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CN1901989B - 具有疏水涂层的陶瓷结构 - Google Patents

具有疏水涂层的陶瓷结构 Download PDF

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CN1901989B
CN1901989B CN2004800394046A CN200480039404A CN1901989B CN 1901989 B CN1901989 B CN 1901989B CN 2004800394046 A CN2004800394046 A CN 2004800394046A CN 200480039404 A CN200480039404 A CN 200480039404A CN 1901989 B CN1901989 B CN 1901989B
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cordierite
coating
main body
ceramic
composition
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CN1901989A (zh
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M·P·布利斯
D·C·布克宾德
R·J·佩斯利
C·J·沃伦
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Corning Inc
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Corning Inc
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Abstract

一种用作NOx催化剂载体，或用作DPF的催化剂载体结构，其包括：(i)由例如堇青石或钛酸铝组成的多孔陶瓷体，优选整体性陶瓷蜂窝体；以及(ii)在至少其外表面上的疏水涂层，这种结构导致了其在接触用于施涂催化剂涂层的工艺过程中的液体催化剂涂层介质和含水介质。在优选的实施方式中，疏水涂层被形成在提供于多孔陶瓷体上的所施涂的外表皮层的里面或上面。

Description

具有疏水涂层的陶瓷结构
本发明的背景
1.本发明的领域
本发明涉及具有钝化层或疏水层的催化剂载体结构，尤其涉及具有疏水性外涂层的堇青石或钛酸铝催化剂载体结构/柴油机过滤器。
2.相关工艺技术的讨论
由于柴油机在其效率、耐用性和经济性方面的优势，近来人们对柴油机十分重视。但是，由于柴油机的排放物会对环境和人类造成危害，所以受到了美国和欧洲的抨击。因而，严格的环境法规要求柴油机达到与汽油机相同的标准。于是，柴油机制造商和排放控制公司正在进行研发，以制造出更耐用、更清洁并在各种运行条件下满足最严格的要求且对用户成本最低的柴油机。
类似于常规发动机，从柴油机排放的废气需要进行脱除氮氧化物(NOx)的净化。然而，不同于简单地采用三向催化剂(three-way catalysts)的常规发动机，柴油机是一种部分贫燃汽油发动机，产生的废气带有过量的氧，是不能只采用三向催化剂的，因为这些类型的催化剂需要在空-燃比基本上为化学计量的条件下才能正常发挥作用。
NOx捕集器似乎是用于柴油机中废气净化的最主要选用对象。NOx捕集器类似于三向催化剂，因为它们都由催化剂载体和涂布在载体上的催化剂组成，所不同的是在NOx捕集器的催化剂涂层中还包括一种附加组分，它贮存所捕集的NOx。作为用于NOx吸收催化剂的NOx吸收组分，已知的有：碱金属，如钾、钠、锂、铯等；碱土金属，如钡，钙等；以及稀土元素，如镧、钇等。
NOx吸收催化剂通常是通过将含有上述NOx吸收组分的催化剂层负载在整体性催化剂载体(整体料)上来形成的，所述整体性催化剂载体(整体料)由氧化物型陶瓷(例如堇青石)或金属材料(例如铁-铬-铝合金)构成。在工业上，堇青石(2MgO-2Al2O3-5SiO2)是优选的用于重型机动车辆中NOx载体/支持体的成本低廉的陶瓷材料，这是由于它在大多数运行条件下兼有优良的耐热冲击、过滤效率和耐用性。近来，钛酸铝基陶瓷材料也被人们接受为另一种合适的NOx载体/支持体材料。
在降低柴油机排放物中的另一个重要难题是控制存在于柴油机排放废气流中的柴油颗粒料的含量。在1998年，California Air Resources Board(加里福尼亚空气资源局)宣告柴油颗粒是一种有毒的空气污染物。已通过立法，对于由可移动的污染源和固定的污染源所产生的柴油颗粒的浓度和粒度加以限制。
柴油颗粒料主要是炭黑，从柴油机废气中除去炭黑的一种方法是使其通过柴油捕集器。使用最广泛的柴油捕集器是堇青石陶瓷柴油颗粒过滤器(DPF)，DPF通过在过滤器结构的多孔壁上捕集炭黑而使柴油机废气得到过滤。将DPF设计成几乎完全过滤炭黑而又不会明显妨碍废气流动，在某些情况下，就像NOx堇青石催化剂载体，DPF还包括一种催化剂材料，例如，一种氧化催化剂。同样，钛酸铝基陶瓷材料(AT)正在作为DPF材料而得到应用。
无论堇青石或AT整体料是呈催化剂载体基材的形式还是作为DPF，冷固化陶瓷胶泥(优选堇青石)长期以来已被用来形成堇青石整体料的外表层。将冷固体陶瓷胶泥混合，并施涂到烧制的成形基材，随后使湿表皮层在环境条件下进行干燥、或者在高温下通过对流或微波干燥法进行干燥。于是，带有外表皮层的基材即可接受催化剂涂层以及所需要的任何进一步后序加工了。
随着柴油机过滤方法和催化剂产品取得进展，而且产品的性能要求改变了催化剂涂覆工艺和化学性质，这些变化可能导致催化剂涂覆工艺和具有外表皮层的陶瓷整体料之间的不相容性，无论是NOx载体基材形式的还是DPF形式的都如此。在涂布有外表皮层的整体料与催化剂涂覆工艺之间不相容性的一个例子是：在进行后续催化剂涂布步骤的过程中或在此过程之后，由于表皮层吸收了涂布液，整体料和/或表皮层可能出现过度的表皮层或涂层开裂或剥落。在对陶瓷整体料施涂催化剂涂料介质后所观察到的涉及整体料性能的其它问题包括CTE(热膨胀系数)的显著增加和/或整体料的弹性模量的增加，这两种现象都导致在最终应用时热冲击性能下降(轴向和径向开裂大)。此外，催化剂涂层能降低整体料的强度。催化剂涂层为本技术领域内所公知，可包括含有铈、铂、铑、钯、胶体氧化铝等的化合物。
在本技术领域中，提供一种加入冷固化成表皮胶泥的陶瓷整体料，而它不受大范围的催化剂涂层化学性质和相关工艺的影响，因而减少因基材表皮层材料与催化剂涂覆工艺之间的不相容性而出现的陶瓷整体料产品中不合格品的数量，将被视为一个进步。另一个进步是提供一种陶瓷整体料，其中，催化剂涂层基本上不改变整体料的CTE、模量、强度或热冲击性能。
本发明的内容
本发明提供一种即可用作NOx催化剂载体又可用作DPF的催化剂载体结构。所述催化剂载体结构包括：(i)一个多微孔陶瓷主体(multicellular body)，优选为由堇青石或钛酸铝制成陶瓷蜂窝体、更优选为整体式陶瓷蜂窝体，所述陶瓷蜂窝体具有入口端、出口端、以及多个沿蜂窝体长度方向从所述入口端向所述出口端延伸的相互邻接的微孔(cell)，这些微孔彼此间由多孔壁分开；以及(ii)附着于陶瓷蜂窝体上的疏水涂层，它使陶瓷蜂窝体在接触用于施涂催化剂涂料的工艺过程中的含水催化剂配制剂和/或其它含水介质时减少其吸收。在一优选的实施方式中，疏水涂层被形成在陶瓷蜂窝体的外表皮层部分之内或之上。
本发明的另一方面是一种制造催化剂载体结构的方法，所述方法包括：(1)提供一种多微孔陶瓷主体，优选陶瓷蜂窝体；(ii)对所述陶瓷主体施涂包含有钝化材料的涂料；(iii)对制得的经涂布的多微孔陶瓷主体进行干燥；以及(iv)可任选地，对经干燥的涂布后的多微孔陶瓷主体进行热处理。较佳地，干燥过程在约低于200℃的温度范围内进行，即，至少进行的时间要足以除去所有过剩的溶剂并在多微孔陶瓷诸体上制得疏水涂层。
在两个备选的实施方式中，钝化材料可以下列方式加入：(i)液态钝化材料可直接加入陶瓷(优选堇青石)胶泥中，然后将混合物直接施涂到催化剂载体上，接着对经涂布的催化剂载体进行干燥；和(2)向已施涂的陶瓷表面涂层(优选堇青石胶泥涂层)上施涂包含有钝化材料的液态涂料，然后干燥施涂后的钝化材料。
附图的简要说明
图1是说明水在非疏水堇青石表皮层或涂层上的吸收效果的相片；
图2是说明水在本发明的疏水堇青石表皮层或涂层上的不吸收效果的相片。
本发明的详细说明
本发明的催化剂载体结构包括一个多微孔陶瓷主体，优选陶瓷蜂窝体。所述蜂窝体具有入口端、出口端、以及多个沿蜂窝体长度方向从所述入口端向所述出口端延伸的相互邻接的微孔，这些微孔由多孔壁使其相互间分开。通常，蜂窝体微孔密度的范围从10微孔/英寸2(1.5微孔/厘米2)到1200微孔/英寸2(188微孔/厘米2)。壁厚通常在0.025毫米到1.5毫米(1密耳到60密耳)的范围内，优选0.1～0.75毫米(4～30密耳)。壁的孔径通常在0.1～100微米的范围，优选1～40微米，而壁的孔隙度通常为15～70％，优选25～50％。
合适的陶瓷蜂窝体包括主要由堇青石组成的整体性蜂窝体，这是一种其氧化物组成接近于Mg2Al4Si5O8的晶态陶瓷；然而，其中的Al若被其它组分如Fe(铁)、Co(钴)、Ni(镍)和Mn(锰)取代Mg(镁)，Ga(镓)作有限取代、而Ge(锗)对Si(硅)作有限取代也是可以接受的。而且，在堇青石相中，每54个氧原子可含有最多3个原子的碱金属(IA族)、2个原子的碱土金属(IIA族)、或一个原子的稀土金属(钪、钇、或镧系金属)。
这些取代物预计将在堇青石相的结晶结构中占据通常空着的“通道位点(channel site)”，虽然也可能发生它们对镁的有限取代。将这些元素加入到堇青石结晶结构中可与其它的化学取代联合，例如，改变铝硅比，以保持负荷平衡。
本发明也可使用由堇青石之外的材料制成的多微孔主体。这些材料包括：陶瓷、玻璃、金属、粘土、及其组合。所谓“组合”是指物理或化学组合，例如，混合物、化学物、或复合物。适合于用作陶瓷主体的其它陶瓷材料包括例如碳化硅、钛酸铝和γ氧化铝。
以如下方式将陶瓷蜂窝体结构制成DPF。入口端的一部分微孔和出口端的一部分微孔被堵塞住，而在入口端堵塞的那部分微孔，不同于在出口端堵塞住的那部分微孔。由于这种构型，废气通过入口端的敞开微孔进入陶瓷蜂窝体结构、再流经多孔壁、并通过出口端的敞开微孔从蜂窝体结构中排出。
本发明的多微孔陶瓷主体(无论是整体式的NOx催化剂载体，还是DPF)表征性地包括疏水表面涂层。疏水表面涂层至少存在于陶瓷主体的外表皮层部分(理想的是作为覆盖陶瓷体的整个圆柱形外表面的外涂层)，也可任选地还存在于陶瓷主体的通道结构内。疏水涂层使所制得的涂布了疏水涂层的陶瓷主体在接触用于施涂催剂涂料的工艺过程中的液态催化剂涂料介质和任何含水介质时显示出低吸收或减少吸收。较佳地，疏水涂层使得陶瓷主体阻止因处于催化过程中而引起的开裂或剥落。
前面提到的低吸收或减少吸收的是由经涂布的陶瓷主体的不润湿特性而实现的，而经涂布的陶瓷体的不润湿特性是通过加入疏水涂层实现的。所述不润湿性用接触角来表征，所述接触角定义为：在液滴置于陶瓷表面上时，在液体和陶瓷主体的表面之间的界面处形成的角。更具体地，接触角是液体润湿固体的定量测度，且接触角在几何学上被定义为液体在液体、气体和固体相交的三相边界处形成的角度。
为了本说明的目的，“低吸收”被定义为不润湿表面的状态，其中，液体(例如，在施涂涂料的过程中施涂到陶瓷主体表面的含水催化剂涂料混合物和/或任何含水介质)在陶瓷主体表面上“形成水珠”，其程度达到表示该表面基本上是不可润湿的程度。基本上不可润湿的表面是那种施于该表面的水滴产生出的接触角高于约50度的表面。接触角值低(＜50°)表示液体铺展良好，而接触角为零则代表完全润湿。角度值高表示不完全润湿或不可润湿的表面。根据本发明，上述50°或50°以上的接触角的要求，即使在陶瓷基材或涂层的孔隙率大致为50％且公称/平均孔径为10-20微米的情况下也能得到满足。
标准的外涂层或表皮层通常是由陶瓷材料(优选堇青石)组成的，并且通过引入钝化材料使其呈疏水性。在自然界里有许多疏水性化合物，它们能与通用的表皮层配合料成份混合，从而制得纯化表皮层或疏水表皮层。能赋予陶瓷或堇青石涂层或表皮层疏水性的合适的钝化材料的实例包括如下材料：氨基甲酸乙酯、有机硅、有机硅树脂、硅烷类、油品、蜡、碳、炭黑。
使用堇青石作为代表性的陶瓷表皮层材料，将钝化材料引入可通过以下三种方法之一来实现。第一种方法，可在施涂堇青石涂料或表皮料之前将钝化材料加入并混合在标准堇青石冷固化表皮层配合料组合物内。换句话说，在该方法中，在表皮层材料的标准制备过程中，即把在干燥时将产生疏水表皮层的钝化材料直接加入到了表皮层配合料组合物中。
第二种方法，钝化材料可在后涂布步骤中直接施涂于事先已施涂到多微孔陶瓷结构上的堇青石表皮层部分上，尤其是在这种情况下，钝化材料的液体涂料可通过浸涂、喷啉涂、喷涂、辊涂、渗吸涂、注射涂等任何一种方式被施涂到柴油机过滤器的外表皮层或NOx催化剂载体结构的外表皮层，所制得的涂层或是厚膜，或是光滑面；或者它可以是一种薄的单层。
第三种方法，可以通过在涂层材料溶液中浸渍整个多微孔陶瓷主体来将钝化材料施涂于整个多微孔陶瓷主体。
在本发明前述的实施方式中，其中的钝化材料是在后涂布步骤中被加到陶瓷涂料中，从而制得具有疏水涂层的经涂布催化剂载体结构，其实际步骤如下：
(a)提供一种经烧制的具有陶瓷外表皮涂层的多微孔陶瓷主体；
(b)将包含有钝化材料的涂料施涂到外表皮涂层上，或施涂到整个陶瓷主体基材；
(c)对制得的经涂布的陶瓷主体进行干燥；以及
(d)任选地，对经干燥的涂布后的多微孔陶瓷主体在一定温度下进行热处理，热处理的时间要足以在多微孔陶瓷主体的表面上产生一疏水涂层。
在另一方法中，如以上所简述，钝化材料被直接加到陶瓷表皮层配合料组合物中。以这种方式来制备具有疏水性外涂层的经涂布的整体性陶瓷基材的实际步骤如下：
(a)提供一种经烧制的多微孔陶瓷主体；
(b)向整体性陶瓷基材的外表面施涂由其中混有钝化材料的陶瓷胶泥组成的涂料；
(c)对所制得的经涂布后的多微孔陶瓷主体进行干燥；以及，
(d)任选地，对经干燥的涂布后的多微孔陶瓷主体在一定温度下进行热处理，热处理的时间要足以在多微孔陶瓷主体上产生一疏水涂层。
在上述任何一种方法中，为了形成疏水涂层，必要的干燥时间或温度很容易由熟练的技术人员予以确定。较佳地，为了至少能从陶瓷主体上除去过剩的溶剂，这两种方法中的干燥步骤是在60～450℃之间的温度范围内进行足够时间的。可以利用一次额外的可任选的热处理，涉及的热处理时间和温度能使钝化材料充分交联；像干燥步骤一样，热处理优选在60～450℃的温度范围内进行。
用于涂布整体性陶瓷基材的优选陶瓷材料包括其中混有钝化材料的堇青石冷固化表皮层组合物；即，一种堇青石/钝化材料疏水涂料。具体说，所述组合物包含：50～65wt％的粉状堇青石、0.1～1wt％的甲基纤维素粘结剂、1～6wt％的胶态二氧化硅、0～20wt％的硅铝酸盐纤维、10～20wt％的水、约0.1～1wt％的流变调节剂和1～6wt％的钝化材料，所述钝化材料选自：有机硅树脂、氨基甲酸乙酯、油品、硅烷、蜡、碳、炭黑、及其混合物。在优选的实施方式中，所述堇青石表皮层/钝化材料的疏水涂料组合物包含：50～60wt％的粉状堇青石、0.1～1wt％的甲基纤维素粘结剂、3～5wt％的胶态二氧化硅、13～20wt％的硅铝酸盐纤维、18～20wt％的水、0.4～0.6wt％的流变调节剂和4～6wt％的钝化材料。
在多微孔陶瓷主体(或者呈NOx催化剂载体形式，或者呈DPF形式)的外表面上引入疏水性陶瓷表皮层或涂层，其中经钝化的冷固化表皮化胶泥不受催化涂层过程所用的催化剂涂料和含水溶液的影响，就产生了众多比具有非疏水性堇青石表皮层的标准堇青石陶瓷蜂窝体强的优点。最重要的，基于钝化表皮层或疏水表皮层不允许表皮层材料和含水催化剂涂布液之间的紧密接触的实际情况，出现表皮层开裂和剥落的现象减少。换句话说，任何可用于催化过程的含水涂布液将被排斥并阻止其吸收进入陶瓷主体的表皮层内，因而防止了可能因所施涂的表皮层和催化剂涂布液或工艺过程之间的化学反应或机械相互作用而产生的任何付作用的发生。
另一个优点是节省了被施涂于陶瓷主体的催化剂涂料介质，因为本发明的经钝化表皮涂层或疏水表皮涂层不会不适当地吸收催化剂溶液。于是包含在催化剂涂料介质中的价格昂贵的贵金属不会沉积在表皮层上对减少排放物不起作用的地方。
实施例
为了进一步说明本发明的原理，将对根据本发明的疏水涂层材料的实施例进行叙述。然而，应理解，所给出的实施例仅为了说明目的，并且本发明不局限于这些实施例，而是对本发明可进行各种修改和改变，而不背离本发明的精神。
实施例1
在如上所述的一个实施方式中，钝化材料直接加入标准冷固化堇青石胶泥中，所述胶泥本身随后能被施涂于基材。表1所列为标准表皮层组合物(wt％)和混有甲基苯基有机硅树脂钝化材料的同一标准表皮层组合物(wt％)，所述钝化材料赋于堇青石表皮层或涂层疏水性。
表I
  标准表皮层组合 经钝化的表皮层组合物
  粉状堇青石62.5％(d50＝40μm/d50＝12μm的50/50混合物的) 粉状堇青石55.5％(d50＝40μm/d50＝12μm的50/50混合物的)
  甲基纤维素粘结剂0.5％(Dow Corning公司的Methocel A4M) 甲基纤维素粘结剂0.5％(Dow Corning公司的Methocel A4M
  胶态二氧化硅4.0％(Ludox)  胶态二氧化硅3.5％(Ludox)
  硅铝酸盐纤维17％(Unifrax  QF-180)  硅铝酸盐纤维15％(Unifrax QF-180)
  去离子水16％  去离子水19.5％
 流变调节剂(Alcogum SL-70)
 有机硅树脂溶液5.5％(溶解在己二酸二乙酯的二元酸酯中的Dow Corning公司DC233有机硅树脂，其粒子分布比率为2∶1)
用如下方法制取由以上每个组合物(标准表皮层组合物和含有钝化材料的标准表皮层组合物)组成的试片。首先将干粉配制料掺混以形成干粉混合物，然后，将液体组分加到干粉混合物中。在这二种情况下，使用标准Kitchen Aid混合器将所述混合物充分混合，从而形成浆料。浆料浇铸在聚四氟乙烯(Teflon)模具中，然后将试片干燥，以分别形成标准表皮层组合物试片和其中混入钝化材料的标准表皮层组合物的试片；从而制得了具体尺寸为20毫米×80毫米、厚度2毫米的试片。
为了进行比较，将水滴施于每个标准表皮层陶瓷片材和其中混入钝化材料的标准表皮层陶瓷试片。图1和图2所示相片，分别说明水在标准表皮层陶瓷试片和混入钝化材料的标准表皮层陶瓷试片上所产生的作用。观察图1的标准表皮层组合物试片，显示出水2并未被排斥，实际上被吸入基质表面1内。这与图2所示的包括本发明疏水表面的含钝化材料陶瓷试片正好相反。观察图2的相片，显示出水2a在试片1的表面上保持水珠状，即，对水的吸附低，并且观察到接触角超过50°。
实施例2
制取四个由表1所示的标准堇青石表皮层组合物组成的堇青石陶瓷试样，并形成具体尺寸为100毫米×200毫米，厚度2毫米的试样。为了比较起见，第一个试样不用钝化材料涂布，而其余三个试样是用本发明疏水涂料涂布的。用于表II所示的本发明试样A、B和C的钝化材料分别包括：有机硅树脂(溶解在己二酸二乙酯的二元酸酯中的Dow Corning DC 233有机硅树脂，其重量比为2∶1)、桐油、以及由Michem 4983R乙烯丙烯酸共聚物组成的共聚物。对于本发明的每个试样，通过将基材浸渍充分时间-大致1分钟-使试样饱和而将钝化材料施涂到标准表皮层组合物试样(wt％同上)。
四个基材试样(一个标准的和三个经涂布的)中的每一个被浸在硝酸铈(CeNO3)3催化剂溶液中历时4小时(720克/升的硝酸铈)，然后使其在60℃干燥过夜，接着使其在500℃焙烧，焙烧时间要足以使硝酸铈转化成氧化铈。测量试样在接触催化剂溶剂前后的重量，典型结果列于表II。表II中“接触后重量”表示被吸收的硝酸铈的量，是与所制得材料的强度一起测量的。此外，用标准4点弯曲试验法按PSI(磅/平方英寸)度量来测量四个试样的在接触硝酸铈溶液前后的弯曲断裂模数(bending MOR)，并将其结果列于表II。
表II
  接触后重量增加的％  接触前的MOR  接触后的MOR
  对比试样：标准表皮层   10.9  526.5  65.1
  本发明试样A   4.5  432.1  427.5
  本发明试样B   3.5  392.3  296.3
  本发明试样C   5.4  602.1  477.5
观察表II的结果，显示出：含有本发明疏水性堇青石涂层的试样相对地不受催化剂溶液的影响，因而不容易吸收含水溶液。即，本发明的经钝化的疏水涂层试样A、B和C与包含标准堇青石涂层的试样相比，前者在接触后增加的重量百分数要低得多，而MOR强度要高得多。未经处理的非疏水试样只保留了其大约12％的强度，而对于本发明的试氧，却分别保留了99％、75％和79％的强度。表皮层或涂层弱化的对照试样很易开裂，尤其在发生温度变化以及在表皮层和基材之间的热膨胀系数失配时。
实施例3
制取62个陶瓷蜂窝体试样，(31个堇青石；31个钛酸铝)；每个试样是从相应组合物的陶瓷蜂窝体上切割下来的8毫米×8毫米×50毫米的棒条。表III所示的31种不同的钝化涂层材料各被施涂到一个堇青石蜂窝棒条和一个钛酸铝蜂窝体棒条上。为施涂这些涂层材料，将这些基材的每一个在室温下浸渍在涂层材料的稀溶液中，历时2分钟。所使用的涂层材料/钝化涂层浓度如表III所示；“10％，溶剂IPA”表示10％的异丙醇稀溶液，“10％，溶剂H2O”表示10％的去离子水稀溶液，而“100％”表示全材料溶液(full strength materialsolution)。然后，过剩的涂料用压缩氮气从试样中吹去。接着，经涂布的试样在60℃的循环烘箱中干燥至少2小时。
用于测量施涂在基材上的涂层的疏水性的试验是接触角的测量。在VC2500XE测角计(AST Products Inc.，Billerica，MA，使用2μL去离子水滴)上测量起始接触角。每个堇青石和钛酸铝基材的相应接触角示于表III中。
表III
  试样编号   涂层材料   浓度   平均初始接触角度数(堇青石)   平均初始接触角度数(钛酸铝)
  1   环氧化豆油(Drapex 392)   10％，溶剂IPA   70   77
  2   环氧化亚麻子油(Vikoflex 7190)   10％，溶剂IPA   73   68
  3   妥尔油脂肪酸的甲基酯(Sylfat MM)   10％，溶剂IPA   87   85
  4   烷基三烷氧基硅烷(TLF-8291)   10％，溶剂水   83   109
  5   烷基三烷氧基硅烷(TLF-8291)   1.0，溶剂水   77   73
  6   硅烷/硅氧烷浓缩物(Dow Corning Z-6689)   10％，溶剂IPA   115   114
  7   棕榈核油   10％，溶剂IPA   113   115
  8   椰子油   10％，溶剂IPA   111   109
  9   二(2-乙基己基)癸二酸酯(Plasthall DOS)   10％，溶剂IPA   52   64
  10   羧酸，多元醇酯(Priolube 3986)   10％，溶剂IPA   99   107
  11   蓖麻油   10％，溶剂IPA   75   69
  12   不饱和脂肪酸二聚物酯类(Uniflex 102)   10％，溶剂IPA   91   80
  13   肪脂酸的乙二醇酯(Uniflex 206)   10％，溶剂IPA   84   85
  14   亚麻子油   10％，溶剂IPA   112   74
  15   豆油   10％，溶剂IPA   87   100
  16   1，1，1，3，3，3-六甲基二硅氮烷(HMDZ)   100％   120   139
  17   环氧化豆油(Drapex 392)   100％   84   71
  18   环氧化亚麻子油(Vikoflex 7190)   100％   61   70
  19   硅烷/硅氧烷乳液(Dow Corning 520)   40％固体   110   121
  20   硅烷/硅氧烷浓缩物(Dow Corning Z-6689)   100％   127   125
  21   C7-C10脂肪酸的季戊四醇酯(Hatcol 5068)   100％   106   102
  22   二(2-乙基己基)癸二酸酯(Plasthall DOS)   100％   69   62
  23   环氧化2-乙基己基妥尔酯(Plasthall S73)   100％   62   52
  24   失水山梨醇三油酸酯(Span 85)   100％   93   104
  25   蓖麻油   100％   71   68
  26   不饱和脂肪酸二聚物脂类(Uniflex 102)   100％   64   68
  27   脂肪酸的乙二醇酯(Uniflex 206)   100％   76   76
  28   豆油   100％   107   119
  29   亚麻子油   100％   93   100
  30   油酸   100％   107   71
  31   无钝化涂料   立即吸收   立即吸收
观察表III，显示出：所有含有钝化材料的经涂布试样(包括堇青石的和钛酸铝的)，其接触角大于50°，并对含水介质中的水吸附小。为比较起见，请留意实施例31，其不包含钝化涂层，并立即吸收施于其表面的2微升去离子水滴。
尽管以上结合本发明的部分优选的具体实施方式对本发明进行了说明，但只要在所附权利要求书的范围可以实施，这些实施方式即只是为了说明，而不是为了限制本发明。

Claims (6)

1.一种制取具有疏水性外涂层的经涂布的催化剂载体结构的方法，所述方法包括：
a.提供一种烧制的多微孔陶瓷主体；
b.将一种堇青石组合物施涂于所述多微孔陶瓷主体的外表面，所述的堇青石组合物包含：
50～65wt％的粉状堇青石、0.1～1wt％的甲基纤维素粘结剂、1～6wt％的胶态二氧化硅、0～20wt％的硅铝酸盐纤维、10～20wt％的水、0.1～1wt％的流变调节剂、以及1～6wt％的钝化材料，所述钝化材料选自有机硅树脂、油、硅烷、蜡、碳、及其混合物；
c.干燥所制得的经涂布的多微孔陶瓷主体；以及
d)对经干燥的涂布后的多微孔陶瓷主体在60～450℃的温度下进行热处理3个小时；热处理的时间至少足以在所述多微孔陶瓷主体上产生一疏水涂层。
2.如权利要求1所述的方法，其特征在于，所述碳是炭黑。
3.一种涂布催化剂载体结构的堇青石组合物，它包含：
50～65wt％的粉状堇青石、0.1～1wt％的甲基纤维素粘结剂、1～6wt％的胶态二氧化硅、0～20wt％的硅铝酸盐纤维、10～20wt％的水、0.1～1wt％的流变调节剂、以及1～6wt％的钝化材料，所述钝化材料选自有机硅树脂、油、硅烷、蜡、碳、及其混合物。
4.如权利要求3所述的堇青石组合物，其特征在于，它包含：50～60wt％的粉状堇青石、0.1～1wt％的甲基纤维素粘结剂、3～5wt％的胶态二氧化硅、13～20wt％的硅铝酸盐纤维、18～20wt％的水、0.4～0.6wt％的流变调节剂、以及4～6wt％的钝化材料。
5.如权利要求4所述的堇青石组合物，其特征在于，它包含：55.5wt％的粉状堇青石、0.5wt％的甲基纤维素粘结剂、3.5wt％的胶态二氧化硅、15wt％的硅铝酸盐纤维、19.5wt％的水、0.5wt％的流变调节剂、以及5.5wt％的钝化材料。
6.如权利要求3所述的堇青石组合物，其特征在于，所述碳是炭黑。
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