CN103482968A - 用于4-路废气处理的高孔隙率过滤体 - Google Patents

用于4-路废气处理的高孔隙率过滤体 Download PDF

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CN103482968A
CN103482968A CN201310415179.2A CN201310415179A CN103482968A CN 103482968 A CN103482968 A CN 103482968A CN 201310415179 A CN201310415179 A CN 201310415179A CN 103482968 A CN103482968 A CN 103482968A
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cte
porosity
pore sizes
mean pore
mor
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I·M·梅尔斯科特-查威尔
G·A·默克尔
S·B·奥古米
T·陶
J·王
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Corning Inc
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Corning Inc
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Abstract

具有至少为64％但是小于80％的高体积百分比孔隙率的堇青石陶瓷制品，该制品具有可控的中值孔径和平均热膨胀系数，从而基本上使得该陶瓷制品具有改善的断裂模数强度（MOR）和抗热冲击性能（TSR）。

Description

用于4-路废气处理的高孔隙率过滤体
本申请是国际申请号为PCT/US2007/015055，国际申请日为2007年6月28日，进入中国国家阶段的申请号为200780024055.4，名称为“用于4-路废气处理的高孔隙率过滤体”的发明专利申请的分案申请。
本申请要求于2006年6月30日提交的、发明名称为“用于4-路废气处理的高孔隙率过滤体”的美国临时申请No.60/817,722的权益。
技术领域
本发明属于工业陶瓷领域并且尤其涉及低热膨胀和高孔隙率耐火堇青石陶瓷，该陶瓷所具有的高强度使其尤其适于生产用于燃烧废气处理的坚固壁流式过滤体。
背景技术
堇青石陶瓷体，尤其是那些作为蜂窝状多孔结构形成的堇青石陶瓷体在许多高温应用中得以利用，例如催化转化器、NOx吸附器、电热催化剂、熔融金属过滤体、蓄热芯、化学加工基质、用于加氢脱硫、氢化裂解或氢化处理的催化剂以及例如柴油机废气微粒过滤器的过滤体。
在柴油机废气过滤中，堇青石作为同时具有低热膨胀系数（CTE）和低成本的材料已经成为一种选择。从20世纪80年代早期开始，壁流式多孔堇青石陶瓷过滤体已经用于从一些柴油机的废气中除去微粒。柴油机微粒过滤体（DPF）理想地应同时具有低CTE（用于抗热冲击阻力）、低压降（用于发动机效率）、高过滤效率（用于从废气中除去最多的微粒）、高强度（在使用中承受处理、封存和振动）以及低成本。
在需要从柴油机废气中除去氮氧化物、NOx的应用中，典型地需要大量的催化剂或NOx吸附剂。为了使压降的增加达到最小，需要高孔隙率和大孔径尺寸以容纳附加的NOx催化剂/吸附剂。然而，孔隙率和较大孔径尺寸的增加都会减少陶瓷蜂窝的强度。
此外，人们经常希望得到非常低的CTE作为增加抗热冲击阻力（TSR）的方式，而且在堇青石和其它现代陶瓷中，低CTEs通常是通过陶瓷材料中存在微裂纹而实现的。然而，遗憾的是微裂纹也会进一步降低这些高孔隙率体的强度。
人们已经制得了同时具有高孔隙率和大孔径尺寸的堇青石陶瓷，例如孔隙率为64-80%、且中值孔径为10-45μm，这些陶瓷具有非常低或非常高的CTE。高CTE陶瓷势必显示出较差的抗热冲击性能，而与非常低的CTE陶瓷相关的广泛的微裂纹会导致较低强度和较差的机械寿命。在典型的柴油机排气***的机械恶劣环境下通过测定实际应用中的断裂模数（MOR）表明后者的机械强度不足。
因此，提供具有高孔隙率和大中值孔径的堇青石陶瓷体从而具有低催化压降并且同时具有中等的CTE以确保综合改善抗热冲击阻力和和强度在本领域中是一种进步。
发明内容
本发明提供了新型的同时具有高体积百分数孔隙率与可控中值孔径和平均热膨胀系数的堇青石陶瓷蜂窝制品。令人意想不到地发现控制中值孔径和平均热膨胀系数二者基本上可改善这些高孔隙率陶瓷的断裂强度模数（MOR）和抗热冲击性（TSR）。在特定的实施方案中，本发明的堇青石陶瓷制品的体积孔隙率为至少64％并且小于80％，但是强度和平均热膨胀系数通常高于依照现有技术生产的高孔隙率陶瓷。
发明的陶瓷制品特别适合用作催化壁流式柴油机微粒过滤体，因为对于CTE和孔径分布的控制限制提供了高断裂强度模数（MOR）和良好的抗热冲击性，并且陶瓷孔隙的显微结构确保即使当涂覆有效量的催化剂和/或NOx吸附剂时也具有低净压降和低烟尘负载压降。在发明的堇青石陶瓷中保持较高的断裂强度模数被认为是由于微裂纹水平的减少，与具有相似孔隙率的现有技术产品相比，这种陶瓷在某种程度上明显表现为具有较高的容许的CTE。因而，在一些实施方案中，本发明包括堇青石陶瓷制品，其孔隙率≥64％并且<80％，中值孔径和25-800℃的平均热膨胀系数（CTE）落入下述范围之一：(i)中值孔径（d50）≥10μm并且<18μm时CTE<6.0×10-7/℃；(ii)中值孔径（d50）≥18μm并且<22μm时CTE<9.0×10-7/℃；（iii）中值孔径（d50）≥22μm并且≤25μm时CTE<10.0×10-7/℃；(iv)中值孔径（d50）>25μm并且<29μm时CTE<13.0×10-7/℃；或(v)中值孔径（d50）≥29μm并且≤45μm时CTE<17.0×10-7/℃并且≥3.0×10-7/℃。本说明书中使用的堇青石陶瓷材料的中值孔径（d50）常规上解释为材料50％的孔隙体积具有更细的孔隙直径时的孔隙直径，所有的孔隙直径和孔隙体积百分数由标准水银孔率法测定。
在另一个更直接反映容许的CTE水平和中值孔径（d50）之间重要关系的方面，本发明包括高孔隙率堇青石陶瓷制品，其中值孔径（d50）至少为10μm并且不超过45μm，且在温度范围（25-800℃）上测定的轴向平均CTE满足以下关系：0.5(d50-24.0)<CTE(25-800℃)<0.5(d50-5.0)，d50以微米表示并且CTE（25-800℃）以单位10-7/℃表示。此外，这些陶瓷是体积孔隙率至少64％并且小于80％的高孔隙率堇青石陶瓷。
依照本发明特定的进一步的实施方案，窄孔径分布使催化剂在孔壁表面上更均匀分布。催化剂涂层在孔壁上更均匀的厚度提供低净压降和3烟尘负载压降，并且在催化剂和烟尘以及催化剂和废气之间提供更高的接触，从而促进催化剂更有效地利用。窄孔径分布进一步为催化过滤体提供较低的压降、较高的过滤效率和较高的强度。
附图说明
参考以下附图对发明做进一步的描述，其中：
图1和2是本发明选定的堇青石陶瓷的中值孔径与25-800℃的平均CTE（10-7/℃）的关系图。
图3和4是本发明选定的堇青石陶瓷的中值孔径与孔隙率的关系图。
图5是具有窄孔径分布的本发明选定的堇青石陶瓷的中值孔径（d50）与25-800℃的平均CTE（10-7/℃）的关系图。
图6是具有窄孔径分布和小体积含量的极小孔径的本发明选定的堇青石陶瓷的中值孔径（d50）与25-800℃的平均CTE（10-7/℃）的关系图。
具体实施方式
如上所述，用作例如用于处理燃机废气的先进蜂窝状载体和过滤体的堇青石陶瓷制品必定包括孔隙率非常高的陶瓷，但是该陶瓷还必须显示出足够高的机械强度和足够低的热膨胀系数，以确保高抗热冲击性。满足高孔隙率条件的陶瓷制品包括那些体积孔隙率至少为64％但是小于80％的陶瓷制品。这样的高孔隙率陶瓷典型地相对脆弱，尤其是对于微裂纹很多的低CTE堇青石陶瓷。
本发明通过仔细控制堇青石材料的热膨胀和孔径分布提供了具有为获得高TSR所需的孔隙率和强度的堇青石陶瓷制品。因此，发现如果在CTE较低的材料中陶瓷的平均孔径降低，则具有低至中等CTE的高孔隙率堇青石陶瓷实际上可提供相当好的断裂强度模数。
提供所需高强度和高抗热冲击性的陶瓷设计区域的面积[平均CTE×中值孔径]图示于图1，由在较宽图示区域内的五个邻接块状容许[CTE-孔径]设计区域表示。本发明的多个堇青石陶瓷制品的平均CTE和中值孔径（d50）画于图中，这些制品在图上的分布表明了对于平均孔径较低的堇青石陶瓷允许CTE降低的一般趋势。
如上所述并如图1所示区域中所反映的，落入容许的陶瓷性能范围之内的本发明的高孔隙率堇青石陶瓷具有落入下述范围之一的中值孔径（d50）（由标准水银孔率法测定）和在轴向上平均于25-800℃温度范围之内的平均热膨胀系数（CTE）：(i)中值孔径（d50）≥10μm并且<18μm时CTE<6.0×10-7/℃；或(ii)中值孔径（d50）≥18μm并且<22μm时CTE<9.0×10-7/℃；或（iii）中值孔径（d50）≥22μm并且≤25μm时CTE<10.0×10-7/℃；或(iv)中值孔径（d50）>25μm并且<29μm时CTE<13.0×10-7/℃；或(v)中值孔径（d50）≥29μm并且≤45μm时CTE<17.0×10-7/℃并且≥3.0×10-7/℃。本发明优选的堇青石陶瓷具有落入下述范围之一的中值孔径和25-800℃的平均热膨胀系数：(i)中值孔径（d50）≥10μm并且<18μm时CTE>2.0×10-7/℃并且<5.0×10-7/℃；或(ii)中值孔径（d50）≥18μm并且<22μm时CTE>3.0×10-7/℃并且<8.0×10-7/℃；或（iii）中值孔径（d50）≥22μm并且≤25μm时CTE>4.0×10-7/℃并且<9.0×10-7/℃；或(iv)中值孔径（d50）>25μm并且<29μm时CTE>5.0×10-7/℃并且<11.0×10-7/℃；或(v)中值孔径（d50）≥29μm并且≤39μm时CTE>6.0×10-7/℃、<14.0×10-7/℃并且≥3.0×10-7/℃。
图2画出了覆盖了图1所示的示例性组成的陶瓷设计区域，其更接近地表示了在平均CTE较低的陶瓷中中值孔径（d50）减小的趋势。由图2中的多边形（A-B-C-D-E）画出的区域包括那些在陶瓷制品的至少一个方向上平均于25-800℃温度范围内的平均热膨胀系数（CTE）满足0.5(d50-24.0)<CTE(25-800℃)<0.5(d50-5.0)关系的本发明的实施方案，此时d50以微米表示并且平均CTE（25-800℃）以单位10-7/℃表示，其中孔隙率为至少64％且小于80％并且中值孔径（d50）为至少10μm且不超过45μm。根据优选实施方案，平均热膨胀系数（CTE）满足0.5(d50-24.0)<CTE(25-800℃)<0.5(d50-5.0)关系，此时d50以微米表示并且平均CTE（25-800℃）以单位10-7/℃表示，其中孔隙率为至少64％且小于80％，中值孔径（d50）为至少13μm且不超过40μm，平均CTE为至少3×10-7/℃且不超过13×10-7/℃。
本发明通过参考以下特定实施例进一步加以描述，其意欲进行说明而不作为限制。适合这些实施例的制备过程的原材料列于下表1中；适当选择适于该应用的这些和类似的材料以确保高矿物和化学纯度。表1中对所选择的原材料进行测定的是这些材料的中值粒径，利用标准激光衍射和/或沉降法进行测定。
表1-示例性原材料
Figure BDA0000381216950000051
包括上述组分材料和一些其它物质组合的用于制备本发明的堇青石陶瓷的所示原材料的组合列于下述表2-8中。
表2-批料混合物
Figure BDA0000381216950000062
Figure BDA0000381216950000071
表4-批料混合物
Figure BDA0000381216950000072
Figure BDA0000381216950000081
表5-批料混合物
Figure BDA0000381216950000082
表6-批料混合物
Figure BDA0000381216950000083
Figure BDA0000381216950000091
表7-批料混合物
Figure BDA0000381216950000092
表8-批料混合物
Figure BDA0000381216950000093
Figure BDA0000381216950000101
在由例如上述表2-8所记载的批料混合物制备堇青石陶瓷蜂窝体的典型工艺中，无机原料和石墨、淀粉面粉或聚合物气孔形成剂与4％-6％的甲基纤维素粘合剂和0.5-1％的硬脂酸钠润滑剂混合，并在不锈钢研磨机中向形成的混合物中加入水形成可塑性批料。然后将所形成的可塑性批料挤出成型成直径为2英寸或5.66英寸圆柱形蜂窝预制体，在气泡壁厚度为0.012-0.020英寸的蜂窝横截面上含有约200-300气泡/平方英寸，还将可塑性批料挤出形成横截面直径约0.3英寸的棒条体。然后干燥这些挤出的蜂窝体和棒条体，随后在气窑或电窑中烧结将挤出蜂窝体中的原料转变成蜂窝陶瓷，其中堇青石构成了主晶相（占蜂窝体结晶相的87重量％以上）。在一些这样的烧结蜂窝体中利用X射线衍射可检测到残余的莫来石、尖晶石+假蓝宝石和α-氧化铝次晶相（小于总结晶相的13重量％）。
表9-18记载了由具有如上表2-8所述批料组成的挤出蜂窝体得到的烧结堇青石和蜂窝产品典型的烧结和产品性能。这些表中记载了每种产品的烧结参数，用于以可控制陶瓷的CTE和中值孔径的方式开始并完成将原料批料蜂窝组分转变为堇青石的反应烧结。对于许多产品还记载了烧结材料典型的选定的物理性能，其由烧结蜂窝体或棒条体测定。
更进一步地参见表9-18中的数据，其中的CTE值与平均于25-800℃上的以10-7/℃为单位的平均热膨胀系数相对应，该值是通过膨胀测量法在平行于蜂窝体孔道的长度方向（“轴向”）上的样品测得的。孔隙率百分比是通过水银孔率法测得的在制品壁上的孔隙容积百分比。术语d10、d50、和d90表示孔隙直径，以微米表示（微米-即10-6米），其分别表示10％、50％和90％的总孔隙量具有细小孔径，这些数据也是通过水银孔率法测得的。因此例如，d90为90％（体积）的孔隙具有较小直径时的孔径（等于累积水银侵入体积等于总水银侵入体积10％时的孔径）。
记载的烧结蜂窝体的弯曲强度或断裂模数（MOR）值通过在直径0.3英寸的棒条体上或长度平行于蜂窝体轴向的1英寸×1/2英寸×5英寸（长）的蜂窝状棒上进行4点弯曲测得。室温下的弹性模数值通过声波共振技术在类似的长度平行于蜂窝体轴向的1英寸×1/2英寸×5英寸的蜂窝状棒上测得。孔的几何特征以“N/w”记载，其中“N”为孔密度，表示每平方英寸蜂窝横截面上孔的数量，“w”为以10-3为单位的孔道壁厚。
表9-18还记载了一些实施例中轴向XRD I比率（I比率在蜂窝体轴向截面上测得）和横向XRD I比率（I比率在作为烧结壁表面的横向上测得）。I比率由如下关系定义：
I比率=I(110)/[I(110)+I(002)]
其中I(110)和I(002)是在堇青石晶格中从(110)和(002)面上XRD反射的峰值高度，基于XRD峰值的六方晶格指数。I比率通过X射线衍射使用铜Kα辐射在轴向截面（垂直于孔道长度方向）或横断面（作为蜂窝壁烧结表面）上的辐射而测得。I比率给出了负热膨胀c轴平行于蜂窝壁平面的的蜂窝制品中堇青石晶粒定向程度的定量标准。高度定向是合乎需要的，因为其降低了蜂窝制品在轴向（在壁平面内，平行于孔道长度方向）和径向（在壁平面内，垂直于孔道长度方向）上的CTE。对于随机定向的堇青石晶体，轴向和横向上的I比率都约等于0.65。大于0.65的横向I比率值和低于0.65的轴向I比率值表示堇青石晶体优选定向于其c轴平行于壁平面。如果所有堇青石晶体的c轴位于壁平面内，则横向I比率值将为1.0。
表9-18还记载了通过在一些烧结蜂窝体上进行X射线衍射测得的残余尖晶石、莫来石和α-氧化铝的重量百分数。
表9-蜂窝产品
Figure BDA0000381216950000111
Figure BDA0000381216950000121
表10-蜂窝产品
Figure BDA0000381216950000122
Figure BDA0000381216950000131
表11-蜂窝产品
Figure BDA0000381216950000132
Figure BDA0000381216950000141
表12-蜂窝产品
Figure BDA0000381216950000151
表13-蜂窝产品
Figure BDA0000381216950000152
Figure BDA0000381216950000161
表14蜂窝产品
Figure BDA0000381216950000162
Figure BDA0000381216950000171
表15-蜂窝产品
Figure BDA0000381216950000172
Figure BDA0000381216950000181
表16-蜂窝产品
Figure BDA0000381216950000182
Figure BDA0000381216950000191
表17-蜂窝产品
Figure BDA0000381216950000192
Figure BDA0000381216950000201
表18-蜂窝产品
Figure BDA0000381216950000202
Figure BDA0000381216950000211
选择如上例示的本发明烧结体的孔隙率、中值孔径和平均CTE，从而当烧结体用作蜂窝壁流式过滤体时在保持低压降和高抗热冲击阻力的同时提供高强度。此时为获得最佳性能，蜂窝体应当由陶瓷形成，通过在（非多孔的）杆状或（非多孔的）条状陶瓷材料上的四点弯曲法测定的陶瓷的断裂模数（弯曲强度）至少为500psi，更优选至少为700psi，更加优选至少为900psi，最优选至少为1000psi。当在多孔体上测定时，MOR值与沿蜂窝状结构轴向方向上横切的多孔体横截面的闭合正面面积（CFA）成正比。CFA定义为样品横截面区域的实心部分，即孔壁和壁交叉处的结合区域。因此，CFA等于{w[2(N-0.5)-w]N}，其中是以英寸计的壁厚，N为单位为英寸－2的孔密度。希望的是用于壁流式过滤体制造的多孔结构的MOR/CFA值应至少为500psi，更优选至少为700psi，更加优选至少为900psi，最优选至少为1000psi。
选择作为壁流式过滤体的堇青石陶瓷还有利地显示出高应变抗性，定义为陶瓷的MOR与弹性模量E的比值，再次指出其中陶瓷的MOR为其在室温下的断裂模数，E为其在室温下的弹性模量。MOR和E值二者都应当在固体棒条体上测得，或者在多孔蜂窝试样上沿着与穿过烧结体的孔道方向平行的轴测定。在后一种情况下蜂窝体还应具有相同的孔几何特征（相同的w和N）。对于壁流式过滤体应用，优选材料烧结应变抗性至少为0.09%。优选0.10%，更优选至少为0.12%，更加优选至少为0.14%，尤其至少为0.16%。高应变抗性由于可以在给定的CTE下产生较高的抗热冲击性能，因而是有利的。
基于如上表1-18列出的组成研究，已经确认了一定范围的堇青石陶瓷的性能，其尤其适于用以生产高孔隙率壁流式过滤体基体。该范围内堇青石陶瓷的孔隙率百分比范围为64％≤％孔隙率≤77％，并且中值孔径（d50）同时满足以下条件：(i)18μm<d50≤50μm；(ii)d50>158-2.0(％孔隙率)；(iii)d50<210-2.5(％孔隙率)。在该范围内的高孔隙率堇青石陶瓷的中值孔径优选低于30μm。
这些陶瓷所处的孔隙率/中值孔径的区域如图3所示，其中同时满足前述对于孔隙率和孔径限制的组成处于图中画出的A-B-C-D四边形区域之内。此外，在公开范围内的高孔隙率材料中提供较低的中值孔径可使这些陶瓷获得比其它的陶瓷更高的MOR强度。
在发明的另一个方面，确定了包括许多图3中画出的陶瓷加上另外的处于图3中A-B-C-D四边形覆盖的设计范围之外的高MOR/高TSR材料的堇青石陶瓷设计区域。落入这些设计范围内的堇青石陶瓷满足下述系列条件之一：(i)中值孔径范围为>25μm并且<46μm，孔隙率范围为>64％并且≤67％，或(ii)中值孔径范围为>21μm并且<42μm，孔隙率范围为>67％并且≤68％，或(iii)中值孔径范围为≥19μm并且<40μm，孔隙率范围为>68％并且<71％，或(iv)中值孔径范围为>18μm并且<35μm，孔隙率范围为≥71％并且<73％，或(v)中值孔径范围为>10μm并且<30μm，孔隙率范围为≥73％并且<75％。在该孔隙率设计区域内的陶瓷优选具有<30μm的中值孔径。
图4画出了多个同时满足根据本发明的上述条件之一的堇青石陶瓷实施例的以微米计的中值孔径（d50）与以体积百分数计的孔隙率的关系。因此所画实施例落入五个矩形之一内，这些矩形重叠在覆盖了对应于上述五组孔隙率和孔径限制的五个孔径设计区域的上述附图区域之上。
由上述以及图1-4所公开的组成中选择堇青石陶瓷材料作为壁流式过滤体，为达到最佳的强度和抗热冲击阻力，特别优选的孔隙率和中值孔径（d50）应落入下述范围：65％≤孔隙率≤75％并且15≤d50≤28μm，尤其是18≤d50≤25μm。25-800℃的平均热膨胀系数，CTE（25-800）最好≤15×10-7/℃，优选≤10×10-7/℃，更优选≤8×10-7/℃，最优选≤6×10-7/℃。
由这些陶瓷制得的壁流式过滤体的烟尘负载压降在某种程度上取决于该材料中较宽的孔径范围内的孔径分布。对于使用这些高孔隙率陶瓷的壁流式过滤体应用来说，优选孔径分布值(d50-d10)/d50≤0.50，更优选≤0.40，最优选≤0.35。此外，孔径分布参数值Db，定义为(d90-d10)/d50并表示材料中孔径分布的宽度应≤1.7，优选≤1.4，更优选≤1.2，最优选≤1.0。此外，d90值应≤60μm，更优选≤50μm，最优选≤40μm，同时d10值应≥10μm，优选≥12μm，最优选≥15μm。
在具有窄孔径分布从而(d90-d10)/d50<1.70的系列高孔隙率（>65%且<80%）堇青石陶瓷中，当在CTE（25-800）值<9.0×10-7/℃情况下中值孔径（d50）保持在>10μm且≤25μm的范围时，或者在CTE（25-800）值≥3.0×10-7/℃且≤17.0×10-7/℃的情况下中值孔径（d50）保持在>25μm且<46μm的范围时，可观察到最佳的热力学性能。图5显示了上述两个孔隙率和CTE范围。显示较高CTE值的组表示较少的微裂纹从而具有较高的强度，在中值孔径（d50）较大时显示良好的TSR。所有画出的材料的孔隙率大于65％并且小于80％，所有的Db值[(d90-d10)/d50]<1.70。特别优选这些烧结体的CTE（25-800）≥3.0×10-7/℃且≤9.0×10-7/℃，中值孔径（d50）范围>10μm且≤25μm，或者CTE（25-800）≥5.0×10-7/℃且≤15.0×10-7/℃，中值孔径（d50）范围>25μm且≤36μm。
在具有窄孔径分布的高孔隙率材料的较窄范围内，即陶瓷孔隙率>65％且<75％，、孔径分布Db[(d90-d10)/d50]<1.70，对于d10值≥10μm并且(i)中值孔径>10μm且<30μm，CTE（25-800）值<15.0×10-7/℃，或者(ii)值孔径≥30μm且≤45μm，CTE（25-800）值≥3.0×10-7/℃且<15.0×10-7/℃的陶瓷来说，此时压降、TSR和MOR对于陶瓷有利。图6画出了在上述中值粒径和CTE范围之内的实施例的中值粒径d50和平均CTE值（25-800，10-7/℃）。在图6所列出的范围之内的所有实施例的孔隙率大于65％并且小于75％，窄孔径分布（Db）满足[(d90-d10)/d50]<1.70的，d10值≥10μm。优选这些烧结体的孔隙率大于65％并且小于75％，孔径分布Db[(d90-d10)/d50]<1.70，d10值≥10μm，中值孔径≥18μm且≤32μm，CTE（25-800）值≥5.0×10-7/℃且≤15.0×10-7/℃。更优选陶瓷的CTE<9×10-7/℃，中值孔径d50范围：18≤d50≤30μm，％孔隙率范围：66％<％孔隙率<73％。
如上所述，本发明的高孔隙率堇青石陶瓷对于例如用以从燃料燃烧废气中、尤其是柴油机废气中去除微粒的蜂窝壁流式过滤体的应用具有特别的优点。这些应用的最难之处涉及使用这些蜂窝结构的陶瓷作为结合过滤体/催化剂载体，其中用于从废气流中去除氮氧化物（NOx）的催化剂或吸附剂置于高孔隙率蜂窝体之上。在后一种情况下，特别优选堇青石蜂窝陶瓷的CTE<10.0×10-7/℃（或更优选<8.0×10-7/℃），中值孔径d50≥20μm且≤28μm，孔隙率>65％且<75％，d10值>11μm，d90值<50μm。选择具有这些性能的Db值[(d90-d10)/d50]<1.5且(d50-d10)/d50值≤0.45的蜂窝体以获得最好的过滤性能。

Claims (8)

1.一种堇青石陶瓷制品，包括孔隙率至少为64％并且小于80％，中值孔径（d50）至少为10μm并且不超过45μm，轴向上的平均CTE(25-800℃)满足0.5(d50-24.0)<CTE(25-800℃)<0.5(d50-5.0)，其中d50以微米表示并且CTE（25-800℃）以单位10-7/℃表示，并且，在非多孔棒或条上测量的断裂模数MOR弯曲强度至少为500psi，或者在多孔条上测量的断裂模数强度/闭合正面面积的比率MOR/CFA至少为500psi。
2.权利要求1所述的堇青石陶瓷制品，包括孔隙率百分比范围为64％≤％孔隙率≤77％，中值孔径（d50）以微米表示，其中：
(i)18μm<d50≤50μm；
(ii)d50>158-2.0(％孔隙率)；并且
(iii)d50<210-2.5(％孔隙率)。
3.权利要求1所述的堇青石陶瓷蜂窝制品，包括平均CTE<10.0×10-7/℃，中值孔径≥20μm且≤28μm，孔隙率>65％且<75％，d10值>11μm且d90值<50μm。
4.一种根据权利要求1的堇青石陶瓷制品，其为蜂窝壁流式过滤体。
5.一种根据权利要求1的堇青石陶瓷制品，其应变抗性（MOR/E）至少为0.10%。
6.一种根据权利要求5的堇青石陶瓷制，其应变抗性比（MOR/E）至少为0.12%，并且(i)在非多孔棒或条上测量的断裂模数MOR弯曲强度至少为600psi，或者(ii)在多孔条上测量的断裂模数强度/闭合正面面积的比率MOR/CFA至少为600psi。
7.一种根据权利要求5的堇青石陶瓷制，其应变抗性比（MOR/E）至少为0.14%，并且(i)在非多孔棒或条上测量的断裂模数MOR弯曲强度至少为700psi，或者(ii)在多孔条上测量的断裂模数强度/闭合正面面积的比率MOR/CFA至少为700psi。
8.权利要求1所述的堇青石陶瓷制品，包括孔隙率≥64％并<80％，中值孔径（d50）和25-800℃的平均热膨胀系数（CTE）落在以下范围：
(i)CTE<6.0×10-7/℃；且中值孔径（d50）≥10μm且<18μm。
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