素纤维材料中除去。另外,如果需要,可以对纤维材料进行杀菌以杀死可能存在于纤维材料上的任何微生物。例如,通过将纤维材料暴露于辐射如红外辐射、紫外辐射或电离辐射如伽马辐射下,可以对纤维材料进行杀菌。通过在一定条件下对纤维材料加热足够时间以杀死任何微生物,或者通过使用化学杀菌剂如漂白剂(例如,次氯酸钠)、双氯苯双胍己烷或环氧乙烷,也可以对纤维材料进行杀菌。
可以例如使用液体如水对任何纤维材料进行清洗以除去任何所不需要的杂质和/或污染物。
在具体应用中,可以将所述纤维材料用作用于各种微生物如酵母和细菌的进料,所述微生物可以对纤维材料产生发酵或其它作用以制造有用材料如燃料,所述燃料例如为醇、有机酸、烃或氢或者蛋白质。
制造的醇可以为一元醇如乙醇或者多元醇如乙二醇或丙三醇。可以制造的醇的例子包括甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙二醇、1,4-丁二醇、丙三醇或这些醇的混合物。制造的有机酸可以为一元羧酸或多元羧酸。有机酸的例子包括甲酸、乙酸、丙酸、丁酸、戊酸、己酸、棕榈酸、硬脂酸、草酸、丙二酸、丁二酸、戊二酸、油酸、亚油酸、羟基乙酸、乳酸、γ-羟基丁酸或这些酸的混合物。制造的烃可以为例如烷烃或烯烃。可以制造的烃的例子包括甲烷、乙烷、丙烷、异丁烯、戊烷、正己烷或这些烃的混合物。
在具体实施方案中,对包括纤维素纤维和/或木质纤维的纤维源进行剪切以提供第一纤维材料。然后将所述第一纤维材料穿过平均开孔尺寸为约1.59mm(1/16英寸,0.0625英寸)以下的第一筛网以提供第二纤维材料。将所述第二纤维材料与细菌和/或酶结合。在该具体实施方案中,细菌和/或酶可以直接利用所述第二纤维材料而不用预处理以制造燃料,所述燃料包括氢、醇、有机酸和/或烃。
在某些实施方案中,在结合细菌和/或酶之前,对所述纤维材料进行杀菌以杀死可能存在于纤维材料上的任何微生物。例如,通过将纤维材料暴露于辐射如红外辐射、紫外辐射或电离辐射如伽马辐射下,可以对所述纤维材料进行杀菌。另外,使用化学杀菌剂如漂白剂(例如,次氯酸钠)、双氯苯双胍己烷或环氧乙烷也可以杀死微生物。
在具体实施方案中,首先将纤维材料的纤维素和/或木质纤维材料分解成低分子量的糖,然后将其添加至使所述低分子量的糖发酵的酵母和/或细菌的溶液中以制造乙醇。使用化学药品如酸或碱,通过酶或二者的组合,可以分解纤维素和/或木质纤维材料。Bjerre在Biotechnol.Bioeng.,49:568(1996)中和Kim在Biotechnol.Prog.,18:489(2002)中描述了纤维素材料的化学水解,这两篇文章全部引入到本文中作为参考。
DiPardo在Journal of Outlook for Biomass Ethanol Production andDemand(EIA Forecasts)(生物质乙醇的生产和需求展望杂志(EIA预测)),2002中;Sheehan在Biotechnology Progress(生物技术进展),15:8179,1999中;Martin在Enzyme Microbes Technology(酶微生物技术),31:274,2002中;Greer在BioCycle(生物循环),61-65,2005年4月中;Lynd在Microbiology and Molecular Biology Reviews(微生物学和分子生物学综述),66:3,506-577,2002中;Ljungdahl等在美国专利4292406中;及Bellamy在美国专利4094742中讨论了生物乙醇策略,这些文章全部引入到本文中作为参考。
现在参考图19,具有低堆密度的纤维材料可以与微生物如冷冻干燥的酵母或细菌和/或酶结合,然后可逆地使其密度增加成具有更高堆密度的纤维材料组合物。例如,通过将纤维材料密封在相对不透气的结构如由聚乙烯制成的袋子或由聚乙烯和尼龙交替的层制成的袋子中,然后从所述结构中排空夹带气体如空气,可以增加堆密度为0.05g/cm3的纤维材料组合物的密度。在从所述结构中排空空气以后,所述纤维材料的堆密度可以例如大于0.3g/cm3,例如0.5g/cm3、0.6g/cm3、0.7g/cm3以上,例如0.85g/cm3。当需要将纤维材料运输到另一个位置如遥远的制造工厂时,这可以是有利的,其中可以将所述纤维材料组合物添加至溶液中,例如来制造乙醇。在刺破基本上不透气的结构以后,密度增加的纤维材料回复至接近于其初始堆密度,例如大于其初始堆密度的60%,例如70%、80%、85%以上,例如其初始堆密度的95%。为了减少纤维材料中的静电,可以向纤维材料中添加抗静电剂。例如,可以向所述纤维材料中添加化学抗静电化合物,例如阳离子化合物如季铵化合物。
在某些实施方案中,所述结构如袋子是由溶于液体如水中的材料形成的。例如,所述结构能够由聚乙烯醇形成以便当其与水基系统接触时溶解。这类实施方案允许密度增加的结构直接添加至例如包含微生物的溶液中,而不用通过例如切割首先释放所述结构的内容物。
其它实施方案
尽管已经描述了某些实施方案,但是其它实施方案也是可行的。
尽管某些实施方案使用筛网来提供所需的纤维材料,但在某些实施方案中,不使用筛网来制造所需的纤维。例如,在某些实施方案中,在限定第一间隙的第一对刀片之间剪切纤维源,得到第一纤维材料。然后在限定第二间隙的第二对刀片之间剪切所述第一纤维材料,得到第二纤维材料,所述第二间隙小于第一间隙。可以将类似的筛分步骤按需要重复多次以制造具有需要性能的所需的纤维材料。
在某些实施方案中,第一纤维材料的平均长径比与第二纤维材料的平均长径比的比值小于1.5。
另外其它的实施方案在所附的权利要求的范围内。
Claims (12)
1.一种制造燃料的方法,所述方法包括:
对纤维源进行剪切以提供第一纤维材料;
将所述第一纤维材料穿过平均开孔尺寸为约1.59mm(1/16英寸,0.0625英寸)以下的第一筛网以提供第二纤维材料;以及
将所述第二纤维材料与细菌和/或酶结合,所述细菌和/或酶利用所述第二纤维材料制造燃料,所述燃料包括氢、醇、有机酸和/或烃。
2.如权利要求1所述的方法,其中所述醇选自:甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙二醇、1,4-丁二醇、丙三醇及它们的混合物。
3.如权利要求1所述的方法,其中所述有机酸选自:甲酸、乙酸、丙酸、丁酸、戊酸、己酸、棕榈酸、硬脂酸、草酸、丙二酸、丁二酸、戊二酸、油酸、亚油酸、羟基乙酸、乳酸、γ-羟基丁酸及它们的混合物。
4.如权利要求1所述的方法,其中所述烃选自:甲烷、乙烷、丙烷、异丁烯、戊烷、正己烷及它们的混合物。
5.如权利要求1所述的方法,其中所述第二纤维材料的BET表面积大于约0.25m2/g。
6.如权利要求1所述的方法,其中所述第二纤维材料的BET表面积大于约1.25m2/g。
7.如权利要求1所述的方法,其中所述第二纤维材料的孔隙率大于约85%。
8.一种制造燃料的方法,所述方法包括:
对纤维源进行剪切以提供第一纤维材料;
将所述第一纤维材料穿过平均开孔尺寸为约1.59mm(1/16英寸,0.0625英寸)以下的第一筛网以提供第二纤维材料;
将所述第二纤维材料进行水解以提供水解物质;以及
将所述水解物质与细菌和/或酶结合,所述细菌和/或酶利用所述水解物质制造燃料,所述燃料包括氢、醇、有机酸和/或烃。
9.一种增加纤维组合物的密度的方法,所述方法包括:
对纤维源进行剪切以提供纤维材料;
将所述纤维材料与细菌和/或酶结合以提供纤维材料组合物;
将所述组合物封装在基本不透气的材料中;以及
从所述封装的组合物中除去夹带气体以增加所述组合物的密度。
10.如权利要求9所述的方法,其中所述基本不透气的材料能溶于水。
11.如权利要求10所述的方法,其中所述基本不透气的材料为袋状。
12.如权利要求9所述的方法,其中在除去夹带气体以后,所述纤维材料的堆密度大于约0.6g/cm3。
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CN103930492A (zh) * | 2011-11-15 | 2014-07-16 | 芬欧汇川集团 | 复合产品、其制造方法及其应用及最终产品 |
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