CN102083768B - 钛酸铝类型的多孔结构 - Google Patents

钛酸铝类型的多孔结构 Download PDF

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CN102083768B
CN102083768B CN2009801256915A CN200980125691A CN102083768B CN 102083768 B CN102083768 B CN 102083768B CN 2009801256915 A CN2009801256915 A CN 2009801256915A CN 200980125691 A CN200980125691 A CN 200980125691A CN 102083768 B CN102083768 B CN 102083768B
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vesicular structure
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oxide compound
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CN102083768A (zh
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S.拉弗
P.奧罗伊
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Saint Gobain Centre de Recherche et dEtudes Europeen SAS
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Abstract

本发明涉及包含陶瓷材料的多孔结构,该陶瓷材料主要地包含以这样的比例含有钛、铝、镁和锆的假板钛矿类型的氧化物材料或者由该氧化物材料组成,所述比例使得该假板钛矿类型的相基本上满足下式:(Al2TiO5)x(MgTi2O5)y(MgTiZrO5)z,所述材料满足以下组成,基于仅仅氧化物Al2O3、TiO2、MgO和ZrO2的摩尔百分比:90<2a+3m<110,100+a<3t<210-a和a+t+m+zr=100,其中a是Al2O3的摩尔百分比;t是TiO2的摩尔百分比;m是ZrO2的摩尔百分比。

Description

钛酸铝类型的多孔结构
本发明涉及多孔结构,如催化剂载体或者颗粒过滤器,其构成过滤和/或活性部分的材料基于钛酸铝。形成根据本发明的载体或陶瓷过滤器的基础的陶瓷材料或者主要由元素Al、Ti、Mg和Zr的氧化物(主要呈钛酸铝Al2TiO5(铁板钛矿)类型的相形式)构成。该多孔结构通常由蜂窝状结构制成并且特别地用于柴油类型内燃机的排气管道,其性能得到改善。
在本说明书的剩余部分中,将描述在可以除去在来自汽油或者柴油内燃机的废气中包含的污染物的特定过滤器或者催化剂载体的领域(本发明涉及的领域)中的应用和优点。目前,所有用于净化废气的结构通常都具有蜂窝状结构。
据已知,在它的使用期间,颗粒过滤器经受一系列的过滤(烟灰积聚)和再生(烟灰去除)阶段。在过滤阶段期间,由发动机排出的烟灰颗粒被保留和沉积在过滤器内部。在再生阶段期间,烟灰颗粒在过滤器内部被烧掉以便恢复其过滤性能。因此将理解的是,构成过滤器的材料在低温和高温时的机械强度性能对于这种应用是极其重要的。同样地,该材料必须具有足够稳定的结构以经受(特别地在安装其的车辆的整个使用寿命期间内)可能局部地上升最高至基本高于1000℃值的温度,特别地如果一些再生阶段没有充分控制时。
目前,过滤器主要地由多孔陶瓷材料制成,最通常地由金刚砂或者堇青石制成。这种类型的金刚砂催化过滤器例如描述在专利申请EP816065、EP1142619、EP1455923或者WO2004/090294和WO2004/065088中。这种过滤器可以获得具有优异的热导率和具有孔隙度特征(特别地平均孔径和孔径分布)的化学上惰性的过滤结构,其对于过滤由热发动机产生的烟灰的应用是理想的。
然而,仍然保持一些这种材料特有的缺点:
第一个缺点与SiC的稍微高的热膨胀系数(大于3×10-6K-1)有关,其不允许制备大尺寸的整料过滤器并且最经常必须将该过滤器分割成使用水泥结合在一起的多个蜂窝状元件,如在专利申请EP1455923中描述的那样。经济性质的第二个缺点与极其高的烧制温度(典型地可以烧结以确保该蜂窝状结构的足够的热机械强度的高于2100℃)有关,特别地在过滤器的连续再生阶段期间。这种温度要求安装特殊设备,这显著地提高了最后获得的过滤器的成本。
从另一观点看,虽然由堇青石制成的过滤器是已知的并且使用很长时间了(由于它们的低成本),然而目前已知的是,在这种结构中可能遇到问题,特别地在没有很好控制的再生循环期间,在其期间,过滤器可能局部地经受高于堇青石的熔点的温度。这些热点的后果可为从过滤器的效率的部分损失至在最严重的情况下它完全的破坏。而且,堇青石不具有足够的化学惰性(从连续的再生循环期间达到的温度来看),并因此它易于反应并被来源于在该过滤阶段期间已经积聚在该结构中的润滑剂、燃料或其它油的残余物的物类腐蚀,该现象还可以是该结构的性能快速退化的原因。
例如,这种缺点已经描述在专利申请WO2004/011124中,其提出用多铝红柱石(10-40重量%)增强的基于钛酸铝(60-90重量%)的过滤器以克服它们,其耐用性得到改善。
根据另一实施方案,专利申请EP1559696提出使用粉末以制备通过在1000-1700℃的铝、钛和镁的氧化物的反应性烧结获得的蜂窝式过滤器。在烧结之后获得的材料呈两种相的混合物形式:铁板钛矿Al2TiO5结构类型的主要相,其包含钛、铝和镁,和NayK1-yAlSi3O8类型的长石相次要相。
然而,由申请人进行的实验已经表明在目前难于保证这种基于钛酸铝类型的材料的结构的性能,特别地难于达到适合于例如使它们能直接地用于颗粒过滤器类型的高温应用中的热稳定性、热膨胀系数和耐腐蚀性的值。
特别地,氧化物种类的材料在过滤器颗粒的特定应用中,必须控制耐腐蚀性以便避免该过滤器的孔隙性被改变。更确切地说,使用作过滤器的组分的材料腐蚀的强烈倾向导致能够封闭孔隙的反应并显著地降低过滤能力,和在最严重的情况下,可以是由于过滤器壁被击穿的渗漏的原因。
本发明的目的因此是提供多孔结构,其包含铁板钛矿(pseudo-brookite)类型的氧化物材料,具有基本上得到改善的如上所述的性能,特别地以使得更有利地使用它们以制备过滤器和/或催化多孔结构,典型地蜂窝状结构。
更确切地说,本发明涉及包含陶瓷材料的多孔结构,该陶瓷材料主要地包含以这样的比例含有钛、铝、镁和锆的铁板钛矿类型的氧化物相或者由该氧化物相组成,所述比例使得该铁板钛矿类型的相基本上满足下式:
(Al2TiO5)x(MgTi2O5)y(MgTiZrO5)z
所述材料满足以下组成(基于单一氧化物Al2O3,TiO2,MgO和ZrO2的mol%):
90<2a+3m<110;
100+a<3t<210-a;和
a+t+m+zr=100,
其中:
-  a是Al2O3的摩尔百分比;
-  t是TiO2的摩尔百分比;
-  m是MgO的摩尔百分比;
-  zr是ZrO2的摩尔百分比。
措辞“基于氧化物”在本说明书的意义上理解为百分比含量(重量百分比或者摩尔百分比)基于对应于存在于陶瓷材料中的元素的氧化物进行计算。
术语“主要地”在本说明书的意义上理解为铁板钛矿类型的相占该材料的总重量的至少60%,优选地至少70%,甚至至少80%。
优选地,该多孔结构由所述陶瓷材料组成。
优选地,在上述式中92≤2a+3m≤108,非常优选地95≤2a+3m≤105。
优选地,在上述式中100+a≤3t≤205-a,非常优选地100+a≤3t≤200-a。根据本发明的一个实施方案,所述材料具有以下组成(基于以下氧化物的重量%):
-  大于25%并低于55%的Al2O3
-  大于35%并低于60%的TiO2
-  大于1%并低于8%的MgO;
-  大于0.7%并低于7%的ZrO2
-  低于20%的SiO-2
优选地,Al2O3占该材料的化学组成的大于25%,所述百分比以基于对应于存在的元素的氧化物的重量%给出。例如,特别地对于过滤器或者催化剂载体类型的应用,Al2O3可以占该化学组成的大于30%更优选地大于35%。优选地,Al2O3占该化学组成的低于55%非常优选地低于50%,所述百分比以基于氧化物按重量计给出。
优选地,TiO2占该材料的化学组成的大于40%。优选地,TiO2占该化学组成的低于60%非常优选地低于55%,所述百分比以基于氧化物按重量计给出。
优选地,MgO占该材料的化学组成的大于1%和非常优选地大于1.5%。优选地,MgO占该化学组成的低于8%非常优选地低于6%,所述百分比以基于氧化物按重量计给出。
优选地,ZrO2占该材料的化学组成的大于0.7%和非常优选地大于1.5%,百分比含量以重量计并基于氧化物给出。优选地,ZrO2占该化学组成的低于7%并且非常优选地低于6%。不脱离本发明的范围,至少一部分甚至所有的ZrO2可以用至少一种选自Ce2O3或HfO2的氧化物进行替换(基于使用元素Ce和/或元素Hf对元素Zr的摩尔百分比替换)。这特别地是当使用的Zr源包含相当大比例的Hf时的情况,如它在目前大多数可商业获得的锆源中是通常的。
除了所有存在的氧化物的重量百分比,根据本发明的结构还可以包含其它微量元素。特别地,所述材料可以以低于20%(基于SiO2),优选地低于10%的量包含硅。硅的量优选地大于0.5%,有利地大于1%甚至大于1.5%或者甚至大于2%。例如,所述量(基于SiO2)是0.5-10%。
除了所有对应于在所述材料中存在的元素的氧化物的重量百分比,该多孔结构还可以包含其它元素,如Ca、Na、K、Fe、Ba和Sr,存在于该材料中的所述元素的总和量基于相应的氧化物优选地为低于6重量%,特别地低于3重量%并且甚至低于2重量%。根据一个实施方案,每种微量元素的百分比含量,基于相应氧化物的重量,优选地低于0.7%。根据另一实施方案,元素Ca、Sr和Ba的百分比含量(基于相应氧化物的重量)大于2%,甚至大于3%,特别地3-5%。
为了避免不必要地增加本说明书的负担,如上所述地,在根据本发明的颗粒的组成的各种优选的实施方案之间的根据本发明的所有可能的组合将不再报道。然而,显然的是,在本说明书的范围内可以设想上面描述的起点值和/或优选值和范围的所有可能的组合并且它们应该被认为是由本申请人进行了描述(特别地两、三种或更多种组合)。
根据本发明的多孔结构的材料可以进一步地包括由硅酸盐相组成的较少相(phase minoritaire),其比例可以为该材料的总重量的0-40%,优选地0-30%,非常优选地该材料总重量的0-25%。根据本发明,所述硅酸盐相可以主要由二氧化硅和氧化铝组成。优选地,在硅酸盐相中的二氧化硅的比例大于50%甚至大于60%。
根据本发明的多孔结构的材料可以进一步地包括基本上包含二氧化钛TiO2和/或氧化锆ZrO2的较少相。措辞“基本上包含”理解为表示在该相中的TiO2和/或ZrO2的重量百分比是约至少80%甚至至少90%。
根据本发明的材料的铁板钛矿类型的氧化物相可以基本满足下式:
(Al2TiO5)x(MgTi2O5)y(MgTiZrO5)z
其中:
-x为0.45-0.94;
-y为0.05-0.50;
-z为0.005-0.06;和
-x+y+z=1。
根据优选的实施方案,在上式中:
-x为0.65-0.90;
-y为0.09-0.40;
-z为0.005-0.05;和
-x+y+z=1。
术语“基本上”在本说明书意义上理解为表示对与存在于该铁板钛矿类型的主相中的元素(Al、Ti和Mg)对应的每种氧化物的计算的百分比含量偏离对应于理想式(Al2TiO5)x(MgTi2O5)y(MgTiZrO5)z的百分比含量不超过5%,优选地不超过2%。
构成根据本发明的多孔结构的材料可以通过任何通常用于本领域中的技术获得。
例如,构成该结构的材料可以直接地通过以适当的比例简单混合初始反应剂以获得希望的组成,然后成型和烧结而直接地获得。所述反应剂可以是简单的氧化物Al2O3,TiO2,MgO和ZrO2和任选地可进入在钛酸铝铁板钛矿结构中的元素(如硅)的其它氧化物,例如呈固溶体形式。根据本发明还可能使用所述氧化物的任何前体,例如呈以上元素的碳酸盐、氢氧化物或者其它有机金属化合物形式。术语“前体”理解为表示在通常在热处理之前的阶段,即在一般地低于1000℃,或者低于800℃甚至低于500℃的加热温度下,其分解成相应的简单氧化物的材料。
根据另一种制备根据本发明的结构的方法,该多孔结构从由所述简单氧化物获得的烧结颗粒获得。预烧结该混合物,即它被加热至可以使简单的氧化物反应以形成包含该铁板钛矿类型的结构的至少一种主相的烧结颗粒的温度。根据这种实施方案还可以使用上述的氧化物的前体。此外,如同上述,烧结前体的混合物,即它被加热至可以使前体反应以便形成包含至少一个主要地铁板钛矿类型结构的相的颗粒的温度。
根据另一可能的制备根据本发明的结构的方法,根据本发明的材料由通过使氧化物Al2O3、TiO2、MgO、ZrO2和任选地SiO2或者其它氧化物(或者其前体)事先熔化获得的颗粒进行合成。
例如,该颗粒通过电熔化方法获得,其可以大量制备,具有高产率和很好的价格/性能比。
用于通过熔化制备该颗粒的连续步骤例如为如下:
a)  将原材料混合以形成原料(charge de départ);
b)  熔化该原料直至获得熔化液体;
c)  冷却所述熔化液体使得该熔化液体完全地凝固,这种冷却可以快速地进行,例如在低于3分钟之内;
d)  任选地,研磨所述固体块以便获得颗粒混合物。
在步骤b),优选地使用电弧炉,但是可以考虑任何已知的炉,如感应电炉或者等离子体加热炉,只要它完全地熔化该原料。烧制优选地在中性条件下进行,例如在氩气下,或者在氧化条件下,优选地在大气压力下。
在步骤c),冷却优选地但不是必须地是快速的,即,以使得熔化液体在低于3分钟之内变得完全地凝固的方式进行。优选地,该冷却由浇铸在如描述在专利US3993119中的CS模型中获得,或者由淬火操作获得。
在步骤d),使用传统方法研磨该固体块直至获得可以制备本发明结构的颗粒尺寸。
一种用于制备这种根据本发明的结构的方法通常为以下:
首先,将初始反应剂(通过烧结获得的颗粒或者通过熔化获得的颗粒,如上所述的或者作为其混合物)以适当的比例混合以获得希望的组成。
以在本领域中熟知的方式,该制造方法一般地包括使反应剂和/或熔化和/或烧结颗粒的最初混合物与甲基纤维素类型的有机粘结剂和致孔剂(例如,淀粉、石墨、聚乙烯、PMMA等等)混合的步骤,并且逐渐加入水直至获得可以进行挤出蜂窝状结构的步骤所需要的可塑性。
例如,在第一步期间,使初始混合物与1-30质量%的至少一种根据所希望的孔径选择的致孔剂混合,然后加入至少一种有机增塑剂和/或有机粘结剂和水。
该混合产生呈糊状物形式的均质产品。使用熟知的技术,使该产品挤出通过具有适当形状的模具的步骤可以获得蜂窝状整料。该方法然后例如可以包括干燥该获得的整料的步骤。在干燥步骤期间,获得的粗制陶瓷整料一般地通过微波干燥或者通过温度干燥进行干燥足够的时间以使非化学结合水的含量为低于1质量%。当希望获得颗粒过滤器时,该方法可以进一步地包括在该整料的每一端使每两个通道阻塞一个通道的步骤。
烧制该整料(其过滤部分基于钛酸铝)的步骤原则上在高于1300℃而不超过1800℃,优选地不超过1750℃的温度下进行。该温度特别地根据存在于多孔材料中的另一相和/或氧化物进行调节。最通常,在该烧制期间,整料结构在包含氧或者中性气体的气氛中被加热至1300℃-1600℃的温度。
虽然本发明的优点之一在于获得其尺寸可被大大提高的整料结构而不需要分割的可能性,与SiC过滤器(如上所述)不同,根据一个可能的实施方案,该方法可以任选地包括将整料装配为使用熟知的技术(例如在专利申请EP816065中描述的那些技术)进行装配的过滤结构的步骤。
由根据本发明的多孔陶瓷材料制成的结构或者过滤结构优选地是蜂窝状类型的。它具有适当的孔隙度,一般地20-65%,优选地30-50%,平均孔径理想地为10-20微米。根据本发明的多孔结构一般地具有蜂窝状类型结构,可以用作为用于汽车应用的催化剂载体或者过滤器,构成所述结构的陶瓷材料具有大于10%的孔隙度和中心在5-60微米的孔径。
这种过滤结构一般地具有包含大量的通过由多孔材料形成的壁分隔的具有互相平行轴的相邻孔道或者通道的中央部分。
在颗粒过滤器中,所述孔道通过塞子在它们的一端或另一端被阻塞以便限定朝着进气口面开口的进气腔室和朝着气体排出面开口的出口腔室,使得该气体穿过该多孔壁。
本发明还涉及从如上面所述的结构并通过沉积,优选地通过浸渍至少一种被负载的或者优选地非负载的活性催化相而获得的过滤器或者催化剂载体,该活性催化相一般地包含至少一种贵金属,如Pt和/或Rh和/或Pd和任选地氧化物如CeO2、ZrO2、CeO2-ZrO2。该催化剂载体还具有蜂窝状结构,但是所述孔道不用塞子阻塞和该催化剂被沉积在该通道的孔隙中。
本发明和它的优点通过阅读以下非限制性实施例而更好地理解。在实施例中,除非另作说明,否则所有的百分比含量以重量计给出。
实施例
在所有实施例中,从以下原材料制备样品:
-  包含大于98%的TiO2的锐钛矿,其由Altichem公司销售,或者包含大于95%的TiO2并且具有约120μm的中值粒径d50的金红石,其由Europe Minerals公司销售;
-  包含大于98%的Al2O3的氧化铝AR75,其由Alcan销售并且具有约85μm的中值粒径d50
-  具有大于99.5%的纯度和208μm的中值粒径d50的SiO2,其由Sifraco公司销售;
-  具有大于98%的纯度同时大于80%的颗粒具有0.25-1mm的直径的MgO,其由Nedmag公司销售;
-  包含约97%的CaO的石灰,其中大于80%的颗粒具有低于80μm的直径;
-  包含大于99.5%的K2CO3的碳酸钾,其由Albemarle公司销售,其中大于80%的颗粒具有0.25-1mm的直径;和
-  具有大于98.5%纯度和3.5μm的中值粒径d50的氧化锆,其以名称CC10由Saint-Gobain ZirPro公司销售。
根据本发明的样品和对比样品由以上反应剂获得,以适当的比例混合并且任选地熔化并且研磨。
更确切地说,对于所有的实施例(除了实施例6外),初始反应剂的混合物使用电弧炉在空气中进行预先熔化。熔化的混合物然后在CS模型中进行浇铸以便快速地冷却。它们然后进行研磨并筛选以保留超过36μm的粉末。这些粉末用来制备被压制为盘形式的样品,其然后在1300℃-1600℃的温度下烧结4小时。由此获得以下实施例的样品或材料。
在实施例6中,替换地直接使用初始反应剂而不用事先熔化。
然后分析所述制备的样品。对实施例1-13的每种样品进行的分析的结果归纳在表1和2中。
在表1和2中:
1) 化学组成(以基于氧化物的重量%显示)通过X射线荧光进行测定;
2)存在于耐火产品中的结晶相通过X-射线衍射和电子探针分析进行表征。在表1中,AMTZ显示为(Al2TiO5)x(MgTi2O5)y(MgTiZrO5)z类型的固溶体,P2显示存在较少的次要相和PS对应于硅酸盐次要相,“M”对应于主相和“~”表示该相以微量形式存在;
3)存在的结晶相的稳定性通过测试进行测定,该测试在于通过RX衍射使最初存在的结晶相与在1100℃的热处理100小时之后存在的结晶相比较。如果表明在这种处理后出现金红石TiO2的主峰的最大强度保持低于该AMTZ相的三个主峰的最大强度的平均值的50%,该产品被认为是稳定的。在表1中给出的值对应于根据下式的该金红石相的主峰的最大强度相对于AMTZ相的三个主峰的最大强度的平均值的比率(百分比):
Figure 769102DEST_PATH_IMAGE001
据认为,如上所述的低于该强度的50%的比率表征该材料的优良稳定性并且能够使用它;
4)热膨胀系数(CTE)对应于通常从25℃-1000℃通过膨胀测量法对由具有相同的粒级的粉末(其中值粒径d50低于50μm)制备的片剂获得的值的平均值。该片剂通过压制然后在表1中指出的温度下的烧结获得;
5)破裂模量(MOR)在室温下在以常规方法对通过均衡压制然后烧结该粉末而获得的条状物(尺寸45mm×4mm×3mm)的四点弯曲中进行测定。
Figure 10728DEST_PATH_IMAGE002
基于表1的数据,可见所述陶瓷材料特征为与作为颗粒过滤器类型的应用相容的稳定性和CTE。特别地,它们具有优良的机械强度。
而且,合成并分析了陶瓷材料,其基本上符合实施例2的组成,但其这次从包含以下的最初混合物获得:
-  90重量%上面描述的电弧炉熔化的颗粒;和
-  10当量重量%(10% en équivalent poids)的氧化物,在该上面描述的原材料的最终组成中。
颗粒和反应剂的最初混合物在1450℃使用传统方法进行烧结。获得的材料的密度为2.8,它的CTE接近1.8。
每个相的组成随后通过电子探针分析进行分析,分析的结果在表2中给出。基于这些结果,每个相的重量百分含量和在该AMTZ主相的通式(Al2TiO5)x(MgTi2O5)y(MgTiZrO5)z中的x、y和z的值能够通过计算进行估算。
Figure 348168DEST_PATH_IMAGE003
Figure 991639DEST_PATH_IMAGE004
还使用与上述相同方法合成和分析了对比样品(不根据本发明),然而进行以下修改:
根据第一对比实施例1,材料最初由熔化颗粒进行制备而不将锆源引入到初始反应剂中。
根据第二对比实施例2,该材料从通过上面描述的原材料的粉末的反应性烧结获得的颗粒进行合成,而不将锆源引入到初始反应剂中。
根据第三对比实施例3,通过在初始混合物中使用过小量的钛来合成该材料,使得3t<100+a和2a+3m>110。
根据第四和第五对比实施例4和5,该材料最初从包含少量铝的熔化浇铸颗粒进行制备。
根据第六对比实施例6,该材料从特征为高锆含量的熔化颗粒进行合成。
根据第七对比实施例7,该熔化颗粒通过使用使得3t<100+a的量的Al2O3和TiO2进行合成。
对于这些对比实施例获得的组合物和结果在表3中给出。
Figure 389123DEST_PATH_IMAGE005
在表3中给出的数据中可以看出不根据本发明的材料与它在多孔结构中的用途不相容:
-  对比实施例1、2、4和5的材料具有过高的CTE值,有时甚至大于SiC的CTE值;
-  不根据本发明的对比实施例3和7的材料具有明显不足够的稳定性;和
-  对比实施例6的材料对于在颗粒过滤器类型的过滤结构中的使用是不可接受的。这是因为它具有CTE曲线,在该曲线中观察到与表征氧化锆的膨胀异常相似的断裂。因此,在所述破裂之前,测量出0.73的平均CTE,而在所述破裂之后,测量出4.99的平均CTE。这种特征易于产生使材料脆化的裂纹。
而且,该材料的耐腐蚀性的性质已对于根据本发明的实施例8和对比实施例2进行测定。更确切地说,0.2克K2SO4粉末均匀地沉积在该盘的表面上。使如此涂覆的样品然后在空气中加热至1300℃达5小时。冷却后,沿着径向切面切割该样品并且进行制备用于使用扫描电子显微镜的切面观测。然后对MEB图片进行视觉评估从该盘的初始表面开始的由腐蚀产生的样品的深度E。对于根据本发明的样品(根据本发明的实施例8),由腐蚀引起的深度E为60微米,和对于对比样品(对比实施例2)为150微米。
对前面根据本发明的实施例2的样品进行的相同的耐腐蚀性测试(但是使用Na2CO3替代K2SO4)表明该样品在5小时之后没有被腐蚀(E=0)。对具有相同组成但是直接地通过反应性烧结初始反应剂(不通过用于获得所述熔化颗粒的中间熔化步骤)获得的样品进行的相同测试相反地得到腐蚀值E=160微米。
应用实施例:用于作为颗粒过滤器的特定用途的材料的性质
为了研究由根据本发明获得的材料(特别地用于作为颗粒过滤器的应用)成型的部件的特征,根据本发明从与先前用于制备样品2和5的相同粉末制备了多孔样品,其化学分析在表4中给出。
根据实施例2和5获得的样品的性能与不根据本发明的新多孔样品(新对比实施例8)进行了比较。根据该对比实施例8,由通过该原材料的粉末(没有将锆源引入到初始反应剂中)的反应性烧结获得的颗粒合成该多孔材料。
如先前在说明书中描述的,多孔陶瓷材料以下列方式获得:使粉末与相对于该粉末混合物总重量5%的甲基纤维素类型的有机粘结剂和8%的致孔剂混合。加入水同时混合直至获得具有能够挤出呈6mm×8mm×60mm尺寸的条状物形式的样品的可塑性的均匀糊状物,该条状物然后在1450℃或者1400℃烧结4小时,如在表4中指出的那样。
为了估算用于“颗粒过滤器”应用中的该材料的值,对在这些样品测量了热膨胀系数,断裂模量和孔隙度特征。通常,这些特征通过熟知的高压水银孔率法技术使用Micromeritics 9500类型孔率计进行测量。
烧结收缩表示根据所述实施例在1450℃或者1400℃的烧结之后样品的尺寸变化。更确切地说,根据本发明,术语“烧结收缩”理解为表示沿着该材料的截面的两个尺寸中的每一个尺寸的平均降低,该降低在低温(即在低于400℃的温度,特别地在室温下)时是持久的。在表4中,报道的收缩值对应于该两个尺寸的收缩的平均值,其以在烧结之前该条状物的最初尺寸(对于所述尺寸的每个尺寸)的百分比表示。这种特征对于评价用于制备多孔结构的方法的可行性是极其重要的。因为,在烧结时的高收缩意味着由该材料形成的蜂窝将具有工业化主要困难,特别地用于以可接受的再现性获得结构,该结构的尺寸特征可以被提供有足够的精度以便能够使它们没有任何困难地特别用于汽车排气管道中。
在室温下以对先前获得的多孔条状物(尺寸60mm×6mm×8mm)的三点弯曲形式测量该断裂模量(MOR)。
所述结果在表4中给出。
Figure 118044DEST_PATH_IMAGE006
在表4中给出的结果表明根据本发明的多孔样品或者多孔材料可以获得具有基本上比传统获得的产品的更好的整体特征的产品。
特别地,通过在表4中数据的比较,可看见存在用于制备整料的孔隙度和机械强度的组合特征的显著改善:对于相同的烧结温度,看出根据本发明的实施例2和5的多孔条状物的强度MOR与对比实施例8是可相比的,而根据这两个实施例的条状物的组成材料具有比根据对比实施例8的传统材料大20%以上的孔隙度和大75%以上的孔隙直径。

Claims (10)

1.包含陶瓷材料的多孔结构,该陶瓷材料主要地包含以这样的比例含有钛、铝、镁和锆的铁板钛矿类型的氧化物相或者由该氧化相组成,所述比例使得该铁板钛矿类型的相基本上满足下式:
(Al2TiO5)x(MgTi2O5)y(MgTiZrO5)z
所述材料满足以下组成,基于仅仅氧化物Al2O3,TiO2,MgO和ZrO2的mol%:
90<2a+3m<110;
100+a<3t<210-a;
a+t+m+zr=100,
其中:
-   a是Al2O3的摩尔百分比;
-   t是TiO2的摩尔百分比;
-   m是MgO的摩尔百分比;
-   zr是ZrO2的摩尔百分比,其中
-x为0.45-0.94;
-y为0.05-0.50;
-z为0.005-0.06;和
-x+y+z=1。
2.根据权利要求1的多孔结构,其中
-x为0.65-0.90;
-y为0.09-0.40;
-z为0.005-0.05;和
-x+y+z=1。
3.根据前述权利要求任一项的多孔结构,其中所述材料具有以下化学组成,基于氧化物的重量%:
-   大于25%并低于55%的Al2O3
-   大于35%并低于60%的TiO2
-   大于1%并低于8%的MgO;
-   大于0.7%并低于7%的ZrO2
-   低于20%的SiO-2
4.根据权利要求3的多孔结构,其中所述材料具有以下组成,基于氧化物的重量%:
-   大于35%并低于50%的Al2O3
-   大于40%并低于55%的TiO2
-   大于1.5%并低于6%的MgO;
-   大于1.5%并低于6%的ZrO2;和
-   大于0.5%并低于10%的SiO-2
5.根据权利要求1-2任一项的多孔结构,其中至少一部分ZrO2用至少一种选自Ce2O3或HfO2的氧化物替换,基于使用元素Ce和/或元素Hf对元素Zr的摩尔百分比替换。
6.根据权利要求1-2任一项的多孔结构,其中所述材料包含由铁板钛矿类型的相组成的主要相和至少一种次要相,所述次要相是硅酸盐相和/或基本上由二氧化钛TiO2和/或氧化锆ZrO2组成的相。
7.根据权利要求6的多孔结构,其中次要相由硅酸盐相组成,其比例为该材料的总重量的0-40%。
8.根据权利要求7的多孔结构,其中所述硅酸盐相主要由二氧化硅和氧化铝组成,在该硅酸盐相中的二氧化硅的质量比例大于50%。
9.根据权利要求6的多孔结构,其中次要相基本包含二氧化钛TiO2和/或氧化锆ZrO2
10.根据权利要求1-2任一项的多孔结构,其具有蜂窝状类型结构,构成所述结构的陶瓷材料具有大于10%的孔隙度和中心在5-60微米的孔径。
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