CN101115695B - 中空陶瓷纤维复合材料及其生产方法和应用 - Google Patents
中空陶瓷纤维复合材料及其生产方法和应用 Download PDFInfo
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- CN101115695B CN101115695B CN2006800041700A CN200680004170A CN101115695B CN 101115695 B CN101115695 B CN 101115695B CN 2006800041700 A CN2006800041700 A CN 2006800041700A CN 200680004170 A CN200680004170 A CN 200680004170A CN 101115695 B CN101115695 B CN 101115695B
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- tubular fibre
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- oxygen
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Abstract
本发明提供包含至少一种由传送氧的陶瓷材料构成的中空纤维的复合材料,所述陶瓷材料是传送氧阴离子和电子的陶瓷材料,或是传送氧阴离子的陶瓷材料和传导电子的陶瓷或非陶瓷材料组合的陶瓷材料,其中中空纤维的外表面与相同的中空纤维或其它传送氧的陶瓷材料构成的中空纤维外表面相接触,接触点经烧结结合在一起。进一步提供的复合材料包含至少一种氧传导陶瓷材料的中空纤维,所述氧传导陶瓷材料是传送氧阴离子和电子的陶瓷材料,或者是传送氧阴离子的陶瓷材料和传导电子的陶瓷或非陶瓷材料的组合,在中空纤维的至少一个端面具有用以引入或引出流体的连接部件,在此中空纤维与连接部件相连接。所述复合材料用于从含有氧的流体获取氧或者适用于进行氧化反应。
Description
本发明涉及特别适用于从含有氧的流体富集氧或者适用于进行氧化反应的中空陶瓷纤维复合材料。
中空陶瓷纤维本身是已知的,其生产已有记载,如在US-A-4222977或US-A-5707584中。
在J.Mem.Sci.193(2001)249-260中,S.Liu、X.Tan、K.Li和R.Hughes报导了由SrCe0.95Yb0.05O2.975生产的陶瓷膜和中空纤维,其生产气密的中空纤维,并研究了它们的机械性能和微观结构。
在CIMTEC2002,249-258页,J.Luyten报导了钙钛矿陶瓷纤维的生产。描述了由La0.6Sr0.4Co0.8Fe0.2O3-δ构成的中空纤维。
在J.Mem.Sci.5229(2002)1-15,J.Tong、W.Yang、B.Zhu和R.Cai报导了应用于氧气分离的掺杂锆的钙钛矿型陶瓷膜的研究。描述了BaCo0.4Fe0.6-xZrxO3-δ膜。
由US-A-6165431、US-A-6146549、US-A-6471921和US-A-6592782已知更多的传送氧的陶瓷材料。
陶瓷材料膜一方面制成气密的,另一方面,经选择的陶瓷材料具有氧渗透性,因此可以用于分离混合物中的氧。特别是这种陶瓷可以用于高温如气体分离或新型的膜反应器。
反应器中用于氧化反应器的氧传导陶瓷膜例如在US-A-6214757、US-A-6033632和US-A-6641626中有描述。
在Electrochemical Society Interface,Sommer2001,22-27页中记载了高温离子传导陶瓷材料及其应用综述。
已知的生产中空陶瓷纤维的工艺包括纺丝工序,其中第一步中,由包含陶瓷材料前体和聚合物的可纺物料生产弹性纤维坯料,聚合物在随后的高温中燃尽然后形成纯的中空陶瓷纤维。
在纺丝中发生倒相过程,一般在第一步中导致多孔膜。通过经控制的温度调控还可以将所述多孔膜紧密烧制。
通过这种方式生产的纤维具有相对高的机械稳定性,但是一般具有陶瓷材料的脆性和易断裂的特性。
令人惊讶的是由经选择的材料构成的中空陶瓷纤维可以与其它成型体或其它的中空陶瓷纤维形成更复杂的结构并通过烧结而复合。可以不使用临时粘合剂进行。得到的结构具有高稳定性,特别是在考虑到安全性时大大提高的可操作性。
中空无机纤维复合材料是现有技术。DE10043666C1记载了一种由无序排列的短纤维碎片组成的陶瓷绝缘材料。这些材料经接触点而相互复合在一起。
GB2022565A记载了具有多孔的壁的由无机材料构成的中空纤维,且在横截面观察到各向异性的孔轮廓。其与捻合在一起但不烧结在一起的中空金属纤维组合公开。
本发明基于令人惊讶的认识,即所选择陶瓷材料的前体与其它材料在接触点在加热下很有效地烧结在一起,而对此无需辅助材料如粘合剂或浆料的使用。
本发明的目的是提供由一种或多种中空陶瓷纤维或中空陶瓷纤维与其它成型体组成的结构。
本发明的另一个目的是提供生产这些结构的简单工艺,在这种工艺中可以使用常用的生产陶瓷成型体的设备。
本发明提供包含至少一种由传送氧的陶瓷材料构成的中空纤维的复合材料,所述陶瓷材料是传送氧阴离子和电子的陶瓷材料,或是传送氧阴离子的陶瓷材料和传导电子的陶瓷或非陶瓷材料组合的陶瓷材料,其中中空纤维的外表面与相同的中空纤维或其它传送氧的陶瓷材料构成的中空纤维外表面相接触,接触点经烧结结合在一起。
本发明另外的实施方式涉及包含至少一种氧传导陶瓷材料的中空纤维,所述氧传导陶瓷材料是传送氧阴离子和电子的陶瓷材料,或者是传送氧阴离子的陶瓷材料和传导电子的陶瓷或非陶瓷材料的组合,在中空纤维的一个端面优选两个端面具有用以引入或引出流体与其相连接的连接部件,优选通过烧结与中空纤维相连接的连接部件。
本发明所用中空纤维的截面可以是任意的,例如,有边角形的、椭圆形的或者特别是圆形截面。
本发明范围内的中空纤维理解为具有空的内腔,并且其外部尺度,即,直径或线性尺度可以是任意的。
本发明范围内的术语中空纤维不仅指传统意义上的中空纤维,还指具有0.5-5mm外部直径的细管和外部直径大于5mm的管子。
优选中空纤维的外部直径或线性尺度的变化范围可以达到5mm。最优选中空纤维的外部直径少于3mm。
本发明描述的中空纤维可以是任意长度,例如中空单纤维或中空Stapelfasern(有限长度的单纤维)。
在本发明复合材料中,通常使用的是长度远超过外部直径的中空纤维。优选所使用的中空陶瓷纤维的长度和外部直径比至少是50∶1,优选至少是100∶1,更优选至少是200∶1。
本发明的复合材料具有预先设定的几何形状(与统计学取向无序堆积的中空纤维集合形成对比),通过加入至少一种中空纤维优选多种中空纤维而形成复合材料,所述复合材料具有至少一个由中空纤维的内部空间形成的内空间和至少一个由围绕该中空纤维的空间形成的外部空间。所述复合材料通常如此构成,即,使流体可流过内腔而氧在通过内腔时减少,在此氧通过中空陶瓷纤维壁传导至外部空间。也可具有使氧以相反方向传导的排列。
本发明的复合材料可以表现为由传送氧的陶瓷材料构成的中空纤维的任意组合。
可以生产如下的复合材料:
·在一个平面纵向排列多种中空纤维
·编织或相互捻合多种中空纤维
·多种中空纤维组合形成的整体(由中空纤维构成的多通道部件)
由于纤维坯料的柔性和弹性,其中的陶瓷(前体)相的量不会太高,可以得到更多几何形状,这种结构的结果是保留了纤维的原始功能性(即传送氧的气体渗透性)。
这样的复合物可进一步装备成膜模块。这些系统特别适用于高温应用,例如气体分离或作为膜反应器的部件。
本发明应用的中空纤维可通过本身已知的纺丝工艺生产,可以是溶液纺丝工艺如干法或湿法纺丝或熔融纺丝工艺。
待纺的物料除了包含细碎的陶瓷材料或其前体也包含可纺的聚合物。
在待纺物料中可纺聚合物的量可以在很宽的范围内变化,但以全部待纺的物料或纺丝溶液的量计,典型地是2-30wt%,优选是5-10wt%。
待纺丝的物料中细碎的陶瓷材料或其前体的量同样也可以在很宽的范围内变化,但以全部待纺的物料或纺丝溶液的量计,典型地是20-90wt%,优选是40-60wt%。
待纺物料中溶剂的量可以在很宽的范围内变化,但以全部纺丝溶液的量计,典型地是10-80wt%,优选是35-45wt%。
可纺聚合物和细碎的陶瓷材料或其前体的类型和量优选如此选择,即刚好获得可纺丝物料,而其中的可纺聚合物的量选择尽可能地低。
通过环形喷嘴挤出纺丝溶液或经加热的且可塑的纺丝物料进行纺丝,然后在空气中冷却和/或引入沉淀浴,沉淀浴包含针对在纺丝物料中所用聚合物不溶的溶剂。
之后,所获得的中空纤维坯料可进行进一步加工工序,例如切割成堆或盘绕用于暂时储存。
在紧随成型之后的加工工序中,将所获得的中空纤维坯料组合制成所需的复合材料。
在此可以涉及多种相同或不同的中空纤维坯料的组合,也可涉及一种或多种中空纤维坯料与其端面的至少一种用于引入或引出流体如液体或特别是气体的连接部件的组合。
中空纤维坯料可以通过任何一种工艺组合。例如手工组合方式如彼此平行走向的中空纤维的相邻放置,也包括纺织生产工艺例如生产针织品、布匹、层压物、针织物、编织物或捻合结构的工艺。
在生产中空纤维坯料的复合材料之后,聚合物以本身已知的热处理方式去除。该工艺步骤也包含了对于陶瓷材料而言由前体形成陶瓷和/或细碎陶瓷颗粒的烧结。可通过本领域技术人员已知的方式选择工艺参数如温度曲线和气氛来控制形成陶瓷的性能。
本发明复合材料中包含的中空纤维由氧传导陶瓷材料构成。这种材料是本身已知的。
本发明复合材料传送氧的典型数值是氧流量至少是0.01标准cm3/(min*cm2),优选至少是0.1标准cm3/(min*cm2),通过测量所讨论的复合材料的总表面积的平均值得到。这里标准cm3是标准立方厘米(在1巴和25℃)。对于本发明的目的,氧流量值是在950℃和氧分压在两端自由气相之间的差为0.2巴的条件下测得的,在此较高的氧分压为0.2巴。
这些陶瓷可以由传送氧阴离子和电子的材料组成。但是,也可能使用不同陶瓷或陶瓷和非陶瓷材料的组合,如由传送氧阴离子的陶瓷和传导电子的陶瓷的组合,或由分别传送氧阴离子和电子的不同陶瓷的组合,或不是其中每一种陶瓷组分都具有氧传导性,或氧传导陶瓷材料和非陶瓷材料如金属的组合。
优选的多相膜体系实例是由具有离子传导性的陶瓷和其它具有电子传导性的材料特别是金属的混合。特别是具有萤石型结构或类萤石型结构的材料与导电材料的组合,如视情况掺杂CaO或Y2O3的ZrO2或CeO2与金属如钯的组合。
优选多相膜体系的其它实例是具有部分钙钛矿型结构的混合结构,即混合体系,其中以固体存在不同晶体结构,至少其中一种是钙钛矿型结构或类钙钛矿型结构。
传送氧的材料优选使用氧化物陶瓷,其中优选这些陶瓷具有钙钛矿型结构、钙铁铝石型结构或Aurivillus结构。
本发明所用的钙钛矿型结构优选具有ABO3-δ结构,其中A是二价阳离子,B是三价或更高价的阳离子,A离子半径大于B离子半径,δ为0.001至1.5的值,优选0.01至0.9,更优选0.01至0.5,以产生材料的电中性。本发明所使用的钙钛矿型结构也可以以不同的A和/或B阳离子的混合物存在。
本发明所使用的钙铁铝石典型地具有A2B2O5-δ结构,其中的A、B和δ如上所述。本发明所使用的钙铁铝石也可能存在不同A和/或B阳离子的混合物。
优选B阳离子以多价氧化态出现。但是,部分或全部B类阳离子也可以是恒定氧化态的三价或更高价的阳离子。
特别优选使用的氧化物陶瓷含有A类阳离子选自第二主族、第I、II副族、镧系阳离子或这些阳离子的混合,优选选自Mg2+、Ca2+、Sr2+、Ba2+、Cu2+、Ag2+、Zn2+、Cd2+和/或镧系元素。
特别优选使用的氧化物陶瓷含有的B类阳离子选自周期表的IIIB至VIIIB族和镧系阳离子,金属选自III至V主族和这些阳离子的混合,优选选自Fe3+、Fe4+、Ti3+、Ti4+、Zr3+、Zr4+、Ce3+、Ce4+、Mn3+、Mn4+、Co2+、Co3+、Nd3+、Nd4+、Gd3+、Gd4+、Sm3+、Sm4+、Dy3+、Dy4+、Ga3+、Yb3+、Al3+、Bi4+和这些阳离子的混合。
还进一步特别优选使用的氧化物陶瓷含有的B类阳离子选自Sn2+、Pb2+、Ni2+、Pd2+、镧系元素或这些阳离子的混合。
本发明使用的Aurivillite典型地具有结构元素(Bi2O2)2+(VO3.5[]0.5)2-或相关结构元素,其中的[]表示氧空位。
最优选的复合材料,其具有钙钛矿型结构的传送氧的氧化物陶瓷具有元素Ba、Sr、Fe、Zn和0或者元素Ba、Co、Fe、Zr和0,特别是具有组成BaCoxFeyZrzO3-δ,其中的x、y和z的总和是1,z为0.1-0.5的值,x为在a*y的区间值,a为0.8-1.2的值,δ值如上定义。
本发明也提供了一种生产如上所述复合材料的生产工艺,其中包括:
i)通过本身已知方法从喷嘴优选是环形喷嘴挤出包含聚合物和陶瓷特别是氧化物陶瓷或陶瓷前体的组合物来生产中空纤维坯料;
ii)通过使由步骤i)生产的一种或多种中空纤维坯料的外表面之间形成接触而由所述中空纤维坯料生产复合材料坯料;和
iii)热处理步骤ii)得到的复合材料坯料以去除聚合物,在步骤i)使用陶瓷前体的情况下形成陶瓷并形成陶瓷中空纤维之间的接触。
本发明进一步的实施方式涉及生产如上所述复合材料的工艺,包括:
i)通过本身已知方式从喷嘴优选是环形喷嘴挤出包含聚合物和陶瓷特别是氧化物陶瓷或陶瓷前体化合物的组合物来生产中空纤维坯料;
iv)通过由一种或多种步骤i)制得的中空纤维坯料和中空纤维坯料的至少一个端面上的至少一个用以引入或引出流体的连接部件生产复合材料坯料,和
v)热处理步骤iv)制得的复合材料坯料以去除聚合物,并且在陶瓷中空纤维和所述至少一个连接部件间形成接触,以及在步骤i)使用陶瓷前体的情况下形成陶瓷特别是氧化物陶瓷。
本发明生产的中空纤维的外径(Da)和内径(Di)可以在很宽的范围内变化。如Da为0.1至5mm,特别是0.5至3mm。Di的实例为0.01至4.5mm,特别是0.4至2.8mm。
更优选中空纤维是以单细丝形式生产,其截面形状是圆形、椭圆形或n边形,n大于或等于3。
对于非圆形截面的纤维,Da是外部截面的最大直径,Di是内部截面的最大直径。
已知的生产陶瓷纤维的聚合物可以用于生产本发明使用的中空纤维。在此原则上聚合物可以是任意可由熔融或溶液纺丝的聚合物,实例为聚酯、聚酰胺、聚砜、聚亚芳基硫化物、聚醚矾和纤维素。
用于生产本发明使用的中空纤维,可以使用本身已知的生产陶瓷纤维的具有氧传导性的陶瓷复合材料或其前体。传送氧的陶瓷物料的实例如上所述。这些陶瓷物料的前体可以涉及例如在成型期间尚且是非晶或部分晶态,直到在型体烧结过程中转变成所希望的晶体结构的混合物。
纺丝物料通过纺丝喷头压挤后,将中空纤维坯料引入到沉淀浴或冷却浴,优选引入水浴,随后盘绕起来。
拉出的速度一般是1到100米/分钟,优选5至20米/分钟。
中空纤维坯料不仅仅包含陶瓷材料或其前体和聚合物,还可以包含其它的辅助物质。例如针对浆料的稳定剂如聚乙烯醇、聚乙二醇,表面活性剂,乙二胺四乙酸盐或柠檬酸,调整浆料粘度的添加剂如聚乙烯吡咯酮或作为掺杂陶瓷的阳离子来源的盐。
在制得中空纤维坯料后,按如上所述方式组合成复合材料,即与其它中空纤维坯料和/或流体入口和出口。入口和出口可以是由金属、陶瓷或陶瓷前体构成的型体。
随后加热复合材料坯料,可以在空气或保护性气氛中进行。温度程序和烧结时间依个体而定。对本领域技术人员来说为达到这个目的所设定的参数是已知的。该加热步骤使前体坯料致密化。首先,聚合物消失,然后,形成的陶瓷中的气孔在适当选择的热处理情况下闭合就得到了气密的复合材料。
替代复合材料坯料与流体的引入和引出口的组合,可以将中空陶瓷纤维构成的复合材料终产物与流体引入和引出口粘结在一起,例如使用陶瓷粘结剂。
本发明的复合材料可以应用于所有工业领域。优选应用于在热或/腐蚀性环境中进行的氧化反应或必须从气体混合物中分离氧的应用。
本发明涉及如上所述的复合材料用于从含有氧的气体混合物特别是空气中分离氧的用途。
本发明进一步涉及如上所述的复合材料用于进行氧化反应特别是有机化合物的催化氧化反应的用途。
下面的实施例表明本发明不仅局限于此。如无其它说明,百分比基于重量。
实施例1:中空纤维坯料的生产
具有组成为BaCo0.4Fe0.4Zr0.2O3-δ的陶瓷粉末与聚砜(UDELP-3500,Solvay和1-甲基-2-吡咯烷酮(NMP)(≥99.0%,Merck)一起搅拌成浆料。随后用球磨均匀化。
通过这种方式得到的纺丝物料通过外径(Da)是1.7mm、内径(Di)是1.2mm的中空核喷嘴纺丝。为此,纺丝物料被填充入压力容器中并被氮气加压。在压力容器的开口打开后,纺丝物料引出并通过中空核喷嘴挤压。纤维坯料丝导入沉淀水浴随后干燥。
实施例2:由中空陶瓷纤维构成的复合材料的生产
如实施例1生产的多种中空纤维相互平行排列,它们沿它们的外壳分别相接触。
这种源自中空纤维坯料的复合材料在窑炉中悬挂烧结。
烧结按照如下温度程序进行:
○ 96℃/h 500℃(保温1h)
○ 120℃/h 1000℃
○ 60℃/h 1300℃(保温6h)
○ 120℃/h 800℃
○ 180℃/h 80℃
在烧结后,得到单根的中空纤维的粘合复合材料。单根中空纤维长度是30-35cm、直径Da是0.8-0.9mm和Di是0.5-0.6mm。
根据实施例2所生产的中空纤维具有对氧的选择渗透性。
实施例3:由中空陶瓷纤维构成的其它复合材料的生产
将实施例1生产的多种中空纤维手工编织并按照实施例2所述的方法进行热处理。
在烧结后得到由单根中空纤维构成的编织体。
根据实施例3所生产的中空纤维具有对氧的选择渗透性。
实施例4:由陶瓷中空纤维构成的其它复合材料的生产
根据实施例1所生产的多种中空纤维在棒形模具表面手工方式相组合,排列成管状多通道部件,其中每个细管是彼此平行走向的中空纤维。
按照实施例2的方式热处理所得到的多通道部件的坯料。
在烧结和除去了棒形模具后多通道部件的内腔是空的。由平行走向并烧结在一起的中空纤维获得的多通道部件对氧具有选择的渗透性。
实施例5:由中空陶瓷纤维构成的其它复合材料的生产
根据实施例1所得到的多种中空纤维沿着棒形模具的表面相编织以排列成螺旋状多通道部件,其中的每一根细管沿着螺旋状物彼此相接触。
按照实施例2的所述方式热处理所获得的多通道部件的坯料。
在烧结并除去了棒形模具之后得到的多通道部件的内腔是空的。由平行且相互螺旋形走向的并烧结在一起的中空纤维获得的多通道部件,具有对氧的选择渗透性。
实施例6:具有引入和引出气体的连接部件的中空陶瓷纤维构成的复合材料的生产
将根据实施例1所生产的大量中空纤维手工组合排列成多通道部件,其中的每一根细管都是相互平行走向的中空纤维。截面观察多通道部件的内腔完全填满了中空纤维。
为引入或引出气体的金属连接部件安置于多通道部件坯料的两端面。
按照实施例2所述的方式热处理所得到的多通道部件的坯料。
在烧结后,由相互平行走向并烧结在一起中空纤维得到多通道部件,其具有对氧的选择渗透性。这种多通道部件通过烧结在两个端面用金属连接部件紧密结合在一起。
实施例7:由中空陶瓷纤维构成的、具有引入或引出气体的连接部件的复合材料的生产
如实施例6所述进行加工,但具有变化,即不安置引入和引出气体的、与多通道部件的坯料相结合的金属连接部件。在烧结多通道陶瓷部件后,借助陶瓷粘合剂将两个连接部件粘合在中空纤维的两个端面,然后在100℃加热该复合材料并得到在两个端面安置有金属连接部件的多通道部件。
Claims (38)
1.包含至少一种由传送氧的陶瓷材料构成的中空纤维的复合材料,该陶瓷材料是传送氧阴离子和电子的陶瓷材料,或由传送氧阴离子的陶瓷材料和传导电子的陶瓷或非陶瓷材料的组合,其中中空纤维的外表面与相同中空纤维或另一种由传送氧的陶瓷材料构成的中空纤维的外表面相接触,且接触点通过烧结相结合,所述传送氧的陶瓷材料是具有钙钛矿型结构ABO3-δ或钙铁铝石型结构A2B2O5-δ的氧化物陶瓷,其中A是二价阳离子,B是三价或更高价的阳离子,A的离子半径比B的离子半径大,δ是0.01至0.9的数值,以产生材料的电中性,A和/或B作为不同阳离子的混合物存在。
2.包含至少一种由传送氧的陶瓷材料构成的中空纤维的复合材料,所述陶瓷材料是传送氧阴离子和电子的陶瓷材料,或由传送氧阴离子的陶瓷材料和传导电子的陶瓷或非陶瓷材料的组合,其中中空纤维的至少一个端面具有一个或两个用于引入或引出流体的连接部件,所述传送氧的陶瓷材料是具有钙钛矿型结构ABO3-δ或钙铁铝石型结构A2B2O5-δ的氧化物陶瓷,其中A是二价阳离子,B是三价或更高价的阳离子,A的离子半径比B的离子半径大,δ是0.01至0.9的数值,以产生材料的电中性,A和/或B作为不同阳离子的混合物存在。
3.如权利要求2所述的复合材料,其中中空纤维的两个端面具有一个或两个用于引入或引出流体的连接部件。
4.如权利要求1至3任一项所述的复合材料,其特征在于具有多种编织或捻合在一起的中空纤维。
5.如权利要求1至3任一项所述的复合材料,其特征在于具有至少两种由氧传导陶瓷材料构成、相互平行走向的中空纤维,且它们的外壳至少部分沿着它们的纵向接触。
6.如权利要求5所述的复合材料,其特征在于具有多种以管状多通道部件形式排列的、相互平行走向的中空纤维或管,它们的外壳至少部分沿着它们的纵向接触。
7.如权利要求6所述的复合材料,其特征在于中空纤维或管形成管状多通道部件的壳,它们的内腔中空或具有棒形增强材料。
8.如权利要求7所述的复合材料,其特征在于中空纤维或管的走向是沿着由气密或多孔材料构成的管的内侧的。
9.如权利要求7所述的复合材料,其特征在于管状多通道部件的中空内腔具有氧化催化剂。
10.如权利要求1至3任一项所述的复合材料,其特征在于该复合材料具有一种或多种相互纺织的中空纤维。
11.如权利要求1至3任一项所述的复合材料,其特征在于该复合材料具有一种或多种相互编织的中空纤维。
12.如权利要求1至3任一项所述的复合材料,其特征在于该复合材料具有一种或多种相互针织的中空纤维。
13.如权利要求1至3任一项所述的复合材料,其中δ是0.01-0.5的数值。
14.如权利要求1至3任一项所述的复合材料,其特征在于A类阳离子选自第II主族、第I副族、第II副族、镧系元素的阳离子或这些阳离子的混合物。
15.如权利要求14所述的复合材料,其中所述阳离子选自Mg2+、Ca2+、Sr2+、Ba2+、Cu2+、Ag2+、Zn2+、Cd2+和/或镧系元素。
16.如权利要求1至3任一项所述的复合材料,其特征在于B类阳离子选自元素周期表的第IIIB至VIIIB族和/或镧系元素的阳离子、第V主族的金属阳离子或这些阳离子的混合物。
17.如权利要求16所述的复合材料,其中所述阳离子选自Fe3+、Fe4+、Ti3+、Ti4+、Zr3+、Zr4+、Ce3+、Ce4+、Mn3+、Mn4+、Co2+、Co3+、Nd3+、Nd4+、Gd3+、Gd4+、Sm3+、Sm4+、Dy3+、Dy4+、Ga3+、Yb3+、Al3+、Bi4+或这些阳离子的混合物。
18.如权利要求1至3任一项所述的复合材料,其特征在于具有钙钛矿型结构的氧化物陶瓷具有元素Ba、Sr、Fe、Zn和O或元素Ba、Co、Fe、Zr和O。
19.如权利要求18所述的复合材料,其特征在于具有钙钛矿型结构的氧化物陶瓷具有组成BaCoxFeyZrzO3-δ,其中x、y和z的总和是1,z为0.1至0.5的值,x具有a*y范围内的值,a为0.8至1.2的值,δ如权利要求1或2所定义。
20.生产权利要求1所述复合材料的方法,包括如下步骤:
i)通过本身已知方法从喷嘴挤出包含聚合物和陶瓷或陶瓷前体的组合物来生产中空纤维坯料;
ii)通过使由步骤i)生产的一种或多种中空纤维坯料的外表面之间形成接触而由所述中空纤维坯料生产复合材料坯料;和
iii)热处理步骤ii)得到的复合材料坯料以去除聚合物,在步骤i)使用陶瓷前体的情况下形成陶瓷并形成陶瓷中空纤维之间的接触。
21.如权利要求20所述的方法,其中所述喷嘴是环形喷嘴。
22.如权利要求20所述的方法,其中所述步骤i)中的组合物包含聚合物和氧化物陶瓷或陶瓷前体。
23.如权利要求20至22任一项所述的方法,其特征在于根据干纺工艺、湿纺工艺或熔融纺丝工艺进行挤出操作。
24.如权利要求20至22任一项所述的方法,其特征在于通过编织、捻合中空纤维坯料或通过相互平行走向的中空纤维坯料的铺叠生产复合材料。
25.如权利要求20至22任一项所述的方法,其特征在于通过纺织中空纤维坯料或通过相互平行走向的中空纤维坯料的铺叠生产复合材料。
26.如权利要求20至22任一项所述的方法,其特征在于通过编结中空纤维坯料或通过相互平行走向的中空纤维坯料的铺叠生产复合材料。
27.如权利要求20至22任一项所述的方法,其特征在于通过针织中空纤维坯料或通过相互平行走向的中空纤维坯料的铺叠生产复合材料。
28.如权利要求24至27任一项所述的方法,其特征在于中空纤维坯料环绕棒形增强部件或环绕管子排列。
29.如权利要求20至22任一项所述的方法,其特征在于在900-1600℃温度下热处理在步骤ii)中产生的复合材料坯料。
30.如权利要求20至22任一项所述的方法,其特征在于按步骤iii)产生复合材料后,在中空纤维的至少一个端面上结合至少一个用于引入或引出流体的连接部件。
31.如权利要求30所述的方法,其特征在于所述结合为粘合。
32.生产权利要求2所述复合材料的方法,包括如下步骤:
i)通过本身已知方式从喷嘴挤出包含聚合物和陶瓷或陶瓷前体化合物的组合物来生产中空纤维坯料;
iv)通过由一种或多种步骤i)制得的中空纤维坯料和中空纤维坯料的至少一个端面上的至少一个用以引入或引出流体的连接部件生产复合材料坯料,和
v)热处理步骤iv)制得的复合材料坯料以去除聚合物,并且在陶瓷中空纤维和所述至少一个连接部件间形成接触,以及在步骤i)使用陶瓷前体的情况下形成陶瓷。
33.如权利要求32所述的方法,其中所述喷嘴是环形喷嘴。
34.如权利要求32或33所述的方法,其中所述陶瓷为氧化物陶瓷。
35.权利要求1至19中任一项的复合材料的应用,其用作从含有氧的气体混合物中获得氧。
36.如权利要求35所述的复合材料的应用,其用作从空气中获得氧。
37.权利要求1至19中任一项的复合材料的应用,其用作进行氧化反应。
38.如权利要求37所述的复合材料的应用,其用作进行有机化合物的催化氧化。
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DE102005005464A DE102005005464B4 (de) | 2005-02-04 | 2005-02-04 | Verbunde keramischer Hohlfasern, Verfahren zu deren Herstellung und deren Verwendung |
DE102005005464.1 | 2005-02-04 | ||
PCT/EP2006/000546 WO2006081959A1 (de) | 2005-02-04 | 2006-01-23 | Verbünde keramischer hohlfasern, verfahren zu deren herstellung und deren verwendung |
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