CN1213961C - 莫来石坯体和形成莫来石坯体的方法 - Google Patents
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Abstract
一种基本上由实质上是化学结合的莫来石晶粒组成的莫来石合成物,其中该合成物至少有两个微观结构本质上不同的相邻区域。通过形成一种或多种具有存在于莫来石中的元素的前体化合物的混合物;使该混合物成型为多孔的初形;向多孔初形的一部分添加晶粒成核控制剂并且然后在大气下加热步骤(c)的多孔初形,并且温度达到足以形成莫来石合成物。
Description
本发明涉及莫来石坯体(mullite bodies)和形成莫来石坯体的方法。多孔陶瓷坯体已广泛应用于诸如催化剂载体、过滤载体、过滤器和高温热绝缘体中。通常是由陶瓷粉末形成坯体,然后将该坯体加热至足以形成均匀多孔整体坯体的温度来制备多孔陶瓷坯体。
用陶瓷形成过滤器时,通常要形成颗粒状的陶瓷坯体。然后将该坯体加热至使颗粒轻度烧结成均匀整体坯体的温度(即,赋予该坯体足够的强度,同时仍具有足够的孔隙度以使液体或气体有效通过)。为了轻度烧结坯体,将一层薄的不同材料的区分层(即,其孔尺寸小于轻度烧结坯体的孔尺寸的层)施加在该坯体的一个表面上。
例如,将低温烧结的胶体陶瓷颗粒的分散体施加在已轻度烧结坯体上,并将该被覆坯体再次加热,以将胶体颗粒烧结形成与轻度烧结坯体结合的敷层。一步烧结几乎从未被用过,因为在烧结过程中载体和区分层有明显不同的收缩行为(例如,收缩率和收缩开始发生的温度),会导致裂缝。
近来Moyer等人描述了用莫来石(化学组成在3Al2O3·SiO2至3Al2O3·2SiO2之间的陶瓷)形成过滤器(专利号为US5,194,154和US5,198,007)。Moyer等人描述了大莫来石晶须的整体过滤器和具有单独施有诸如烧结的胶体氧化铝层、聚合的有机化合物或分子筛(例如沸石)等区分层的莫来石过滤器。
在多孔陶瓷(如多孔莫来石)上敷加独立区分层的工艺需要附加的步骤(如两次或多次加热步骤)。因而使处理产生损坏的可能性和由于结合的不足和热膨胀系数的不匹配而产生的区分层的分层的可能性增加了。通常这些会导致过滤器和类似产品成本的增加。
因此,需要提供克服现有技术的一个或多个问题,比如上述问题之一的形成方法和陶瓷过滤器及类似产品。
本发明的第一方面是制备莫来石合成物的方法,该方法包括:
a)形成一种或多种具有存在于莫来石中的元素的前体化合物的混合物,
b)使该混合物成型为多孔的初形(a porous green shape),
c)向多孔初形的一部分添加晶粒成核控制剂和
d)在一种气氛下加热步骤(c)的多孔初形,并且温度达到足以形成基本上由实质上是化学结合的莫来石晶粒组成的莫来石合成物,其中该合成物至少有两个微观结构本质上不同的相邻区域。
令人惊讶的是,本方法允许在原位形成薄的、孔尺寸比莫来石合成体孔尺寸小得多的区分层(discriminating layer)。还令人惊讶的是,该方法在整个合成物的一个或多个方向上能形成具有不同微观结构的交替区域的莫来石合成物。
本发明的第二方面是莫来石合成物,它基本上由基本上是化学结合的莫来石晶粒组成,其中该合成物至少有两个微观结构基本不同的相邻区域并且至少一个区域有莫来石晶须组成。
本发明的莫来石坯体可被用在任何适于用莫来石之处。尤其是,该莫来石坯体可用于需要坯体有两个或多个不同微观结构区域的应用中。例子包括过滤器、难熔材料、热和电绝缘体、催化剂和催化剂载体。
图1是用莫来石颗粒成核控制剂制备的本发明的莫来石合成物的扫描电子显微照片(60x的放大倍数)。
图2是不存在任何成核控制剂时制备的莫来石合成物的扫描电子显微照片(60x的放大倍数)。
图3是本发明的用莫来石颗粒成核控制剂制备的莫来石合成物的扫描电子显微照片(50x的放大倍数)。
图4是本发明的用莫来石颗粒成核控制剂制备的莫来石合成物的扫描电子显微照片(250x的放大倍数)。
莫来石合成物基本上由莫来石晶粒组成。“基本上由莫来石晶粒组成”意味着按体积计合成物至少含有90%的莫来石晶粒。优选莫来石合成物至少含有95%的莫来石晶粒,更优选至少98%,甚至更优选按体积计至少占合成物的98%,最优选基本上所有的合成物是莫来石晶粒。
莫来石合成物除莫来石晶粒外还可含有填充剂。该填充剂是不形成莫来石的化合物并且基本上不与莫来石发生反应。填充剂的例子包括石墨、金属(例如贵金属)、金属氧化物(例如氧化铈)和金属硫化物(例如二硫化钼)。
实质上所有的莫来石合成物晶粒与莫来石坯体的其它莫来石晶粒是化学结合的。这意味着按体积计至多1%的莫来石晶粒不能与其它的莫来石晶粒化学结合。优选基本上所有的莫来石晶粒被化学结合。化学结合一般是指晶粒是烧结或熔融在一起。晶粒间的相互化学结合使得莫来石坯体甚至是多孔的莫来石坯体在操作条件下,例如作过滤器时有足够的强度。
莫来石坯体的晶粒的化学计量可以是任何在3Al2O3·SiO2至1.3Al2O3·SiO2之间(即3-1.3)的适合的化学计量。优选化学计量至多为2.5,更优选至多为2.25,最优选至多2.1至优选至少1.4,更优选至少1.5,最优选至少1.6。最优选的莫来石的实施方式是Al2O3与SiO2的化学计量为1.6-1.85。化学计量可由任何合适的方法,如本领域已知的方法(例如,X-射线衍射或电子衍射)来确定。
晶粒可以具有任何莫来石可呈现的形态,只要一些晶粒是晶须。换言之,至少有一个区域由莫来石晶须组成。“晶须”是指纵横比大于2(例如长是宽的2倍)的晶粒。一般地,至少其中的一个区域是由平均纵横比大于10的晶须组成。优选莫来石坯体中所有的区域由晶须组成。
莫来石坯体也至少有两个微观结构基本不同的相邻区域。“不同的微观结构”是指相邻区域之一的区域,其至少下述特性中的一个特性的至少25%不同于其它的相邻区域的特性,这些特性选自平均孔尺寸、晶粒形态(例如平均纵横比)、晶粒尺寸(例如当量球径)和密度。优选微观结构至少50%不同,更优选至少100%,甚至更优选至少500%,最优选至少1000%不同。每一个特性可由合适的技术,例如本领域已知的技术(例如,抛光部分的电子显微镜)来测定。
一般地,一个区域是相当明显的合成物的一块,例如是其至少在两个相互正交方向上的尺寸至少比整个合成物最小平均当量球径晶粒尺寸大10倍的一块。区域的例子如合成物表面的一层(如区分层)。
相邻的不同区域可以惊人地具有窄的界面区域。例如,区域间的界面通常至多是2mm。依次优选地,界面至多是1mm,至多是0.75mm,至多是0.5mm,0.25mm,0.1mm,50μm,最优选至多是25μm。
本文的界面长度和宽度是由在相邻区域之间的接触形成的平面确定的。界面的厚度是与界面的长和宽垂直测得的距离。例如,当从一个区域向另一个区域测量界面厚度时,界面厚度是从至少一种微观结构性能,如晶粒尺寸与区域的整体性质有10%的不同的起始点处开始,到相同的性能与相邻区域的整体有10%的不同的点处之间的距离。
测量或微观结构的测量是在抛光的部分进行的。例如,平均莫来石颗粒尺寸可由莫来石坯体的抛光部分经扫描电子显微照片(SEM)测定,其中平均颗粒尺寸可由Underwood(安得伍得)在
Quantiative stereology(定量立体测量学),Addison Wesley,Reading,MA,(1970)中描述的截线法测量。
优选的莫来石合成物的实施方案有两个相互邻近的区域,其中一层的平均孔尺寸小一个数量级并且每一个区域由晶须组成。也优选较小孔尺寸区域的晶须具有约至少小于其它区域一个数量级的平均颗粒尺寸。最后,优选两个区域都由化学计量在1.5-2之间的莫来石晶须组成。
另一个优选实施方案是由莫来石晶须组成的合成物,该合成物有底区、顶区和介于底区和顶区之间的中区,其中中区不同于顶区和底区。优选顶区和底区与本文描述的不同。还优选中区的平均当量晶粒尺寸比顶区和底区的平均当量晶粒尺寸小一个数量级。
坯体中存在的杂质(即除上述莫来石中存在的元素之外的元素)总量通常至多占坯体重量的5%。优选杂质总量至多是1%,更优选至多是0.5%,甚至更优选至多是0.1%,最优选莫来石坯体中基本上不存在杂质(微量)。杂质量可由任何合适的全分析技术,诸如那些本领域熟知的(例如X-射线荧光)技术来测定。
制备莫来石合成物时,将含Al、Si和O的前体化合物混合以形成可形成莫来石的混合物。美国专利US5,194,154;5,198,007;5,173,349;4,911,902;5,252,272;4,948,766和4,910,172中描述了可以使用的前体化合物。该混合物也可含有其它的化合物,比如填充剂(前文有述)和有机化合物,以有利于混合物的成型(例如,粘合剂和分散剂,比如
Introduction to the Principles of Ceramic Processing(陶瓷加工原理介绍),J.Reed,Wiley interscience,1988中描述的那些)。一般地,该混合物由化合物,比如粘土(即,水合铝硅酸盐)、氧化铝、二氧化硅、三氟化铝、氟黄玉(fluorotopaz)和沸石组成。优选的前体化合物选自粘土、氧化铝、二氧化硅及其混合物。最优选该混合物由粘土和氧化铝组成。
通常前体化合物按比例选择,以使制备的莫来石具有如上所述的1.3-3的化学计量。
该混合物可由任何适宜的方法,如本领域熟知的方法来制备。实例包括球磨带混、垂直螺旋混合、V-混合和磨碎(attrition milling)。该混合物可干法(即无液体介质存在)或湿法制备。
然后将该混合物以任何适宜的方法,如本领域熟知的方法成型为多孔形坯体,实例包括喷射成型法、挤压、等静压、浇铸成型、轧辊压制和带铸(tape casting)。这些中的每一种方法在
Introduction to the Principles of Ceramic Processing(陶瓷加工原理介绍),J.Reed,Wiley interscience,1988中有详细描述。
多孔形的一部分中加入了成核控制剂。一般地,“一部分”是指成核控制剂加在多孔坯体的表面。成核控制剂或抑制或增强了莫来石的成核。一般地,成核控制剂是在加热多孔坯体之前加施加在成型的多孔坯体上的固体颗粒。成核控制剂的例子包括与混合物有相同化学组成的颗粒,不同的是控制剂颗粒或基本上大于或基本上小于混合物中的颗粒。“基本上大于或小于”是指平均颗粒尺寸至少约与混合物中颗粒的平均尺寸差一个数量级。控制剂也可以是莫来石颗粒。优选的成核控制剂是莫来石颗粒。
成核控制剂可以任何方便的方法,例如浸渍、喷射和涂漆应用。在应用之前,成核控制剂可与其它材料,比如上述的前体化合物和有机化合物组合使用。也可将成核控制剂形成成型坯体并用机械力加在多孔成型坯体上(例如,通过压力将多孔坯体与含控制剂的成型坯体层压在一起)。也就是说,成核控制剂可与前体混合,并用诸如带压延、共挤出、浸渍、喷射或涂漆等方法使混合物在不具有成核控制剂的前体上成层,以形成具有和没有成核控制剂区域的多孔坯体。
该工艺的最终步骤是在一种气氛下加热步骤(c)的多孔初形,并且温度足以形成莫来石合成物。希望的是,至少在部分加热过程中,氟存在于以比如以SiF4、AlF3,HF Na2SiF6 NaF和NH4F为气源的气氛中。优选用在气氛中的氟源是SiF4。
优选地,将多孔坯体在第一温度下加热足以使多孔坯体中的前体化合物转化成氟黄玉的时间,然后升至足以形成莫来石合成物的第二温度。温度也可以在第一温度和第二温度之间循环,以确保完全形成莫来石。第一温度可以是500℃-950℃。优选第一温度至少是550℃,更优选至少是650℃,最优选至少是725℃-750℃,优选至多是850℃,更优选至多是800℃,最优选至多是775℃。
第二温度可以是任何合适的温度,它取决于例如SiF4的分压的变化。一般地,第二温度至少是1000℃至至多1700℃。优选第二温度至少是1050℃,更优选至少是1075℃,最优选至少是1100℃,优选至多是1600℃,更优选至多是1400℃,最优选至多是1200℃。
一般地,在加热至第一温度的过程中,当希望引入含氟的气体时,在至少500℃之前,气氛是惰性的(如氮气)或真空的。在加热至第一温度的过程中,有机化合物和水可被除去。它们也可以经与Introduction to the Principles of Ceramic Processing(陶瓷加工原理介绍),J.Reed,Wiley interscience,1988中描述的本领域常用的独立加热步骤除去。
莫来石合成物特别适合用作催化剂的载体,比如用于汽车的催化式排气净化器的、通常被称之为催化剂涂料层(wash coat)的氧化铝颗粒上的贵金属催化剂的载体。优选莫来石晶粒是晶须。也优选涂料层在莫来石晶粒的至少一部分上成为一薄层。一般地,一部分是指一个区域的晶粒面积的10%被催化剂层覆盖。优选一个区域的所有晶粒被覆盖。更优选合成物所有的晶粒基本上被覆盖。
“薄层”是指催化剂涂料层的厚度一般小于被覆盖的晶粒的平均最小尺寸。一般地,层厚是至多一半的厚度,优选至多是三分之一,最优选至多是被覆盖晶粒的平均最小尺寸的四分之一。
莫来石合成物也特别适合用作移动能源应用(如柴油机发动机)和固定能源应用(如发电厂)的颗粒(粉尘)捕获和氧化(即排气)催化剂。如上所述,莫来石合成物至少有一部分莫来石晶粒有催化剂层,但优选合成物基本上所有的晶粒都覆有一层。然后将被覆的莫来石合成物放置在比如柴油机排气系统中从而气体通过合成物。在这样的装置中,粉尘一般在有小尺寸孔隙的区域被捕获,排出的气体通常在有较大孔隙的区域中被催化。由于粉尘颗粒保存在催化剂中,惊人的是,当催化剂加热至操作温度时,粉尘颗粒可能被燃烧,随后产生的气体如排出的气体一样被催化。
实施例
将25.1重量份的球粘土(Todd Dark grade,Kentucky-Tennessee ClayCompany,Mayfield,KY)与27.6重量份的-氧化铝,1.5份的羟丙基甲基纤维素(METHOCEL J75MS-N,The Dow Chemical Company,Midland,MI)和25份的去离子水混合制备的化学计量为1.67的莫来石前体压成圆片。在使用前将球粘土在110℃下干燥48小时。通过将氢氧化铝(HYDRAL 710,Alcoa,Pittsburgh,PA)在1000℃下加热1小时制得-氧化铝。将该圆片在下面的进度下素烧(bisque-fired)以除去有机粘接剂(即METHOCEL)和使粘土脱水:每分钟1℃下从室温加热至115℃,以每分钟3℃从115℃至350℃,以每分钟5℃从350℃至600℃,在600℃下保持3小时,以每分钟7℃从600℃加热至1025℃,在1025℃下保持1小时,以每分钟10℃冷却至室温。
然后陶瓷素烧坯圆片被莫来石粉体的分散层覆盖以形成成核控制剂的表面层。通过将17克的莫来石粉体(MULCR,Biakowskiinternational,Charlotte,NC)加入到100mL的0.2重量百分数NARVAN821A(R.T.Vanderbilt Company,Norwalk,CT)溶液的去离子水中制备出莫来石分散液。该圆片浸入该分散液中60秒后移去,空气中干燥,然后按上述的进度素烧。
然后将该圆片置于炉内的衬有镍箔的石英管中。在真空下将该圆片加热至950℃,然后在真空下冷却至640℃。此时,将SiF4气体引入管中直至得到了750托的气压。在640℃下将温度保持1小时。然后将该管以每分钟4℃加热至1015℃,然后将加热速度降至每分钟1℃。当温度达到1200℃时,管中的气压即刻减至100托并且允许升至550托,此时,气体以足以维持550托气压的速度被移走。当SiF4的释放基本上停止时(T=1084℃),将该圆片置于真空中并冷却至室温。该实施例的莫来石合成物的SEM显微照片示于图1。
对比例1
除了圆片不加成核控制剂(即莫来石粉)外,按照与实施例1中同样的方式形成圆片。将没有成核控制剂的圆片与实施例1的圆片同时加热并转化成莫来石。该对比例的莫来石圆片的SEM显微照片示于图2。
实施例2
将与实施例1中描述的相似的球粘土(Todd Dark grade,Kentucky-Tennessee Clay Company,Mayfield,KY)和-氧化铝的混合物压成圆片。在1000℃下素烧1小时后,该圆片按如下方法被覆莫来石粉。通过将0.431克的莫来石粉(MULCR,Biakowski international,Charlotte,NC)加入80mL的无水乙醇中并且在100瓦下声波处理(sonicating)40秒制备出分散液。将约0.8mL的分散液用点滴器加在圆片的一面上,使其干燥,同时以圆周运动轻轻地连续旋转该圆片。
将该圆片在100℃下干燥1小时,然后转移至与实施例1描述的相似的管中。在真空下将该圆片加热至700℃并且在此温度保持2小时,然后在真空下冷却至675℃。此时,将SiF4气体引入管中直至得到了600托的气压并以每分钟1℃加热至680℃。在维持600托的恒压下,将该圆片以每分钟3℃加热至1040℃,然后以每分钟1℃加热至1075℃。此时起,手控温度以1℃的步长慢慢的接近SiF4明显开始释放的点(1082℃)。慢慢的升温并且以足以维持600托气压的速度将气体从反应器除去。当SiF4的释放基本上停止时(T=1104℃),将反应器撤出并冷却至室温。该实施例得到的莫来石的SEM显微照片示于图3。
实施例3
将与实施例1中描述的相似的球粘土(Todd Dark grade,Kentucky-Tennessee Clay Company,Mayfield,KY)和-氧化铝的混合物挤成管。在1050℃下素烧1小时后,按如下方式将管转化成氟黄玉:在真空下加热至950℃,然后在真空下冷却至650℃。然后将SiF4气体引入管中至730托的气压并且在650下反应2小时40分钟。然后将反应器撤出并冷却至室温。此时管已转变成氟黄玉。
通过将管的内壁在短时间内置于以与实施例1中描述的相同的方法制备的、含按重量计4%的MULCR莫来石粉的粉浆中,管的内壁沉积了一层莫来石粉(MULCR,Biakowski international,Charlotte,NC)。在120℃下干燥一整夜后,该管在550℃下烧1小时。然后在真空下以每分钟10℃将该管加热至650℃,以每分钟4℃加热至1015℃,以每分钟1℃加热至1040℃,然后在1040℃下温度保持40分钟,然后以每分钟1℃直至SiF4的变化达到了每克黄玉0.43SCCM。在580托的恒压下操作维持SiF4恒速释放的过程中升温直至反应完全。然后将反应器撤出并冷却至室温。该实施例得到的莫来石管的SEM显微照片示于图4。
Claims (29)
1.一种制备莫来石合成物的方法,该方法包括:
a)形成一种或多种具有存在于莫来石中的元素的前体化合物的混合物,
b)使该混合物成型为多孔的初形,
c)向多孔初形的一部分添加成核控制剂固体颗粒和
d)在一种气氛下加热步骤(c)的多孔初形,并且温度达到足以形成基本上由实质上是化学结合的莫来石晶粒组成的莫来石合成物,其中该合成物有至少两个微观结构实质上不同的相邻区域并且至少一个区域由莫来石晶须组成。
2.如权利要求1的方法,其中所述前体化合物选自粘土、氧化铝、二氧化硅、氟黄玉、沸石、AlF3及其混合物。
3.如权利要求2的方法,其中所述前体化合物选自粘土、氧化铝、二氧化硅、氟黄玉、沸石及其混合物。
4.如权利要求3的方法,其中所述前体化合物是粘土和氧化铝的混合物。
5.如权利要求1的方法,其中所述固体颗粒是莫来石、平均粒度与多孔的初形中的前体化合物的平均粒度有一个数量级的差别的前体化合物、或其混合物。
6.如权利要求5的方法,其中所述固体颗粒是莫来石。
7.如前述权利要求任一项所述的方法,其加热至形成氟黄玉的第一温度然后加热至形成莫来石的第二温度。
8.如权利要求7的方法,其中在第一温度形成的所述氟黄玉在由SiF4组成的气氛中形成。
9.如权利要求7的方法,其中所述第一温度是500℃-950℃。
10.如权利要求9的方法,其中所述第一温度是725℃-750℃。
11.如权利要求10的方法,其中所述第二温度是1000℃-1700℃。
12.一种莫来石合成物,它基本上由实质上是化学结合的莫来石晶粒组成,其中该合成物有至少两个微观结构实质上不同的相邻区域并且至少一个区域由莫来石晶须组成。
13.如权利要求12的莫来石合成物,其中基本上所有的晶粒是晶须。
14.如权利要求12的莫来石合成物,其中Al2O3与SiO2的化学计量是1.3-3。
15.如权利要求14的莫来石合成物,其中所述化学计量是从1.3到2.5。
16.如权利要求15的莫来石合成物,其中所述化学计量是1.6-1.85。
17.如权利要求13的莫来石合成物,其中所述两个相邻区域的平均孔尺寸至少有一个数量级的差别。
18.如权利要求13的莫来石合成物,其中所述两个相邻区域之间的界面至多是2mm。
19.如权利要求18的莫来石合成物,其中所述界面至多是0.1mm。
20.一种汽车催化式排汽净化器,其特征是它由权利要求12的莫来石合成物组成。
21.如权利要求20的汽车催化式排汽净化器,其中在莫来石晶粒的至少一部分表面上有贵金属涂料层。
22.如权利要求21的汽车催化式排汽净化器,其中所述贵金属涂料层的厚度至多是被覆晶粒的平均最小尺寸的厚度的一半。
23.一种颗粒捕获-氧化催化剂,其含有权利要求12的莫来石合成物,其中所述莫来石合成物的至少一部分被覆有催化剂。
24.权利要求23的颗粒捕获-氧化催化剂,其中基本上所有的莫来石合成物被覆有催化剂。
25.权利要求23的颗粒捕获-氧化催化剂,其中所述莫来石合成物由两个相邻区域组成。
26.权利要求23的颗粒捕获-氧化催化剂,其中所述催化剂是贵金属涂料层。
27.权利要求26的颗粒捕获-氧化催化剂,其中所述贵金属涂料层的厚度至多是被覆晶粒的平均最小尺寸的厚度的一半。
28.一种颗粒捕获器,其特征是含有权利要求12-19的任何一种莫来石合成物。
29.一种颗粒捕获器,其含有权利要求1-11所得到的任何一种莫来石合成物。
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-
1999
- 1999-08-27 US US09/384,639 patent/US6306335B1/en not_active Expired - Lifetime
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2000
- 2000-08-17 EP EP00959269A patent/EP1218311B1/en not_active Expired - Lifetime
- 2000-08-17 JP JP2001519621A patent/JP5068909B2/ja not_active Expired - Fee Related
- 2000-08-17 MX MXPA02002109A patent/MXPA02002109A/es unknown
- 2000-08-17 BR BRPI0013566-6A patent/BR0013566B1/pt not_active IP Right Cessation
- 2000-08-17 WO PCT/US2000/022687 patent/WO2001016050A1/en active IP Right Grant
- 2000-08-17 KR KR1020027002487A patent/KR100692114B1/ko active IP Right Grant
- 2000-08-17 AT AT00959269T patent/ATE249400T1/de not_active IP Right Cessation
- 2000-08-17 DE DE60005203T patent/DE60005203T2/de not_active Expired - Lifetime
- 2000-08-17 CA CA002382312A patent/CA2382312C/en not_active Expired - Fee Related
- 2000-08-17 CN CNB008120641A patent/CN1213961C/zh not_active Expired - Lifetime
- 2000-08-17 AU AU70620/00A patent/AU7062000A/en not_active Abandoned
- 2000-08-17 ES ES00959269T patent/ES2200923T3/es not_active Expired - Lifetime
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ATE249400T1 (de) | 2003-09-15 |
AU7062000A (en) | 2001-03-26 |
KR100692114B1 (ko) | 2007-03-12 |
US20020014723A1 (en) | 2002-02-07 |
ZA200201222B (en) | 2003-07-30 |
BR0013566B1 (pt) | 2009-05-05 |
EP1218311A1 (en) | 2002-07-03 |
WO2001016050A1 (en) | 2001-03-08 |
DE60005203T2 (de) | 2004-07-15 |
JP5068909B2 (ja) | 2012-11-07 |
DE60005203D1 (de) | 2003-10-16 |
MXPA02002109A (es) | 2002-09-18 |
ES2200923T3 (es) | 2004-03-16 |
EP1218311B1 (en) | 2003-09-10 |
BR0013566A (pt) | 2002-07-02 |
JP2003508329A (ja) | 2003-03-04 |
CN1371343A (zh) | 2002-09-25 |
CA2382312A1 (en) | 2001-03-08 |
CA2382312C (en) | 2009-05-26 |
US6306335B1 (en) | 2001-10-23 |
KR20020037040A (ko) | 2002-05-17 |
US6596665B2 (en) | 2003-07-22 |
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