CN104703944B - 改进的包含多铝红柱石的多孔主体和其形成方法 - Google Patents

改进的包含多铝红柱石的多孔主体和其形成方法 Download PDF

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CN104703944B
CN104703944B CN201380052352.5A CN201380052352A CN104703944B CN 104703944 B CN104703944 B CN 104703944B CN 201380052352 A CN201380052352 A CN 201380052352A CN 104703944 B CN104703944 B CN 104703944B
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mullite
weight
carbon
fluorine
porous bodies
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CN104703944A (zh
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J·蔡
M·T·马兰加
P·C·沃塞普卡
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Dow Global Technologies LLC
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Abstract

适用于制造微粒过滤器的多孔陶瓷主体包含通过陶瓷晶界相结合在一起的针状多铝红柱石晶粒，其中所述多孔针状多铝红柱石主体的整体碳含量为所述主体的0.005重量％到10重量％。所述多孔主体可以通过以下来制备：形成多铝红柱石前体(例如氧化铝和二氧化硅)与为无机碳的化合物(石墨或非晶形碳)、含有碳的无机化合物(例如金属碳化物)或分解形成无机碳或含有碳的无机化合物的有机化合物的混合物，以及在含有氟的气氛中加热形成所述针状多铝红柱石主体并去除所述氟。

Description

改进的包含多铝红柱石的多孔主体和其形成方法
技术领域
本发明涉及包含多铝红柱石的主体和形成这些主体的方法。具体来说，本发明涉及具有熔融互锁针状晶粒的主体和其形成方法。
背景技术
近年来，欧洲和美国已经通过或设想关于柴油机和汽油机(如汽油直喷式发动机)所排放的微粒物质的更严格的规定。为了符合这些规定，微粒过滤器一般已经成为必要的并且预期将为必要的。
这些微粒过滤器必须符合多个相互制约的严苛要求。举例来说，过滤器必须具有足够的孔隙率(孔隙率一般大于55％)，同时仍能保留排放的大多数微米级柴油微粒(一般捕获超过90％的排放微粒)。过滤器还必须有足够的可透过性以使得不会太快出现背压过量，同时在再生之前仍能够负载大量烟尘。过滤器必须经得住长期腐蚀性废气环境。过滤器必须具有初始强度以放置到与排气系统连接的容器中。过滤器必须能够经得住来自烧除截留于过滤器中的烟尘(再生)的数千个循环的热循环(即保留适当强度)，其中局部温度可以高达1600℃。根据这些严格的标准，陶瓷过滤器为选用于研发柴油机微粒过滤器的材料。
已研究烧结堇青石陶瓷过滤器作为可能的柴油机微粒过滤器。堇青石由于其低成本和用作汽车排气系统中的三元催化剂载体的用途而被加以研究。已将堇青石过滤器用于大卡车应用中，但却遭遇背压高、积聚的灰渣需要清洁前的寿命短以及由于局部热点发生热降解的问题。
最近，已将碳化硅用于轻型柴油机中，主要是由于其比堇青石能经得起更多烟尘以及其更具热稳定性。然而，碳化硅遭遇例如必须使用昂贵精细碳化硅粉末高温烧结的问题。因为碳化硅被烧结了，所以产生的孔结构导致在过量背压产生之前烟尘负载量有限，就如同堇青石一样。
另外，美国专利第5,098,455号已描述了用作柴油机微粒捕集器的多铝红柱石，其晶体交错生长在一起。这些过滤器有低压降和热稳定性的优点，但可具有进一步改进的特性(例如改进的热冲击特性)以更广泛地利用。
因此，需要提供具有改进的热冲击特性或解决了现有技术问题中的一或多个(如那些上述问题中的一个)的改进的陶瓷微粒过滤器。
发明内容
本发明的第一方面为制造包含多铝红柱石的主体的方法，其包含，
(a)混合具有多铝红柱石中所存在的元素的一或多种前体化合物与含碳材料形成混合物，所述含碳材料即：(i)含有碳的有机化合物，其在步骤(b)中加热时分解形成石墨、非晶碳或含有碳的无机化合物；(ii)石墨碳；(iii)非晶碳；(iv)含有碳的无机化合物或(v)其组合，
(b)在具有含氟气体的气氛下加热步骤(b)的混合物形成包含多铝红柱石并且氟的量大于1重量％的多孔主体，以及
(c)去除氟形成包含多铝红柱石的多孔主体，其中氟的量小于主体的1重量％。
本发明的第二方面为包含通过陶瓷晶界相结合在一起的针状多铝红柱石晶粒的多孔主体，其中整体碳含量一般为主体的0.005重量％到10重量％并且氟量小于主体的1重量％。碳量可以为至少约0.001％、0.0015％到至多5％或1％。氟量典型地小于0.8％、0.6％、0.5％、0.3％、0.1％或甚至无氟。
出人意料地，多孔主体中碳的存在相比于在不存在这一碳下制备的相同组合物改进了热冲击因数。另外，包含多铝红柱石的主体也可以展示改进的耐废气环境腐蚀性(即改进随时间推移其耐热冲击性的保持)。
本发明的主体可以用于适用于多孔耐火陶瓷的任何应用中。实例包括过滤器、耐火材料、热和电绝缘体、金属或塑料复合体的强化物、催化剂以及催化剂载体。具体来说，其适合于微粒过滤器，如内燃废气过滤器。
附图说明
图1为显示陶瓷晶界相内的结晶硅酸盐相的本发明的多孔主体的抛光部分的能量色散X射线光谱法显微照片。
图2为具有分散在陶瓷晶界相内的SiC的本发明的多孔主体的抛光部分的能量色散X射线光谱法显微照片。
具体实施方式
包含多铝红柱石的主体
包含多铝红柱石的主体包含通过陶瓷晶界结合在一起的多铝红柱石晶粒。希望多铝红柱石晶粒占主体的至少约25体积％。优选地，多铝红柱石晶粒占组合物的至少约40体积％，更优选地至少约50体积％，甚至更优选地至少约99体积％。除多铝红柱石晶粒之外，主体可以含有其它陶瓷晶粒，如堇青石，和包含铝硅酸盐玻璃的陶瓷晶界相。适用于本发明的含有多铝红柱石和堇青石的组合物的实例包括PCT专利公开案第WO/2010/033763号和PCT申请第PCT/US12/031053号中所述的那些组合物。铝硅酸盐玻璃可以含有除Si和Al之外的呈氧化物形式的金属，其可以为铝硅酸盐玻璃内的非晶形或结晶沉淀。这类金属可以由用以制造多铝红柱石的前体材料(例如粘土)中所产生、多铝红柱石制造中引入(例如由混合设备磨损)或为获得如美国专利第7,485,594号中所述的某些形态或玻璃组合物所引入的杂质产生。这类金属也可以例如由通过使用金属碳化物制造组合物引入的金属产生。
典型地，这类其它金属的量不超出多铝红柱石陶瓷主体的约5重量％。理想地，金属为至多2％、1.5％、1％、0.5％、0.25％、0.1％到低到可行量(例如10重量百万分率)。
陶瓷晶界相一般位于晶粒表面和交叉晶粒表面。
多铝红柱石晶粒一般为在本文中称为“针状”的纵横比大于约2(例如长度为宽度的两倍)的晶粒。理想地，主体中所存在的针状晶粒的平均纵横比为至少约3。优选地，平均纵横比为至少约4，更优选地至少约5，甚至更优选地至少约8并且最优选地至少约10到至多约100或50。
微观结构可以通过合适技术，如抛光部分上的显微术来测定。举例来说，平均多铝红柱石晶粒尺寸可以由主体的抛光部分的扫描电子显微照片(scanning electronmicrograph，SEM)来测定，其中平均晶粒尺寸可以通过安德伍德(Underwood)在定量体视学(Quantitative Stereology)，艾迪生韦斯利(Addison Wesley)，雷丁·马(Reading，MA)，(1970)中所描述的截距法来测定。
尽管理论Al/Si多铝红柱石化学计量为3(3Al2O3·2SiO2)，但主体内多铝红柱石的整体Al/Si化学计量可以为任何合适化学计量，如4.5Al/Si到2Al/Si。大多数合适化学计量由如所用前体和加工工艺的因素而定。整体化学计量意指多铝红柱石晶粒主体(即并非每一个别晶粒)中Al与Si的比率。优选地，主体中多铝红柱石的整体化学计量可以为至少3、3.2、3.5或3.8到至多4.4或4.2。整体化学计量可以通过任何合适技术来测量，如所属领域中已知的那些技术，包括例如X射线荧光技术。
虽不了解，但如下文所进一步详述，已发现在多孔主体形成期间添加碳会出人意料地改进耐热冲击性、强度，并且可以改进针状多铝红柱石主体的耐腐蚀性。人们相信但不以任何方式限制，添加这类碳对于在具有改进特性的陶瓷晶粒之间形成晶界相有益。
典型地，包含多铝红柱石的多孔主体将具有仅来自环境中所见的经过吸附的化合物的一些整体碳和材料加工工艺中引入的痕量。这一量典型地小于多孔主体的0.005重量％。相比之下，本发明的主体的整体碳典型地为0.005重量％到10重量％。整体碳的量可以为至少约0.01％或0.015％到至多1％。应了解，多孔主体的整体碳会防止碳成为粘合剂，所述粘合剂可以用于粘着单独的本发明的单块多孔主体以形成较大多孔结构(例如包含已经使用粘合剂粘着在一起的较小的本发明的单块多孔蜂巢的蜂巢)。
整体碳含量可以通过已知技术，如燃烧红外检测技术使用如购自密歇根州的圣约瑟夫(St.Joseph，MI)的美国力可公司(LECO Corporation)的CS844系列碳/硫分析仪的设备来测定。
碳可以例如呈玻璃内的氧碳化物结晶或非晶形物质形式或分散于陶瓷晶界相内的金属碳化物形式。理想地，仅一部分碳以陶瓷晶界相内的金属碳化物夹杂物(微粒)形式存在。这部分以金属碳化物形式存在的碳可以为至多50％、60％、70％、80％、90％、95％并且甚至不可使用如X射线衍射或能量色散X射线光谱测定的典型分析技术检测到。
在一具体实施例中，多孔主体包含分散在陶瓷晶界相内的金属碳化物。例示性金属碳化物包括碳化硼、碳化硅、碳化钨、碳化铪、碳化锆、碳化铝硼、碳化铝、碳化钛以及碳化钒。还应了解，碳化物可以呈相同金属的氧碳化物、硝基碳化物或氧硝基碳化物形式。在一优选实施例中，金属碳化物为具有多铝红柱石前体元素(例如Si或Al)的碳化物。优选地，金属碳化物为碳化硅。
本发明的多孔主体也可以具有存在于陶瓷晶界相中的结晶二氧化硅相。在一具体实施例中，陶瓷晶界相可以包含相分离的铝硅酸盐玻璃和结晶二氧化硅相。
一般来讲，主体的孔隙率为至少约40％到至多约85％。优选地，主体的孔隙率为至少约45％，更优选地至少约50％，甚至更优选地至少约55％，并且最优选地至少约57％到优选地至多约80％，更优选地至多约75％，并且最优选地至多约70％。
出人意料地，含有前述碳的主体相比于不具有所述碳同时具有基本上相同的孔隙率的多铝红柱石主体具有改进的热冲击因数(TSF)。举例来说，本发明的多铝红柱石主体的TSF可以为缺乏这类碳或在不存在含碳材料下以相同方式制备的相同多铝红柱石主体的TSF的110％、120％、130％、140％、150％、160％、170％、180％。TSF甚至可以为缺乏所述碳或在不存在含碳材料下制备的多铝红柱石主体的两倍。一般来讲，热冲击因数为至少约200℃，更优选地至少约225℃，并且最优选地至少约250℃。热冲击因数(TSF)通过以下等式给出：
其中CTE为以(1/℃)给出的热膨胀系数。作为说明，多铝红柱石的平均CTE为约5×10-6/℃(注意，CTE随温度而略有变化，但典型地在使用以上等式时使用室温到约800℃的平均CTE)。
举例来说，在用碳化硅作为含碳材料制备时，小程度的TSF增加可以归因于CTE的降低，但出人意料地，强度实质上增加，而模数不增加。举例来说，当主体用作废气微粒捕集器而经得住放置于连接到排气系统的金属罐中以及使用中遇到的机械力时，这一强度增加适用。举例来说，本发明的主体的TSF的强度可以为缺乏这类碳或在不存在含碳材料下以相同方式制备的相同主体强度的110％、120％、130％、140％、150％、160％、170％、180％。
一般来讲，强度为至少约15MPa。优选地，强度为至少约17MPa，更优选地，保留强度为至少约19MPa，甚至更优选地为至少约20MPa，并且最优选地为至少约25MPa。保留强度一般通过自如适用于制造微粒过滤器的蜂巢的主体切下的条的4点弯曲来测定。强度测量可以使用已知技术，如ASTM C1161所述的技术来进行。
形成包含多铝红柱石的主体
在主体制造中，使含有Al、Si以及氧(即多铝红柱石中所存在的元素)的前体化合物与含碳材料混合形成混合物。可使用的前体化合物描述于美国专利第5,194,154号；第5,198,007号；第5,173,349号；第4,911,902号；第5,252,272号；第4,948,766号以及第4,910,172号中。
一般来讲，混合物包含粘土(即含水铝硅酸盐)和前体化合物，如氧化铝、二氧化硅、三氟化铝、氟黄玉(fluorotopaz)以及沸石。前体化合物可包括粘土、二氧化硅、氧化铝以及其混合物。优选地，混合物包含粘土和氧化铝或二氧化硅和氧化铝。混合物可含有其它化合物，如描述为如美国专利第7,485,594号，第5栏，第50-67行所描述的特性增强化合物的那些化合物。
前体化合物按比例进行选择以使得所得主体具有如先前所描述的Al/Si整体多铝红柱石化学计量。在本文中应了解，Al/Si化学计量是指实际上形成多铝红柱石的前体中的铝和矽。也就是说，如果氟来源为例如AlF3，那么为达到化学计量的目的，前体中所存在的SiO2的量必须减少通过来自AlF3的氟与SiO2反应形成SiF4而挥发掉的SiF4的量。
含碳材料为(i)含有碳的有机化合物，其在步骤(b)的加热时分解形成石墨、非晶碳或含有碳的无机化合物；(ii)石墨碳；(iii)非晶碳；(iv)含有碳的无机化合物或(v)其组合以形成混合物。
当含碳材料为含有碳的有机化合物时，应了解所述化合物需要形成石墨碳、非晶碳或含有碳的无机化合物。用以产生碳的量和环境可以由所属领域的普通技术人员在无负载下测定。典型地，分解这类有机化合物以形成含碳材料可以如下文所述通过加热进行。这类加热可以作为包含下文进一步描述的在氟气下加热的加热循环的一部分在同一锅炉中进行，或可以分别进行。
加热的温度和时间必须足以分解有机化合物并形成含碳化合物，但不能太大以使得在氟气氛中加热时混合物反应或以其它方式有害地影响主体的形成。一般来讲，加热温度为至多约800℃，但优选地偏好递增为至多约750℃、700℃、650℃、600℃、550℃以及500℃。温度一般为至少300℃，否则分解和形成含碳陶瓷的时间可能比所需更长。典型地，温度依次递增为至少350℃、400℃以及450℃。温度下的时间可以为任何适合于形成含碳材料的时间。典型地，时间可以在数分钟到数天的范围内，其中几分钟到几天的实际时间为典型的。
如果有机化合物形成如上所述的碳，那么其也可以有助于使混合物成形为成形主体(例如蜂巢)。这类有机化合物的实例包括例如粘合剂和分散剂，如《陶瓷加工原理简介》(Introduction to the Principles of Ceramic Processing)，J·里德(J.Reed)，威利国际科学(Wiley Interscience)，1988中所述的那些粘合剂和分散剂。这类有机化合物的其它实例包括美国专利第5,384,291号，第3栏第3行到第4栏第34行所述的那些有机化合物。
有机化合物的其它实例为分解时可形成金属碳化物的化合物。这些类型的有机化合物通常称为预制陶瓷聚合物。这些有机化合物的实例通过美国专利第4,226,896号；第4,310,482号；第4,800,221号；第4,832,895号；第5,312,649号；第6,395,840号以及第6,770,583号以及美国国防技术信息中心出版(Defense Technical Information Centerpublication)，预制陶瓷聚合物：过去、现状和未来(Preceramic Polymers：Past，Present and Future)，赛菲尔特(Seyferth)，迪特玛(Dietmar)，寄存编号：ADA258327，1992年11月2日以及聚碳硅烷、聚硅氮烷以及聚碳硅氮烷作为陶瓷前体的综合分析化学(Comprehensive Chemistry of Polycarbosilanes，Polysilazanes，and Polycarbosilazanes as Precursors of Ceramics)，M·比罗(M.Birot)等人，化学评论(Chem.Rev.)1995，95，1443-1477描述当制造碳化硅化合物或氧碳化硅化合物时，聚合物可以为硅酮或硅酮油，如通过市售硅酮油热分解产生高产量高表面积SiC纳米棒(Thermal Decomposition of Commercial Silicone Oil to Produce High Yiele High Surface Area SiCNanorods)，V·G·波尔(V.G.Pol)等人，物理化学杂志B(J.Phys.Chem.B)2006，110，11237-11240所述。一个具体的实例为购自纽约(NY)市马耳他(Malta)的星火系统公司(StarfireSystems Inc.)的市售聚合物STARFIRE SMP-10。
典型地，气氛为充分缺乏氧以使得以上有机化合物并不仅仅氧化形成例如水、氧化亚氮、一氧化碳、二氧化碳或金属氧化物的气氛。然而，可以存在一些氧以使得必要时形成氧碳化物。典型地，气氛可以为惰性的(例如惰性气体)或自生的(即密封并且由聚合物氧化产生的CO足以形成含碳材料)。
含碳材料可以为石墨碳或非晶碳颗粒，如所属领域中已知的那些含碳材料。典型地，微粒尺寸和分布为任何适用于制造混合物的微粒尺寸和分布，但典型地具有至多约20微米的平均粒度。理想地，平均尺寸为以重量计至多15微米、10微米、5微米、3微米、1.5微米或甚至1微米到至少约10纳米。合适的石墨碳包括在所属领域中熟知和市售的那些石墨碳。非晶形碳包括被称为碳黑、乙炔黑、灯黑等并且购自如马萨诸塞州的波士顿(Boston，MA)的卡巴特公司(Cabot Corporation)的公司的那些非晶形碳。
含碳材料也可以为含有碳的无机化合物。含有碳的无机化合物可以为例如金属碳化物、金属氧碳化物、金属硝基碳化物或金属氧硝基碳化物。这类化合物的金属的实例可以为产生实质上耐火的碳化物的那些金属中的任一种。这类金属的实例为Si、Al、W、Hf、Zr、Ti、V、B以及其组合。具体的实例包括碳化硅、碳化铝、碳化铝硼、碳化钨、碳化锆、碳化铪以及其组合。应了解，这类碳化物可以具有不同化学计量并且本文中涵盖这类不同化学计量。
将一定量的含碳材料添加到混合物中使得混合物具有获得如上所述主体中的所需整体碳的碳量。典型地，这一量意指占混合物的约0.1重量％到约30重量％。应了解，当使用有机化合物时，分解形成石墨碳、非晶碳或含有碳的无机化合物时损失的碳量不包括在前述范围中。一般来讲，碳量为混合物的至少0.2重量％、0.2重量％、0.3重量％、0.5重量％、0.75重量％、0.9重量％或1重量％到至多2重量％、3重量％、4重量％、5重量％、6重量％、7重量％、8重量％、9重量％、10重量％、12重量％、15重量％或20重量％。
含有碳的无机化合物理想地具有与先前针对石墨碳和非晶碳所述相同的粒度。
混合物可以通过任何合适的方法，如所属领域中已知的那些方法制备。实例包括介质研磨(例如球磨或磨碎研磨)、带式混合、立式螺旋混合以及V混合。混合物可以干式(即在不存在液体介质下)或湿式制备。当混合物以湿式制备时，液体介质可以为任何适用于制造这类混合物的溶剂，如水或有机溶剂(例如醇、烷烃、酯、醚或其组合)。典型地，使用水。
接着混合物典型地通过如所属领域中已知的那些方法的任何合适的方法成形为多孔形状。实例包括注射模制、挤压、均压、注浆成型、滚筒压制以及流延成型。这些方法中的每一种更详细地描述于陶瓷加工原理简介，J·里德，威利国际科学，1988中。
成形多孔形状接着在含有氟的气氛下加热到足以形成多铝红柱石组合物的温度。气态气氛中氟可自如SiF4、AlF3、HF Na2SiF6NaF以及NH4F的来源提供。优选地，氟来源为来自SiF4。优选地，单独提供氟。“单独提供”意指含氟气体并非自混合物中的化合物(例如AlF3)供应，而是自泵入加热混合物的锅炉中的外部气体供应。这一气体优选地为含有SiF4的气体。
一般来讲，在所述方法中，将多孔主体加热到第一温度维持足以在存在含氟气体下使多孔主体中的前体化合物转换成氟黄玉的时间，并且接着升高到第二温度，所述温度足以形成多铝红柱石组合物，其中自气氛去除或清除氟气体。温度也可以在第一与第二温度之间循环以确保多铝红柱石完全形成。第一温度典型地为约500℃到约950℃。优选地，第一温度为至少约550℃，更优选地至少约650℃，并且最优选地至少约725℃到优选地至多约850℃，更优选地至多约800℃并且最优选地至多约775℃。
第二温度可以为视如气氛中SiF4分压的变数而定合适的任何温度。一般来讲，第二温度为至少约960℃到至多约1700℃。优选地，第二温度为至少约1050℃，更优选地至少约1075℃，并且最优选地至少约1100℃到优选地至多约1600℃，更优选地至多约1400℃并且最优选地至多约1200℃。
视用于混合物中的含碳材料而定，在加热到第一温度期间，气氛典型地为惰性的(例如氮气)或真空直到至少约500℃，这时理想地引入单独提供的含氟气体。在加热到第一温度期间，可以去除水或其它液体溶剂，并且有机化合物分解形成如上所述含碳材料。也可以去除其它有机化合物(例如蒸发而非分解，如低分子量表面活性剂和润滑剂)。也可以在如上所述的各别加热步骤中去掉水去除和有机化合物分解。
在冷却并形成包含多铝红柱石并具有氟的多孔主体之后，多铝红柱石组合物经过进一步热处理形成包含多铝红柱石但去除氟的最终主体。在这一热处理之后主体中的氟量为小于1重量％，并且一般为小于主体的0.8重量％、0.6重量％、0.3重量％、0.1重量％、0.01重量％或甚至无氟存在。在不存在这类热处理下，氟典型地为至少约2重量％。这一热处理可以在空气、水蒸气、氧气、惰性气体或其混合物中进行足以形成本发明的另一多孔主体的时间。惰性气体的实例包括氮气和惰性气体(即He、Ar、Ne、Kr、Xe以及Rn)。优选地，热处理气氛为惰性气体、空气、水蒸气或其混合物。更优选地，热处理气氛为氮气、空气或含有水蒸气的空气。
热处理温度下的时间与热处理气氛、具体多铝红柱石组成以及所选温度有关。举例来说，在湿空气(在约40℃下以水蒸气饱和的空气)中热处理一般需要在1000℃下几小时以上到48小时。相比之下，理想地将环境空气、干燥空气或氮气(在室温下相对湿度为约20％到80％的空气)加热到1400℃维持至少约2小时。
一般来讲，热处理温度下的时间为至少约0.5小时，并且由所用温度而定(即一般来讲，温度越高时间可能越短)。优选地，热处理温度下的时间为至少约1小时，更优选地至少约2小时，甚至更优选地至少约4小时并且最优选地至少约8小时到优选地至多约4天，更优选地至多约3天，甚至更优选地至多约2.5天并且最优选地至多约2天。
多孔主体可以尤其适用作催化剂的载体，如披贵金属催化剂的氧化铝粒子，典型地称为用于汽车催化转换器的催化剂洗涤涂布。同样优选的是洗涤涂布在构成多孔主体的晶粒的至少一部分上制造薄涂层。一部分一般为这时一个区域的晶粒面积的至少约10％被催化剂涂层覆盖。优选地，一个区域的实质上所有晶粒都被涂布。更优选地，组合物的实质上所有晶粒都被涂布。多孔主体可能使用的其它催化剂应用包括例如催化燃烧器。
薄涂层意指催化剂洗涤涂层的厚度一般小于被涂布的晶粒的平均最小尺寸。一般来讲，涂层的厚度为被涂布的晶粒的平均最小尺寸的至多约一半厚度，优选地至多约三分之一，并且最优选地至多约四分之一厚度。
多孔主体还可以尤其适用作用于移动功率应用(例如柴油机)和固定功率应用(例如电厂)的微粒(烟尘)捕集器和氧化(即废气)催化剂。多孔主体在用作柴油微粒捕集器时，如上所述至少一部分晶粒可以涂布有催化剂。当然，本身无任何催化剂的多孔主体也可以适用作烟尘捕集器。
实例
比较例1a和1b
制备挤压糊剂，其由63.7重量％的多铝红柱石前体粉末、4.5重量％的甲基纤维素(METHOCEL A4M，购自密歇根州的米德兰(Midland，MI)的陶氏化学公司(The Dow ChemicalCo.))以及31.8重量％的水组成。多铝红柱石前体粉末为以下各物的混合物：25.35重量％的球磨研磨粘土(EUBC01 Hywite Alum，购自法国萨兰德雷(Salindres)的陶瓷技术工业公司(Ceramiques Techniques&Industrielles S.A.)，“CTI”)、46.40重量％的氧化铝粉末(CTIKA01，购自CTI)以及25.35重量％的高岭土粉末(EUBC03 Argical-C 88R，购自CTI)、0.30重量％的铁氧化物(Fe-601，购自新泽西州伯根菲尔德(Bergenfield，NJ)的大西洋设备工程公司(Atlantic Equipment Engineers)、2.60重量％的原料滑石(WC&D talc MB50-60，购自佐治亚州亚特兰大(Atlanta，GA)的应用陶瓷公司(Applied Ceramics))。多铝红柱石前体的化学组成为69.7重量％的Al2O3、27.3重量％的SiO2、1.0重量％的MgO、1.0重量％的Fe2O3、0.6重量％的TiO2、0.3重量％的K2O以及0.1重量％的CaO。
使用来自汉德股份有限公司(HNDLE GMBH)(德国)的实验室挤压机将挤压糊剂挤压到尺寸为12.7毫米×2.5毫米×75毫米的条中。所述条在空气中在每分钟1.25℃的升温速率下加热到1050℃并且在那一温度下保持2小时以去除含碳有机添加剂，形成经过煅烧的条。
接着在3托真空下在1℃/分钟的升温速率下将经过煅烧的条加热到700℃。条在700℃下平衡时，引入流动四氟化硅气体以形成氟黄玉。基于反应器压力初始降低，接着随时间推移趋于平衡达恒定压力，完成SiF4的吸收。自反应器去除未被吸收的气体。在去除期间，反应压力降低到38托。反应器接着回填100％SiF4达到分压为150托。在回填时，首先在2℃/分钟下将反应器内含物加热到980℃，接着降低到1℃/分钟，由980℃加热到1150℃。接着停止四氟化硅的流动并且接着去除反应器中剩余的气体。随后在反应器冷却到室温时，用氮气净化反应器。
这些初生针状多铝红柱石条是指“初生”针状多铝红柱石条(对比例1a)。其氟含量为约2重量％。针状多铝红柱石条在冷却并自锅炉移出之后，随后在空气中加热到1400℃的温度维持6小时(最终多铝红柱石条-对比例1b)。这些最终条的氟量小于主体的1重量％。
最终多铝红柱石条的杨氏模量(Young′s Modulus)使用ASTM C 1259-94，“通过振动的脉冲激发进行的先进陶瓷的动态杨氏模量、剪切模量以及泊松比的标准测试方法(Standard Test Method for Dynamic Young′s Modulus，Shear Modulus，and Poisson′sRatio for Advanced Ceramics by Impulse Excitation of Vibration)”中所概述方法用GrindoSonic脉冲激发仪c仪器(MK5工业，来自密苏里州布里奇顿(Bridgeton，MO)的莱蒙斯公司(J.W.Lemmens，Inc))来测定。条的强度使用4点弯曲测试经INSTRON 5543负载框(伊利诺伊工具公司(Illinois Tool Works)，马萨诸塞州诺伍德(Norwood，MA))遵循ASTM标准C1161来测定。使用热机械分析仪(TMA)测量蜂巢样品的热膨胀系数(CTE)。所用仪器为来自TA仪器公司(TA Instruments)的TMA 2940。制备高度约10毫米的蜂巢样品用于CTE测量。在CTE测量中，样品处于0.05牛顿负载下并且在氮气下以5℃/分钟升温速率由室温加热到800℃。CTE通过扩展度除以室温到800℃的温度变化来计算。经Micromeritics Autopore IV9520(微粒学仪器有限公司(Micromeritics Instrument Corporation)，佐治亚州诺克斯(Norcross，GA))进行汞压孔率测定分析。在120℃下干燥样品2小时并且接着在分析之前以机械方式抽出气体到真空状态下以自样品表面去除任何物理吸附物质(即水分)。每一样品使用约0.8克进行分析。这一比较例的多铝红柱石的孔隙率和微孔尺寸通过汞压孔率测定法来测定。最终条的整体碳使用燃烧分析利用LECO CS844分析仪使用燃烧红外检测技术来测定。这一比较例1a和1b的杨氏模量、弯曲强度以及CTE、整体碳、孔隙率以及微孔尺寸示于表1中。
实例1a和1b：
这一实例的多铝红柱石条以与比较例1a相同的方式来制备，但其中改将用以制造由95重量％的比较例A的多铝红柱石前体粉末和5重量％的碳化硅粉末组成的挤压糊剂的多铝红柱石前体粉末预混合。挤压糊剂由64.3重量％的多铝红柱石前体粉末(即61.1重量％的比较例1a的多铝红柱石前体粉末加3.2重量％的碳化硅粉末)、4.5重量％的甲基纤维素(METHOCEL A4M，购自密歇根州的米德兰的陶氏化学公司)、31.2重量％的水组成。所用碳化硅粉末为平均粒度为0.6微米的HSC490N，购自伊利诺斯州芝加哥(Chicago，IL)的优良石墨公司(Superior Graphite Co.)。
未经过处理(初生)和经过进一步热处理的这一实例的条的特性示于表1中。未经过处理的条的氟含量为主体的约2重量％。经过热处理的条的氟含量小于主体的1重量％。应了解，这一未经过处理(初生)的实例并非主体的实例，但为本发明方法的一部分的说明。
图1展示实例1b的抛光部分的扫描电子显微照片，其中多铝红柱石晶粒(10)通过硅酸盐玻璃(20)、具有富镁硅酸盐玻璃(40)区域的硅酸盐玻璃(20)中的结晶二氧化硅(30)区域结合在一起。在这一具体图中，SiC颗粒未示出。
实例2：
这一实例的多铝红柱石条以与比较例1a和1b所述相同的方式来制备，但其中改将用以制造由90重量％的比较例A的多铝红柱石前体粉末和10重量％的碳化硅粉末组成的挤压糊剂的多铝红柱石前体粉末预混合。挤压糊剂由64.6重量％的多铝红柱石前体粉末(58.1重量％的比较例1a的多铝红柱石前体粉末加6.5重量％的碳化硅粉末)、4.5重量％的甲基纤维素(METHOCEL A4M，购自密歇根州的米德兰的陶氏化学公司)以及31.0重量％的水组成。
经过热处理的这一实例的条的特性示于表1中。图2为这一实例的能量色散X射线光谱法显微照片，展示多铝红柱石晶粒(10)与具有富镁玻璃(40)和碳化硅(50)的硅酸盐玻璃(20)的晶界相结合在一起。
实例3：
这一实例的多铝红柱石条以与比较例1a和1b所述相同的方式来制备，但其中改将用以制造由85重量％的比较例1a的多铝红柱石前体粉末和15重量％的碳化硅粉末组成的挤压糊剂的多铝红柱石前体粉末预混合。挤压糊剂由64.5重量％的多铝红柱石前体粉末(54.8重量％的比较例1a的多铝红柱石前体粉末加9.7重量％的碳化硅粉末)、4.5重量％的甲基纤维素(METHOCEL A4M，购自密歇根州的米德兰的陶氏化学公司)以及31.0重量％的水组成。
经过进一步热处理的这一实例的条的特性示于表1中。
实例4：
这一实例的多铝红柱石条以与实例1a和1b所述相同的方式来制备，但其中改用碳化硅粉末，即平均粒度为4.5微米的购自宾夕法尼亚州沃里克(Warwick，PA)的番迪公司(Warwick)的F1000碳化硅粉末。在进一步热处理之后这一实例的条的特性示于表1中。
实例5：
这一实例的多铝红柱石条以与实例1a和1b所述相同的方式来制备，但其中改用碳化硅粉末，即平均粒度为23微米的购自宾夕法尼亚州沃里克的番迪公司的F360碳化硅粉末。经过进一步热处理的这一实例的条的特性示于表1中。
实例6：
这一实例的多铝红柱石条以与实例1a和1b中所述相同的方式来制备，但替代使用碳化硅粉末，使用购自伊利诺斯州芝加哥的优良石墨公司的平均粒度为0.6微米的碳化硼粉末HSCB4C。在进一步热处理之后，这一实例的条的特性示于表1中。
实例7：
这一实例的多铝红柱石条以与实例1a和1b中所述相同的方式来制备，但其中条不经历加热到1050℃温度以去除含碳有机材料以便形成经过煅烧的条。经过挤压的条仅在空气中干燥并且接着直接多铝红柱石化并且如比较例1a和1b中所述进一步热处理。在进一步热处理之后这一实例的条的特性示于表1中。
根据表1，实例展示如果通过在含氟气体中加热以及随后去除氟形成包含多铝红柱石的多孔主体时存在足够量的碳，那么主体的特性得以改进。具体来说，特别是当使用碳化硅时展示改进的特性，在混合物中SiC的量为起始混合物的约5％到10％时，由此致使主体中的碳为约0.018重量％。看起来碳化硅较少也是有益的，这不应理解为但可以是其会比如实例2所示的较大尺寸更容易或更均匀地并入玻璃中而不限制本发明。
表1
*比较例1b为100％。变化％为实例的TSF/比较例1b的TSF乘以100。

Claims (12)

1.一种制造包含多铝红柱石的主体的方法，其包含，
(a)混合具有多铝红柱石中所存在的元素的一或多种前体化合物与含碳材料形成混合物，所述含碳材料为金属碳化物，其中所述金属碳化物为碳化硅且平均粒度为至多3微米，并且其中所述混合物中碳材料的量足以使所述包含多铝红柱石的多孔主体的整体碳含量为所述主体的0.005重量％到10重量％，
(b)在具有含氟气体的气氛下加热步骤(a)的所述混合物形成包含多铝红柱石并且氟的量大于1重量％的多孔主体，以及
(c)去除所述氟形成所述包含多铝红柱石的多孔主体，其中氟的量小于所述主体的1重量％。
2.根据权利要求1所述的方法，其中所述前体化合物为粘土、氧化铝、二氧化硅、氟黄玉、沸石、三氟化铝或其混合物。
3.根据权利要求1所述的方法，其中所述金属碳化物为碳化硅、碳化硼、碳化铝、碳化铝硼、碳化钨、碳化钛、碳化钒或其组合。
4.根据权利要求1所述的方法，其中所述平均粒度为至多1.5微米。
5.根据权利要求1所述的方法，其中所述混合物的Al/Si比率为大于3，并且小于或等于4.5。
6.根据权利要求5所述的方法，其中所述Al/Si比率为3.8到4.2。
7.根据权利要求1所述的方法，其中所述混合物的金属杂质浓度为所述混合物的至多0.5重量％。
8.根据权利要求1所述的方法，其中所述多铝红柱石包含为针状的晶粒。
9.根据权利要求8所述的方法，其中所述去除通过在含氧气氛中加热以便所述氟的量降低到小于0.3重量％来实现。
10.一种多孔主体，其包含通过陶瓷晶界相结合在一起的针状多铝红柱石晶粒，其中整体碳含量为所述多孔主体的0.005重量％到10重量％并且氟的量为小于1％，其中所述陶瓷晶界相在其中分散有金属碳化物，其中所述金属碳化物为碳化硅且平均粒度为至多3微米。
11.根据权利要求10所述的多孔主体，其中所述陶瓷晶界相为其中具有结晶二氧化硅相的铝硅酸盐玻璃。
12.一种微粒过滤器，其包含根据权利要求10所述的多孔主体。
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US20150225302A1 (en) 2015-08-13
CN104703944A (zh) 2015-06-10
KR20150065174A (ko) 2015-06-12
JP2016501805A (ja) 2016-01-21

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