Patent Application
20080032091
The present invention is directed to porous honeycomb ceramics and methods of manufacturing same, and more particularly porous cordierite honeycomb ceramics useful in catalytic converters and particulate filters, such as for engine exhaust after-treatment.
Porous ceramic honeycomb structures are widely used as catalytic converter substrates and/or diesel particulate filters. The earliest cordierite ceramic honeycombs for these applications consisted of reaction-sintered cordierite substrates prepared from extruded mixtures of talc, alumina, and kaolin such as described in U.S. Pat. No. 3,885,977, for example. These were found to have suitable chemical durability, inertness, refractoriness, and thermal shock resistance for the application, and were generally cost effective to manufacture. For purposes of the present description the term “cordierite” used alone refers to orthorhombic cordierite (orthorhombic Mg2Al4Si5O18 and its solid solutions), indialite (hexagonal Mg2Al4Si5O18 and its solid solutions), and mixtures thereof unless expressly stated otherwise.
The high thermal shock resistance of reaction-sintered cordierite ceramics, which is proportional to the ratio of the modulus of rupture (MOR) to the elastic (Young's) modulus (E) of the ceramic and inversely proportional to the coefficient of thermal expansion (CTE) of the ceramic, is attributed to the development of a specific microstructure during firing that depends on an appropriate choice of raw materials, as well as on the forming and firing methods employed. Desirably, the cordierite crystallites within the ceramic will tend to be preferentially oriented with their negative-expansion z-axes aligned near the plane of the wall, thereby reducing the CTE in the axial and radial directions of the honeycomb.
Further, the development of large (>50 μm) fan-like “domains” of radiating prismatic cordierite crystallites creates internal stresses during cooling that produce microcracks throughout the body. The re-closing of these microcracks during subsequent reheating accommodates some of the expansion of the positive-CTE x- and y-axes of the cordierite crystals, thereby further lowering the overall CTE of the body. The very low CTE which results by virtue of preferred orientation and high degree of microcracking has been considered essential to the thermal durability of the substrates.
The technology developed for catalytic converter substrates is generally adaptable to ceramic diesel particulate filters (DPFs). A monolithic DPF may be prepared from a porous ceramic honeycomb by plugging adjacent channels on alternative ends for example, such as in a checkerboard pattern, to form a “wall-flow” filter with inlet and outlet channels. That structure forces entering exhaust gas to pass through the porous honeycomb walls to traverse the wall structure, thereby acting to collect exhaust particulates, such as soot, on the walls of the inlet channels. Relative to converter substrates, which have a relatively low porosity (25-35%) and fine pore size (about 4 μm median pore size) suitable for the application and adherence of catalyst washcoats, DPFs of the prior art have required a higher porosity and coarser pore size to reduce the back pressure through the wall. This has been achieved by utilizing coarser talc and coarser silica raw materials in conjunction with the addition of a coarse pore former (e.g., graphite powder). The pore former burns out of the walls during firing and contributes to obtaining high porosity.
Recent trends in exhaust after-treatment for both gasoline and diesel engines have placed greater demands on the converters and DPFs. For converters, the shift toward higher cell densities and thinner walls (e.g., 900/2) has created challenges in meeting requirements for strength and erosion resistance. The most recent applications requiring low cell densities and thin walls (e.g., 300/4 or 600/3 configurations (cpsi/twall)) for reduced back pressure offer similar challenges, as does the growing interest in higher porosity converters with lower thermal mass for faster light-off to meet emission standards.
Likewise, whereas 45%-50% porosity has been adequate in the past for DPFs used in retrofit applications, the move toward catalyzed DPFs may require even higher porosities and coarser pore diameters to accommodate the catalyst within the porous walls. Porosities as high as 60%-70% and pore diameters of 20-25 μm are being considered.
All of these trends increase honeycomb strength requirements, yet the need to secure low CTEs in cordierite ceramic honeycombs has continued to dictate that microcracking necessarily be present. Microcracking may place a limit on the maximum strength achievable in the ceramic matrix itself. Thus, changes in the honeycomb cell geometry, such as filleting the wall intersections or providing thicker walls near the periphery of the honeycomb near the skin, have been employed to improve the strength of the body in thin wall designs.
A second problem arising from the use of converters and DPFs comprising microcracked cordierite may be the penetration of very fine catalyst washcoat particles into the microcracks formed in the cordierite matrix. The presence of particles within the microcracks may interfere with closure of the microcracks during heating, essentially pinning the cracks open. This may result in an increase in CTE, and also an increase in elastic modulus, both factors contributing to reduced thermal shock resistance. This may be especially problematic for DPFs, where the catalyst washcoats are normally disposed within the porous walls of the filters.
Finally, the high degree of preferred “planar” orientation of cordierite required for low CTE can also present issues in cases where the degree of preferred orientation between the skin and the cellular matrix is different. This can occur due to a different degree of alignment of the platy raw materials resulting from different shear and flow in the skin and matrix during extrusion through the die. Because of the difference in cordierite orientation, the skin and matrix may have different CTEs. Consequently, during cooling from firing, the skin and matrix can contract at different rates, creating tensile stresses within the skin that may lead to the formation of cracks therein. These cracks may reduce both strength and thermal shock resistance.
Based upon the above discussion, it is apparent that, while microcracking and preferred crystallite orientation have been essential in the past for achieving low CTE combined with high thermal shock resistance in reaction-sintered cordierite ceramics, both of these microstructural features can also create problems that may limit the utility of the material for certain applications. For example, microcracking may result in strength reductions, and may facilitate CTE increases where the microcracks are penetrated by catalysts or particulates. Additionally, variable cordierite domain alignment can result in residual stresses in cordierite honeycombs.
The present invention ameliorates or reduces such issues associated with prior art, highly microcracked materials. Accordingly, the present invention relates to a substantially non-microcracked, porous, cordierite ceramic honeycomb body. According to embodiments of the invention, the cordierite ceramic honeycomb bodies exhibit high thermal shock resistance and low coefficient of thermal expansion. Further, the bodies may exhibit high strain tolerance by virtue of a relatively high ratio of MOR/E at room temperature. More particularly, the inventive bodies, in accordance with embodiments, exhibit a thermal shock parameter (TSP) value of at least 400° C., combined with relatively low CTE (25° C.-800° C.)≦15×10−7/° C., wherein TSP is defined by the equation:
TSP=MORRT/[ERT][CTEH],
wherein MORRT corresponds to the modulus of rupture of the cordierite ceramic in 4-point bending at room temperature, and CTEH corresponds to the mean value of the high temperature coefficient of thermal expansion of the material, that coefficient being or calculated on heating over the temperature range of 500° C. to 900° C. The walls of the honeycomb bodies may have a random or preferred cordierite crystal orientation, although it has been discovered that a preferred orientation (cordierite crystal z-axes parallel to the wall surfaces) in accordance with an alternative aspect of the invention provides relatively lower CTE as compared to random crystal orientation.
Additionally, and in another broad aspect of the invention, a porous ceramic honeycomb structure is provided, comprising a primary cordierite ceramic phase exhibiting a room temperature elastic modulus (ERT) at 25° C., and a high temperature elastic modulus (EH) at 1000° C., and
an Eratio 1000≦1.05, wherein Eratio 1000=EH/ERT, and
TSP≧525° C. wherein the thermal shock parameter (TSP) is defined as
TSP=MORRT/[ERT][CTEH]
(MORRT) is a room temperature modulus of rupture strength, and (CTEH) is high temperature thermal expansion coefficient between 500° C. and 900° C. MOR, E, and CTE are all measured on a cellular specimen parallel to the length of the channels, also referred to as the axial direction. EH is measured during heating from room temperature. Additionally, the invention may exhibit ERatio 1000≦1.01, ERatio 1000≦1.00, ERatio 1000≦0.98, ERatio 1000≦0.95, or even ERatio 1000≦0.93. Further, the honeycomb structures of the invention may exhibit relative low CTE, such as CTE (25-800° C.)≦18×10−7/° C., CTE (25-800° C.)≦16×10−7/° C., CTE (25-800° C.)≦15×10−7/° C., CTE (25-800° C.)≦14×10−7/° C., CTE (25-800° C.)≦12×10−7/° C., CTE (25-800° C.)≦10×10−7/° C., or even CTE (25-800° C.)≦9×10−7/° C. In addition to Eratio 1000≦1.05 and TSP≧525° C., as described above, further embodiments of the invention may be characterized by a pore microstructure of the porosity further including a relatively narrow pore size distribution. In particular, embodiments may additionally include a narrow pore size distribution wherein a porosity d-factor (df), defined by the equation df=(d50−d10)/d50, may be df≦0.48, df≦0.40, df≦0.37, df≦0.35, df≦0.30, df≦0.28, or even df≦0.25. Furthermore, the narrowness of the pore size distribution of the low microcracked honeycomb may be further defined by a pore microstructure wherein the overall pore size breadth (db), defined as db=(d90−d10)/d50, may be db≦1.65, db≦1.23, db≦1.21, db≦1.15, db≦1.00, db≦0.90, db≦0.80, or even db≦0.70. Lowering db increases filtration efficiency for filters, and strength for both filter and substrate applications.
Furthermore, the walls of the porous ceramic honeycombs of the invention may further include a preferred orientation wherein the cordierite crystallites in walls of the honeycomb structure have an preferred orientation exhibiting ΔI>0.1 wherein ΔI=IT−IA. In particular, the structure may include IA≦0.6, IA≦0.5, or even IA≦0.4. Additionally, for oriented examples, the structure may include IT≧0.7, or even IA≧0.8. The preferred orientation of the low-microcracked honeycomb reduces CTE in at least one direction. Furthermore, the cordierite structural honeycomb bodies of the present invention additionally may exhibit high pore connectivity, as defined by a Pore Connectivity Factor (PCF), defined by the relationship PCF=% P/(db), wherein PCF may be PCF≧40%, PCF≧45%, PCF≧50%, or even PCF≧55%. Moreover, PCF≧60%, PCF≧70%, PCF≧80% or even PCF≧90% have been demonstrated according to selected embodiments of the invention.
In certain embodiments, the cordierite bodies are useful in the form of honeycomb ceramic substrates useful as flow-through substrates (non-plugged embodiments) for the support of gasoline engine emissions control catalysts. For some of these applications, the honeycomb ceramic bodies may require relatively higher porosity, for example to accommodate catalyst storage within the honeycomb channel walls. Likewise, relatively higher porosity is required to provide high wall permeability for plugged ceramic honeycomb wall-flow filters (particulate filters) used for diesel engine exhaust treatment. In such relatively high porosity applications, the honeycomb ceramic bodies may have total porosities (% P) wherein % P≧46%, or even % P≧50%. In some embodiments, % P≧55%, % P≧60%, % P≧65%, or even % P≧70% is demonstrated. Certain applications for fast light-off catalyst flow-through substrates which exhibit thin walls (e.g., less than 10 mils, less than 7 mils, or even less than 6 mils or 4 mils) may require total porosity greater than 46%, greater than 50%, or even greater than 55%.
According to another aspect, the invention is a method for making a porous ceramic honeycomb structure, comprising the steps of mixing inorganic raw materials, an organic binder, and a liquid vehicle to form a plasticized batch, forming a green body from the plasticized batch, drying the green body, and firing the body to provide a cordierite ceramic structure having relatively low microcracking and relatively high thermal shock by exhibiting Eratio≦1.05 and TSP≧525° C.
According to another aspect, the invention is porous ceramic honeycomb structure, comprising a primary cordierite ceramic phase exhibiting low microcracking as exhibited by Δαmc≦5.0, CTE (25-800° C.)≦15×10−7/° C., and % P≧46%.
The invention is further described below with reference to the attached drawings, wherein:
Securing a relatively low ratio of elastic modulus, Eratio 1000=EH 1000° C./ERT in the cordierite ceramic honeycomb bodies of the invention is achieved by providing bodies formed of a substantially non-microcracked porous, cordierite ceramic material. Eratio 1000 values above 1.00 and below 1.05 are indicative of very minor, but tolerable, levels of microcracking (see
Therefore, in accordance with embodiments of the invention, values of Eratio 1000 of less than or equal to 1.05 are desired, and values of Eratio 1000 defined as EH 1000/ERT≦1.01 or even EH 1000/ERT≦1.00 are more desired. However, in accordance with embodiments of the invention, Eratio 1000≦0.98, Eratio 1000≦0.96, Eratio 1000≦0.95, or even Eratio 1000≦0.93 are demonstrated. These are exemplary of relatively low levels of microcracking. High temperature elastic modulus values may be determined by referring to ASTM C 1198-01 or co-pending U.S. patent application Ser. No. ______ filed Jun. 27, 2007 and entitled “Methods And Apparatus For Measuring Elastic Modulus Of Non-Solid Ceramic Materials By Resonance,” the disclosure of which is hereby incorporated by reference herein.
The Thermal Shock Limit (TSL) of ceramic honeycomb bodies according to the invention is conventionally considered to be the maximum temperature to which the center of the body can be heated when the surface of the body is 500° C., without suffering cracking damage. TSL may be estimated by adding 500° C. to the value of Thermal Shock Parameter (TSP) as hereinabove defined. In other words, TSL=TSP+500° C. Illustrating improved thermal shock limit (TSL) in accordance with another aspect of the invention, therefore, are values of TSP achieved by embodiments of the invention which are TSP≧400° C., TSP≧450° C., TSP≧525° C., TSP≧550° C., and even TSP≧600° C. In some embodiments, TSP≧700° C. (see examples 4-6, 8-9, 11, 13-14, 27-32, 35-39, 41-43, and 46), TSP≧800° C. (see examples 4, 6, 13-15, 18, 20, 27-28, 31, 36-39, and 41-43), TSP≧900° C. (see examples 14, 18, 27-28, 31, 37-38, and 41-42), and even TSP≧1000° C. (see examples 18, 27, and 41) are achieved.
Moreover, in certain embodiments, the present invention low microcracked honeycombs achieve a desirable combination of both relatively low CTE and high TSP. For example, in accordance with a broad aspect of the invention, a low microcracked honeycomb including a combination of TSP≧400° C. and CTE (25-800° C.)≦18×10−7/° C., or even CTE (25-800° C.)≦15×10−7/° C. are achieved by embodiments of the invention (
A high proportion of well interconnected pores with a narrow pore size distribution of the cordierite honeycomb bodies of the invention may contribute importantly to the high TSP values observed (
As noted above, the relative narrowness of the pore size distribution of the porosity of the porous body of the invention may be characterized by df≦0.48 and/or db≦1.65, wherein df=(d50−d10)/d50 and db=(d90−d10)/d50. The parameters d10, d50, and d90 in these equations are conventionally and defined herein as the pore diameters at which 10%, 50%, and 90%, respectively, of the pore volume of the material resides in pores of smaller pore diameter, as measured by standard mercury porosimetry. Thus, d10<d50<d90 in these measurements. For improved TSP performance, values for the porosity d-factor (df) achieved by embodiments of the invention are df≦0.45, df≦0.40, df≦0.37, df≦0.35, and df≦0.30. Certain embodiments achieve relatively very low porosity d-factor (df), wherein df≦0.28 (see examples 27, 36, 39, and 44-45), df≦0.25 (see examples 36 and 44-45), or even df≦0.23 (See examples 44-45). Additionally, overall breadth of the pore size distribution as defined as db=(d90−d10)/d50 may also be relatively narrow. For example, values of db achievable by embodiment of the invention are db≦1.65, db≦1.4, db≦1.20, db≦1.00, or even db≦0.90. Certain exemplary embodiments exhibit db≦0.80 (see examples 21, 27-28, 30-31, 36, 38-39, 41-42, 44, 46), db≦0.70 (see examples 27-28, 36, 44), or even db≦0.65 (see examples 27 and 44).
Relatively high Pore Connectivity Factors (PCF), defined by the relationship PCF=% porosity/(db), may be achieve by embodiments of the invention. Accordingly, embodiments may achieve PCF≧40%, PCF≧45%, PCF≧50%, PCF≧55%, or even PCF≧60%. Other embodiments exhibit PCF≧70% (see examples 14, 18, 21, 27-28, 30-31, 36, 38-39, 41-44, 46, and 55), PCF≧80% (see examples 27-28, 30, 36, 38, 41-42, and 44), or even PCF≧90% (see examples 27-28 and 44).
In the high-porosity honeycombs according to embodiments of the invention, i.e. cordierite honeycombs having a total porosity (% P) of % P≧46%, the median pore diameter (d50) targeted may depend, in part, upon the particular end use for the honeycomb. For use as a flow-through honeycomb substrate for the support of catalysts, the median pore size (d50) of a ceramic honeycomb in accordance with the invention may be in the range of about 1-30 μm, with values of d50≧10 μm, or even 10-30 μm being especially beneficial when the pores are to contain a catalyst material; and values of median pore size (d50) of between 1-10 μm being desired when the high porosity ≧46%, is required to reduce the thermal mass of the substrate and improve light-off characteristics, for example, such as in non-plugged flow-through catalyst substrate applications.
On the other hand, when the high-porosity honeycomb is to be used as a wall-flow particulate filter, such as in diesel exhaust filtering applications, the median pore diameter (d50) may be in the range of 5-15 μm in cases where the filter is to support a low loading of catalyst or is absent a catalyst, and in the range of 15-30 μm where the filter is to support a relatively higher loading of a catalyst. For both of these applications, the total porosities of the walls may be, for example, % P≧46%, % P≧50%, % P≧55%, or even % P≧60%, and in some cases % P≧65%, or even % P≧70%. Many embodiments of the inventive honeycomb structure exhibit the combination of d50≧8 μm, and a total porosity ≧50%.
The ceramic honeycomb bodies may be porous cordierite ceramic honeycomb bodies having a plurality of cell channels extending between a first and second end as shown in
The crystalline microstructure of cordierite ceramic honeycomb bodies provided in accordance with the invention may include the low-microcracked feature exhibiting Eratio 1000≦1.05, or even Eratio 1000≦1.01, defined as Eratio 1000=(E1000° C./ERT)), and also may be characterized by either a random orientation of the cordierite crystallites within the honeycombs, or by a net degree of preferred crystallite orientation (having a preferred orientation), most typically with crystallite z-axes having some degree of alignment parallel to the surfaces of the walls of the honeycomb. Random orientations are exemplified by cordierite crystallites in walls of the honeycomb structure exhibiting ΔI≦0.1 wherein ΔI=IT−IA. IT is the transverse I ratio and IA is the axial I ratio (see discussion below for definitions). Examples 21-26 exemplify randomly oriented embodiments in accordance with aspects of the invention. On the other hand, cordierite crystallites in walls of the low-microcracked honeycomb structure of the invention which have a preferred orientation exhibit ΔI≧0.1 wherein ΔI=IT−IA (see examples 1-20 and 27-55). In accordance with embodiments of the present invention porous ceramic honeycomb, the walls of the honeycomb structure including a preferred orientation may further include IA≦0.6, IA≦0.5, or even IA≦0.4. Furthermore, the walls of the honeycomb structure may further include IT≧0.7, IT≧0.8, IT≧0.85, or even IT≧0.9. In another aspect, the low-microcracked honeycomb structures of the invention which exhibit preferred orientation may exhibit ΔI≧0.2, ΔI≧0.3, ΔI≧0.4 or even ΔI≧0.5 wherein ΔI=IT−IA.
In order to preserve good thermal shock resistance, the average coefficient of thermal expansion of the cordierite ceramic honeycomb body over the 25° C.-800° C. temperature range (hereinafter the CTE) should be relatively low. Accordingly, CTE≦18.0×10−7/° C. (25° C.-800° C.) along at least one direction in the ceramic body may be exhibited by embodiments of the invention. In further embodiments, CTE≦16.0×10−7/° C. (25° C.-800° C.), or even CTE≦14.0×10−7/° C. (25° C.-800° C.) along at least one direction are provided. In additional embodiments of the low-microcracked honeycombs, the coefficient of thermal expansion of the cordierite ceramic honeycomb body along at least one direction over the temperature range is CTE≦12.0×10−7/° C. (25° C.-800° C.), CTE≦10.0×10−7/° C. (25° C.-800° C.), or even CTE≦9.0×10−7/° C. (25° C.-800° C.). The relatively low level of microcracking of the invention generally provides that 7×10−7/° C.≦CTE (25-800° C.)≦15×10−7/° C. According to some embodiments microcracking provides a honeycomb body wherein 9×10−7/° C.≦CTE(25-800° C.)≦15×10−7/° C., or even 10×10−7/° C.≦CTE(25-800° C.)≦15×10−7/° C. In other embodiments of the invention, the CTE may be such that CTE(25-800° C.)≧0.20(% P)−4.5, or even CTE(25-800° C.)≧0.20(% P)−3.0.
The CTE of a cordierite body is largely determined by the intrinsic CTE of the cordierite crystals, by the overall degree of textural orientation of the cordierite crystals within the ceramic in the direction along which the CTE of the body is measured, by the amount of secondary crystalline phases in the ceramic body, and by the extent of microcracking in the ceramic body. Accordingly, each of these contributions to the CTE of the ceramic honeycomb body along a given direction may be evaluated individually.
It has been discovered that excessive development of secondary crystalline phases such as mullite, spinel, sapphirine, and corundum in these ceramics will raise the CTE to higher values and, thus, should be avoided, if practical. In practice, it has been observed the average CTE increases with the total amount of residual mullite+spinel+sapphirine+corundum present in a predominantly cordierite body by a rate of about 0.6×10−7/° C. per 1% total of these secondary crystalline phases. Accordingly a “normalized” CTE, corresponding to the component of the thermal expansion coefficient attributable to the cordierite phase only, may be computed as CTE−0.6 (% 2nd crystalline phases). Accordingly, to achieve relatively lower CTE, where desirable, these 2nd crystalline phases should be present in less than 6% collectively, or even less than 4% collectively.
It has also been discovered by the inventors that, in the absence of microcracking and secondary phases, the CTE of a cordierite honeycomb body in the direction of the lengths of the channels (“axial” CTE) from 25-800° C. is related to the axial XRD I-ratio, IA, by the relation CTE=76.8(IA)3−129.5(IA)2+97.9(IA)−12.8, wherein the axial I-ratio IA=I(110)/[I(110)+I(002)] as determined by x-ray diffractometry in accordance with known practice on a cross section orthogonal to the lengths of the channels of the honeycomb (
It is recognized that excessively low CTEs are generally indicative of excessive microcracking in cordierite honeycombs, which microcracking should be avoided as possibly deleterious to strength and thermal shock resistance (TSR). The degree of microcracking in cordierite honeycomb ceramics, whether or not comprising such secondary crystalline phases, is found to be reflected in a thermal expansion differential factor Δαmc, defined as:
Δαmc=[76.8(IA)3−129.5(IA)2+97.9(IA)−12.8]+0.6(% Mu+Sp+Sa+Al)−CTE,
wherein % (Mu+Sp+Sa+Al) is the sum of the weight percentages of mullite, spinel, sapphirine, and corundum present in the honeycombs, and wherein IA is the axial I-ratio as described above.
In accordance with another aspect of the invention, where the cordierite crystallites comprising the honeycomb body are randomly oriented in the walls, such as when exhibiting ΔI≦0.1 wherein ΔI=IT−IA, then CTEs for the honeycombs may be achieved which are less than 18×10−7/° C. (25° C. to 800° C.), and exemplary embodiments range between 12×10−7/° C. and 18×10−7/° C. (25° C. to 800° C.), and with many less than 16×10−7/° C. (25° C. to 800° C.), or even between 12-15×10−7/° C. (25° C. to 800° C.).
For the purposes of the present description, references to cordierite ceramic bodies or honeycombs are intended to include bodies or honeycombs of similar physical properties comprising “stuffed” cordierites as well. Stuffed cordierites are cordierites having molecules or elements such as H2O, CO2, Li, K, Na, Rb, Cs, Ca, Sr, Ba, Y, or a lanthanide element in the channel site of the cordierite crystal lattice, such constituents imparting modified properties such as improved sinterability or reduced lattice thermal expansion or thermal expansion anisotropy that may be useful for some applications. Also included are cordierites wherein chemical substitutions of Fe, Mn, Co, Ni, Zn, Ga, Ge, or the like for the basic cordierite constituents are made for reasons such as improved sinterability, color, electrical properties, or catalytic properties.
In another broad aspect, the invention includes a method for making the porous cordierite ceramic honeycomb structure such as hereinabove described. In accordance with that method, inorganic raw material sources of MgO, Al2O3, SiO2 or combinations thereof are combined with an organic binder, a liquid vehicle and one or more optional constituents including pore-forming agents, plasticizers, and lubricants to form a plasticized batch. The plasticized batch is then formed by shaping, such as by extrusion, into a green honeycomb. These green honeycombs are then dried, such as by microwave or RF drying, and fired in a kiln to sinter or reaction-sinter the inorganic raw material sources into unitary cordierite ceramic honeycomb bodies. The green bodies are fired for a time and at a temperature sufficient to provide a sintered cordierite honeycomb including relatively low microcracking and relatively high thermal shock as exhibited by achieving ERatio≦1.05 and TSP≧525 psi.
Inorganic ingredients suitable for use as raw materials for compounding such plasticized batches include natural or synthesized cordierite powders, as well as inorganic powders or combinations of inorganic powders capable of reacting to form non-microcracked cordierite bodies through high-temperature reactions. Examples include (1) cordierite powders, also called “grogs,” consisting predominantly of a cordierite phase ceramic; (2) magnesium aluminosilicate-based glass powders, also called frits; (3) powders wherein each particle comprises an assemblage of multiple phases that will react to form a cordierite; (4) mixtures of two or more compositionally different powders, each of which may be single-phase or multi-phase powder; and (5) chemically precipitated magnesium aluminosilicate powders such as sol-gel powders that will react to form a cordierite microstructure.
The median particle diameter of the powders is not critical; particle sizes may be routinely adjusted to those diameters effective to provide a median pore size in the final body that is suitable for the particular application. For example, when the application is a catalytic converter substrate, the median particle size of the raw materials may be between 2 and 20 microns. When the application is a diesel particulate filter, the median particle size may be between 15 and 50 microns. However, it is normally preferred that the particle size distribution of the inorganic powder or inorganic powder combinations be made narrow so as to preferably provide a narrow pore size distribution, high pore connectivity, and a high MOR/E ratio in the fired body.
The bulk composition of the raw materials present in the starting powders, exclusive of volatile components such as H2O, CO2, SO2, and organics, should be adjusted to provide a net oxide composition of approximately 48-54% SiO2, 33-37% Al2O3, and 11-16% MgO, with the cumulative weights of these three oxides constituting at least 95% of the total weight of batch exclusive of volatile or evaporable components. Preferably, the ratios of these oxides will be adjusted so that the fired ceramic bodies will constitute at least 90% by weight of cordierite, or even 95% or 97% by weight of cordierite.
Other components that may be present in these batches in minor proportions include oxides of impurity elements or intentional dopants such as calcium, iron, titanium, sodium, potassium, boron, tungsten, bismuth, etc. The ratio of magnesia, alumina, and silica components in the bulk raw material mixture may be chosen to form only stoichiometric cordierite, or may be selected to allow the formation of some spinel, sapphirine, mullite, forsterite, enstatite, or a glass phase. However, the sum of CaO+Na2O+K2O may be less than 1.0 wt. %, or even less than 0.5 wt %, and cristobalite development in the body should be limited to less than 1.0 wt %, or more preferably entirely avoided.
When synthesized cordierite powders are selected for use in the batch, the cordierite particles, when coarser than about 20 microns, are preferably not single-crystal particles, but preferably comprise a polycrystalline aggregate of cordierite crystallites. The cordierite crystallites may be randomly oriented with respect to adjacent crystallites within the particles. If the cordierite raw material particles comprises, entirely, or in part, “domains” of crystallites sharing a near-parallel orientation with respect to one another within a domain, then these domains are should not larger than about 20 microns, and in some cases not larger than 10 μm.
Cordierite powders suitable for the intended purpose can be obtained, for example, by the complete or partial pre-reaction of inorganic precursor materials, including mineral combinations such as clay+talc+alumina, spinel+silica, magnesia+alumina+silica, forsterite+kaolin, etc., or by the partial or complete devitrification (crystallization) of a magnesium alumino-silicate glass frit; or by the partial or complete crystallization of a chemically precipitated magnesium alumino-silicate material, such as a sol-gel powder. Alternatively naturally occurring cordierites, ground to suitable particle sizes, can be used.
When the cordierite powder is prepared by reacting inorganic mineral raw materials or chemically precipitated materials, it may be formed, for example, by fabricating a mass of the mixed precursors or chemical precipitates, heating the mass to a temperature sufficient to form cordierite, and then crushing the mass to the desired particle size with optional sieving or air classification. Alternatively, the raw materials or precipitates could also be pre-powdered by spheroidizing, such as by spray drying or other atomization method, and the resulting granules heated to temperatures effective to form cordierite. When the cordierite powder is prepared from a glass precursor, the molten glass may be formed into a convenient shape and crushed, or it may be “drigaged” by pouring the molten glass into a quenching liquid such as water. The resulting glass feeds may then be ground to a desired particle size with optional sieving or air classification to select an appropriately necessary particle size range.
When the final particle size of the glass is to be larger than about 20 μm, the glass may contain a nucleating agent, such as titanium oxide, to promote the nucleation of cordierite at many locations throughout the interior of the glass particle during subsequent devitrification to prevent formation of crystal domains larger than 20 μm. The glass powder is then heated so as to nucleate and grow cordierite by devitrification, or “ceramming.” Optionally, the devitrified glass may be subjected to additional powder processing after heating to obtain the desired particle size distribution.
In accordance with a preferred batch method, the mixture of inorganic raw materials includes talc, an alumina-forming source, a silica-forming source, and, optionally, kaolin or calcined kaolin. In particular embodiments, the raw material mixture may further include a colloidal metal oxide source. The colloidal metal oxide source is capable of forming a colloidal suspension in a solvent preferably and contains 0 to 97 wt % SiO2, 0 to 97% MgO, 0 to 97% Al2O3, and at least 3.0 wt. % of one or more metal oxides selected from the group comprising Li2O, Na2O, K2O, CaO, Fe2O3, and TiO2. The metal oxides may further comprise at least 4%, at least 5%, or even at least 6 wt. % of the colloidal metal oxide source. According to embodiments, the colloidal metal oxide source may comprise a colloidal silicate phase containing at least 50 wt % SiO2 when the chemical formula is calculated on an anhydrous basis. For example, the colloidal silicate may be a colloidal phyllosilicate, such as an attapulgite or bentonite clay. According to further embodiments, the mixture of inorganic raw materials may contain a nucleating agent for promoting the nucleation of cordierite by reaction of the inorganic raw materials. One useful nucleating agent is a pre-reacted cordierite powder.
In addition to the mixture of inorganic raw materials, the batch may further include a pore-forming agent. The pore-forming agent may comprise greater than or equal to 50% by weight, or even 60% by weight, of the inorganic raw materials by superaddition. The pore-forming agents may comprise combinations of graphite and starch, for example. The starch may comprise corn or potato starch. In the case where a combination of graphite and starch is employed, the pore-forming agents may comprise greater than or equal to 40% graphite and greater than or equal to 10% starch, as a superaddition based upon 100% weight of the inorganic raw materials.
According to embodiments of the method, to produce ceramic honeycomb articles exhibiting low microcracking as well as high strain tolerance (MOR/E), and, therefore, high TSP, certain components of the batch should be appropriately selected, in particular, the raw inorganic raw materials and the pore former, and the firing conditions should be appropriately controlled. It has been discovered that achieving a factor PMC≦5.0 tends to yield very low microcracking (
PMC=7.06+0.164 (wt % raw kaolin)+0.095 (wt % calcined kaolin)−0.00870 (wt % alumina-forming sources)(d50 of alumina-forming sources)-0.0657 (wt % pore formers)+0.022 (heating rate from 800° C. to 900° C.)+0.025 (heating rate from 1200° C. to 1300° C.)−0.018 (heating rate from 1350° C.−Tmax)−0.462 (wt % colloidal metal oxide source), and
PST=0.067+0.000967 (wt % pore former)−0.00000516 (wt % pore former)(d50 of pore former)−0.000921 (wt % kaolin+wt % calcined kaolin)+0.0000502 (wt % alumina-forming sources)(d50 of alumina-forming sources)−0.0000143 (wt % talc)(d50 of talc)+0.00392 (wt % colloidal metal oxide source).
To achieve relatively lower microcracking, PMC≦3.0, PMC≦2.0, or even PMC≦1.0 may be provided. Similarly, to achieve relatively higher strain tolerance (MOR/E) and thus relatively higher TSP, then PST≧0.100, PST≧0.120, or even PST≧0.140. In order to achieve relatively lower CTE (25° C.-800° C.), the raw material mixture may be absent of pre-reacted cordierite or other cordierite nucleating agent.
In additional embodiments, the method may include inorganic raw materials which are absent of kaolin or calcined kaolin. Lack of kaolin or calcined kaolin may provide a lesser degree of microcracking, and may also narrow the pore size distribution. Similarly, the raw material mixture may be absent of an aluminum trihydrate [gibbsite or Al(OH)3] having a median particle diameter smaller than 4 microns, as a lack of fine aluminum trihydrate may also provide a lesser degree of microcracking. Additionally, the raw material mixture may be absent of kaolin or calcined kaolin and further comprise a talc source, one or more alumina-forming sources, a silica-forming source, at least 20 wt % pore former, and 0-10 wt % of a colloidal phyllosilicate which contains at least 4 wt % (Li2O+Na2O+K2O+CaO+Fe2O3+TiO2). The presence of colloidal phyllosilicate may help introduce impurities and, therefore, may help produce more of a glassy phase which may generally reduce microcracking. According to further embodiments of the invention, the talc source and the silica-forming source may each be relatively fine and may have a median particle diameter of less than 12 μm, the colloidal phyllosilicate may constitute at least 3 wt. %, and the pore former may have a median particle diameter of not more than 40 μm. According to other embodiments, the talc source and the silica-forming source each have a median particle diameter of at least 12 μm and not more than 35 μm, and each pore former possesses a median particle diameter of not less than 30 μm and not greater than 60 μm.
Examples of cordierite ceramics both inside (Inventive) and outside (Comparative, designated with a C) of the scope of the present invention are set forth in Tables 1-18 below. These include materials with varying porosities, pore size distributions, degrees of pore connectivity (via varying PCF), as well as material strength (MOR) and thermal properties (CTE, etc.). Included in Table 1 is a list of the various raw materials that may be used in the batches formulating these inventive porous ceramic honeycombs. The batch compositions for the various examples of the present invention are provided in Tables 3-9. All particle sizes listed for the raw materials are obtained by laser diffractometry such as on a Model FRA9200 or Model S3000 Microtrac particle analyzer (products of Microtrac Inc.) unless noted otherwise. Included in Tables 11-18 are relevant physical properties for exemplary embodiments of the low-microcracked cordierite ceramics honeycomb products of the invention, both as measured and as calculated from the measured values. Properties of the comparative examples are provided in Table 10. These values include the % Porosity (% P) of each material by volume, various pore diameters (e.g., d1, d10, d50, d90, etc.) of the materials, the porosity d-factor (df) defined as df=(d50−d10)/d50, the porosity breadth factor (db) defined as db=(d90−d10)/d50, the pore connectivity factor (PCF), defined as PCF=% P/(db), various measures of Coefficient of Thermal Expansion (CTE) of the honeycombs over various ranges (25-800° C., 500-900° C., and 200-1000° C.), the thermal expansion differential factor attributable to microcracking (Δαmc), the transverse I-ratios (IT) and axial I-ratios (IA) determined in individual cases on extruded honeycomb shapes of the materials, as well as the I ratio difference (ΔI), defined as ΔI=IT−IA, the percents of secondary crystal phases mullite, spinel+sapphirine, and alumina present in the material (the remaining percentage made up of cordierite phase and intercrystalline glass), the cell densities (in cpsi or cells/in2 of the honeycomb taken in cross-section) and wall thicknesses (in mils or thousandths of inches) of sample cellular honeycomb ceramics made of the materials, the Closed Frontal Area (CFA), the room temperature modulus of rupture strength (MOR), the ratio of room temperature modulus of rupture strength to Closed Frontal Area (MOR/CFA), the elastic modulus of each material (psi) at various temperatures during heating (@ RT (25° C.), @900° C. and 1000° C.) as determined on a honeycomb ceramic sample of that material, the Eratio at various temperatures (@900° C. and @1000° C.), the microcrack parameter Nb3 (as defined below), the room temperature (at 25° C.) strain tolerance (MOR/E), thermal shock parameter (TSP), and thermal shock limit (TSL) of the materials, wherein TSP is defined as TSP=MORRT/[ERT][CTEH], wherein (ERT) is the room temperature elastic modulus, (MORRT) is the room temperature modulus of rupture strength, and (CTEH) is the high temperature (500-900° C.) thermal expansion coefficient. TSL is defined as TSL=TSP+500° C. Also computed is a thermal shock parameter based upon a near-skin temperature of 200° C., TSP*=MORRT/[ERT][CTE200-1000° C.], and the corresponding thermal shock limit TSL*=TSP*+200° C., which the estimated temperature to which the core of the honeycomb may be heated without fracture when the skin is at 200° C.
The microcracked parameter Nb3 is a measure of the level of microcracking in ceramic bodies, such as a cordierite ceramics. The present inventors have discovered that for a low-microcracked cordierite body, the elastic modulus gradually decreases with increasing temperature. This decrease in the elastic modulus is believed to be attributable to the increasing distance between atoms within the crystal structure with increasing temperature. An example of the decrease in elastic modulus with increasing temperature for a porous, non-microcracked cordierite honeycomb body is depicted in
ΔEo/ΔT=−7.5×10−5(EoRT) EQ. 1
The superscript “°” elastic modulus term (EO) denotes the elastic modulus of the ceramic in a non-microcracked state. Based upon EQ. 1, one can calculate the ratio of the elastic modulus of a non-microcracked cordierite body at 900° C. or at 1000° C. to that of a non-microcracked cordierite body at 25° C. as being E900° C./ERT=1+875(−7.5×10−5)=0.934 or E1000° C./ERT=1+975(−7.5×10−5)=0.927. These values of Eo900° C./ERT and Eo1000° C./EoRT provide a baseline against which to compare the E900° C./ERT and Eo1000° C./EoRT values of a microcracked ceramic body. For non-microcracked cordierite bodies, the temperature dependence of the elastic modulus during cooling after heating to a high temperature, such as 1,200° C., is essentially identical to the temperature dependence during the original heating, so that, at any given temperature, the value of the elastic modulus during cooling is nearly the same as its value at that temperature during heating. This is also illustrated in
An example of the temperature dependence of the elastic modulus for a highly microcracked cordierite ceramic body is displayed in
The elastic modulus increases gradually, and then more steeply, with increasing temperature up to 1,200° C. This increase is believed to be due to the re-closing, and eventual annealing, of the microcracks with heating, so that the ceramic body has progressively fewer open microcracks at higher temperatures. The increase in E due to the reduction in microcracking more than offsets the decrease in E of the individual cordierite crystallites with heating, resulting in a more rigid body at high temperature. As the ceramic is cooled from 1,200° C., the microcracks do not immediately re-open, because micro-stresses are initially too low. As a result, the trend in elastic modulus with cooling is initially that of a non-microcracked cordierite body. The increase is steep at first due to the increase in viscosity of any liquid or glass phase, possibly accompanied by a reduction in volume fraction of the liquid or glass due to crystallization or devitrification, respectively. Between about 1,000 and 800° C. in the example in
The extent of microcracking in the cordierite ceramic is reflected in two features of the elastic modulus heating and cooling curves. One manifestation of the degree of microcracking is the extent to which the elastic modulus increases from 25° C. to 900° C. or to 1000° C. during heating, as this increase is believed to be caused by a re-closing of the microcracks. For example, in
Another indication of the degree of microcracking is the gap between the elastic modulus heating and cooling curves. A method to quantify this hysteresis is based upon the construction of a tangent to the cooling curve in a temperature region where the sample is still in a non-microcracked state. In
Eotangent=(EoRT){1−7.5×10−5(T−25)} EQ. 2
In practice, the inventors have devised an analytical method for determining EoRT from the experimental measurements of the elastic modulus during cooling, after heating to about 1,200° C. In accordance with this method, a second-order polynomial is fit to the elastic modulus measurements made during cooling between about 1,000° C. and 500° C., as a function of temperature (° C.). This equation is of the following form:
E=c+b(T)+a(T2) EQ. 3
In practice, the upper limit of the temperature range over which the experimentally measured elastic modulus values are fit by EQ. 3 may be further restricted to a temperature less than 1000° C. if it is determined that the trend in E versus temperature exhibits a very high curvature at, or below, about 1000° C., due to, for example, softening of a glass phase or formation of a small amount of liquid. Likewise, the lower limit of the temperature range over which the experimentally measured elastic modulus values are fit by EQ. 3 may be further restricted to a temperature greater than 500° C. if it is determined that the trend in E versus temperature exhibits a very high curvature at, or above, about 500° C., due to, for example, reopening of the microcracks. The method of least-squares regression analysis is used to derive the values of the regression coefficients “a,” “b,” and “c” in EQ. 3.
The value of EoRT is obtained by solving for the elastic modulus and temperature at which the tangent line, given by EQ. 2, intersects the polynomial curve fit to the elastic modulus data during cooling, given by EQ. 3. The values of the elastic modulus and temperature at this point of intersection are denoted Ei and Ti, respectively. In the example in
Ei=(EoRT){1−7.5×10−5(Ti−25)}=c+b(Ti)+a(Ti2) EQ. 4
Also, at the point of tangency, the slope of the polynomial curve must equal that of the tangent line. Therefore, it follows that
(EoRT)(−7.5×10−5)=b+2a(Ti) EQ. 5
EQ. 4 and EQ. 5 provide two equations relating the two unknown quantities, EoRT and Ti, to one another. To solve for EoRT and Ti, EQ. 5 is first rearranged to yield
(EoRT)={b+2a(Ti)}/(−7.5×10−5) EQ. 6
EQ. 6 is then substituted into EQ. 5 to give the following expression:
{{b+2a(Ti)}/(−7.5×10−5)}{1−7.5×10−5(Ti−25)}=c+b(Ti)+a(Ti2) EQ. 7
EQ. 7 may be rearranged to yield the following:
0={c+b(Ti)+a(Ti2)}−{{b+2a(Ti)}/(−7.5×10−5)}{1−7.5×10−5(Ti−25)} EQ. 8
Gathering terms in EQ. 8 gives the following relation:
Further simplifying EQ. 9 yields
EQ. 10 may be re-expressed as
0=C+B(Ti)+A(Ti2) EQ. 11
where C={c−{b/(−7.5×10−5)}{1+7.5×10−5(25)}}, B={−2a/(−7.5×10−5)}{1+7.5×10−5(25)}, and A=−a. The value of Ti can then be found by solving the quadratic formula:
Ti={−B+{B2−4(A)(C)}0.5}/2A EQ. 12
Ti={−B−{B2−4(A)(C)}0.5}/2A EQ. 13
EQ. 12 and EQ. 13 provide two possible values of Ti, of which only one will have a physically realistic value, that is, a value lying between 25 and 1,200° C. The physically realistic value of Ti computed in this manner is then substituted into EQ. 6, from which the value of EoRT is calculated.
Once EoRT has been solved for, the ratio of the elastic modulus for the hypothetically non-microcracked sample at 25° C., EoRT, to the actual measured value of the elastic modulus of the microcracked sample at 25° C., ERT, is proportional to the degree of microcracking in the initial sample before heating. That is, a greater degree of microcracking at room temperature will lower the value of ERT, and thereby raise the value of EoRT/ERT.
Modeling of the relationship between elastic modulus and microcracking has provided a relationship between the ratio EoRT/ERT and the quantity Nb3, where N is the number of microcracks per unit volume of ceramic and b is the diameter of the microcracks (see D. P. H. Hasselman and J. P. Singh, “Analysis of the Thermal Stress Resistance of Microcracked Brittle Ceramics,” Am. Ceram. Soc. Bull., 58 (9) 856-60 (1979).) Specifically, this relationship may be expressed by the following equation:
Nb3=(9/16){(EoRT/ERT)−1} EQ. 14
Although based upon a number of simplifying assumptions, the quantity Nb3, referred to herein as the “Microcrack Parameter,” provides another useful means to quantify the degree of microcracking in a ceramic body. For a non-microcracked body, the value of Nb3 is 0.00. In the example in
Suitable batch raw materials which may be utilized according to an aspect of the invention are provided in Table 1 below.
As can be seen, the present invention may be manufactured from batches of organic and inorganic materials as described in Tables 3-9 herein. Properties of the comparative and inventive examples of the invention are described in Tables 10-18 below.
Examples C1-C4 (labeled C standing for Comparative) in Table 9 above illustrate properties typical of microcracked cordierite ceramics utilized in the “prior art” for ceramic honeycombs. The Δαmc values in the axial directions of these examples indicate an extensive level of microcracking. Inventive Examples 1-55 shown in Tables 3-9 (batches) and 11-18 (properties) according to the present invention are representative of ceramic honeycomb bodies exhibiting a relatively lower degree of microcracking and relatively high thermal shock values, and may also include higher thermal expansion coefficients (as compared to highly microcracked cordierite materials), such as CTE between 7×10−7/° C. and 15×10−7/° C. (25-800° C.).
Values of the delta CTE microcracked parameter, Δαmc, of less than 5.0 also indicate a relatively low level of microcracking. Lower (less positive) values of Δαmc, indicate a relatively lesser degree of microcracking is likely to be present in the body. Values of Δαmc s≦4.8, Δαmc≦3.5, Δαmc≦3.0, or even Δαmc≦2.0 express very low amounts of microcracking and are often associated with higher TSP (
Another indicator of the degree of microcracking present in the walls of the honeycomb body is the Eratio 1000 or the Eratio 900, wherein Eratio 1000=E1000° C./ERT and wherein Eratio 900=E900° C./ERT, wherein ERT is the room temperature elastic modulus, E900° C. is the elastic modulus at 900° C., and E1000° C. is the elastic modulus at 1000° C.
The computed strain tolerance (MOR/E) for examples from Table 10-17, together with MOR/E data for additional cordierite ceramics outside of the scope of the invention, are plotted versus the Pore Connectivity Factor (PCF) in
Additionally, according to embodiments of the invention, the porous ceramic honeycomb may further comprise MOR/CFA≧1000 psi on a cellular bar, wherein MOR is the room temperature modulus of rupture strength (psi), and CFA is the closed frontal area fraction (wall area in axial cross section (excluding plugs) divided by the total area of the ceramic honeycomb). In other embodiments, MOR/CFA≧1500 psi, MOR/CFA≧2000 psi on a cellular bar, or even MOR/CFA≧2500 psi on a cellular bar.
Certain exemplary embodiments exhibit a combination of attributes which result in a relatively high porosity honeycomb structure having good thermal shock and relatively low through-the-wall backpressure characteristics. These embodiments are excellent candidates for particulate filter applications. In particular, certain embodiments exhibit cordierite crystallites in walls of the honeycomb structure which have a preferred crystal orientation whereby ΔI≧0.1 wherein ΔI=IT−IA, CTE≦15×10−7/° C. between 25-800° C., % P≧46%, a pore size distribution characterized by a pore connectivity factor (PCF)>65%, and TSP≧550° C.
In summary, increasing the pore connectivity (as measured by increased PCF) of these non-microcracked cordierite honeycomb ceramics helps to reduce the elastic modulus, and to increase the strain tolerance of the porous material. This enables the use of higher-expansion, low-microcracked cordierites while maintaining a sufficiently high thermal shock resistance for many combustion engine pollution control applications. Additionally, the presence of an intercrystalline glass phase has been discovered to further reduce microcracking and increase strength and strain tolerance in the inventive bodies. An illustration of the intercrystalline glass phase for an inventive example employing 5% of an aftapulgite clay in the raw material mixture is shown in
Further, randomly oriented embodiments of the present inventive ceramic bodies lack a high degree of preferred crystallite orientation, exhibit reduced microcracking, and possess well interconnected porosity. As a result, the microstructure of the skin and matrix are similar in such embodiments. This may help reduce physical properties differences that can induce stress giving rise to skin defects, such as cracking. The desirable pore morphologies of these ceramic honeycombs may additionally improve filtration efficiency and reduce pressure drops in clean and soot-loaded ceramic filters.
Further advantages of such low-microcracked ceramic honeycombs may include high mechanical strength, strength being particularly important for thin-walled, low-cell density, and/or high porosity structures that are needed for reduced exhaust back pressure (such as in wall-flow filters), or for reduced thermal mass (for faster catalyst light-off), and/or for high catalyst loading capacities. The minimization of, or relative absence of, microcracks additionally stabilizes the structures against properties (or at least makes them less sensitive to) changes arising from the application of catalyst coatings and/or the accumulation of non-combustible particulates present in exhaust gases. The lack of a dependence of thermal shock on microcracking may provide more consistent products and possibly fewer manufacturing upsets.
This application claims priority to, and the benefit of, U.S. Provisional Application Ser. No. 60/840,806 filed Aug. 29, 2006 entitled “Non-Microcracked, Thermally Durable, Porous Ceramics,” U.S. Provisional Application Ser. No. 60/817,722 filed Jun. 30, 2006 entitled “High Porosity Filters for 4-Way Exhaust Gas Treatment,” and U.S. patent application Ser. No. 11/544,271 filed Oct. 6, 2006 and entitled “High Porosity Filters for 4-Way Exhaust Gas Treatment.”
| Number | Date | Country | |
|---|---|---|---|
| 60840806 | Aug 2006 | US | |
| 60817722 | Jun 2006 | US |
