(19)
(11)EP 2 176 188 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
02.09.2020 Bulletin 2020/36

(21)Application number: 08794682.8

(22)Date of filing:  22.07.2008
(51)International Patent Classification (IPC): 
C04B 28/00(2006.01)
C04B 35/185(2006.01)
C04B 35/478(2006.01)
C04B 28/24(2006.01)
C04B 35/195(2006.01)
C04B 38/00(2006.01)
(86)International application number:
PCT/US2008/008949
(87)International publication number:
WO 2009/017642 (05.02.2009 Gazette  2009/06)

(54)

METHODS FOR MANUFACTURING POROUS CERAMIC FILTERS AND COMPOSITIONS FOR APPLYING TO CERAMIC HONEYCOMB BODIES

VERFAHREN ZUR HERSTELLUNG VON PORÖSEN KERAMISCHEN FILTERN UND ZUSAMMENSETZUNGEN ZUM AUFTRAGEN AUF KERAMISCHE WABENKÖRPER

MÉTHODES DE FABRICATION DES FILTRES POREUX CÉRAMIQUES ET COMPOSITIONS POUR L'APPLICATION À DES CORPS EN NID D'ABEILLES EN CÉRAMIQUE


(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

(30)Priority: 31.07.2007 US 962715 P

(43)Date of publication of application:
21.04.2010 Bulletin 2010/16

(73)Proprietor: Corning Incorporated
Corning, NY 14831 (US)

(72)Inventors:
  • BOOKBINDER, Dana, C.
    Corning, New York 14830 (US)
  • GRIFFIN, James, A. Jr.
    Corning, New York 14830 (US)
  • TENNENT, David, L.
    Campbell, New York 14821 (US)
  • WU, Lung-Ming
    Horseheads, New York 14845 (US)

(74)Representative: Sturm, Christoph et al
Quermann - Sturm - Weilnau Patentanwälte Partnerschaft mbB Unter den Eichen 5
65195 Wiesbaden
65195 Wiesbaden (DE)


(56)References cited: : 
WO-A-02/081054
US-A1- 2007 182 072
DE-A1-102007 000 475
US-A1- 2007 262 497
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Background



    [0001] The present invention relates to the manufacture of porous ceramic particulate filters, and more particularly to improved plugging mixtures and processes for sealing selected channels of porous ceramic honeycombs to form wall-flow ceramic filters.

    Technical Background



    [0002] Ceramic wall flow filters are finding widening use for the removal of particulate pollutants from diesel or other combustion engine exhaust streams. A number of different approaches for manufacturing such filters from channeled honeycomb structures formed of porous ceramics are known. The most widespread approach is to position plugs of sealing material at the ends of alternate channels of such structures which can block direct fluid flow through the channels and force the fluid stream through the porous channel walls of the honeycombs before exiting the filter. The particulate filters used in diesel engine applications are formed from inorganic materials, chosen to provide excellent thermal shock resistance, low engine back-pressure, and acceptable durability in use. The most common filter compositions are based on silicon carbide, aluminum titanate, mullite and cordierite. Filter geometries are designed to minimize engine back-pressure and maximize filtration surface area per unit volume.

    [0003] Diesel particulate filters can consist of a parallel array of channels with every other channel on each face sealed in a checkered pattern such that exhaust gases from the engine would have to pass through the walls of the channels in order to exit the filter. Filters of this configuration are formed by extruding a matrix that makes up the array of parallel channels and then sealing or "plugging" every other channel with a sealant in a secondary processing step. Current aluminum-titanate (AT) and cordierite plugging mixtures have resulted in the formation of large pin holes and dimples during the drying step. On occasion, these can extended over the entire length of the plug and cause the part to be rejected by quality control procedures. Dimpling (which can lead to leaks) has also been a known problem and is made worse with high porosity ceramics such as AT and cordierite substrates.

    [0004] During the plugging process, the preformed slug of plugging mixture, which is fed into the substrate part (from the ram to the interface between the slug and the substrate) can run or slump in the reservoir of the piston/cylinder, resulting in nonuniform plugging and in some cases, unplugged areas of the substrate, as well as difficulties in manufacturing and yields. Additionally, current plugging mixture formulations have a pot life which is short due to changes in viscosity over time.

    [0005] Accordingly, there is a need in the art for improved plugging mixtures for forming ceramic wall flow filters. In particular, there is a need for plugging mixtures that do not result in the formation of pin holes, dimples or large internal voids. There also is a need for plugging mixtures having the rheological properties sufficient to hold their shape while in the form of a preform slug yet that can also flow properly during pressing of the mixture into the substrate.

    [0006] WO 02/081054 A discloses a method for manufacturing a porous ceramic wall flow filter, said method comprising: extruding a viscous plastic paste containing non-oxide ceramic particles, and an organic binder to form a"green" body, solidifying the "green" body by drying, and subjecting the dried solidified body to sintering under conditions sufficient to result in a porous structure, the viscous plastic paste having such rheological properties with respect to viscosity and plasticity that the extrusion results in an extrudate substantially without flaws or cracks at an extrusion pressure of at least 30 bar and an extrusion velocity of at least 60 mm per minute, these rheological properties being: an apparent viscosity within the range of 5.103 - 1.105 Pa·s, as measured by a capillary rheometer at a temperature of 35°C and within a shear rate range of 0.4 - 3.0 s-1, and such a yield stress that the paste starts flowing through a rectilinear passage, which is defined by a smooth, circularly cylindrical inner passage wall and which has an axial length of 80 mm and an inner diameter of 26 mm, when the paste is exposed to a pressure difference in the range of 100 - 400 kPa between the opposite ends of the passage and maintained at a temperature of 35°C as well as when the paste is exposed to a pressure difference of 400 - 800 kPa and maintained at a temperature of 25°C.

    Summary



    [0007] The present invention provides improved compositions for applying to honeycomb bodies. The compositions are used as plugging mixtures for forming ceramic wall flow filters. The plugging mixtures comprise one or more rheology modifiers which, when added to the mixture formulation, provide high yield strength and low viscosity under shear. Resulting from the improved rheological properties, the plugging mixtures exhibit improved performance with respect to plugging depth, and a reduction or even elimination of the formation of dimples, pinholes or large internal voids that are significantly larger than the desired pore size in the dried or fired plugs. For example, a large internal voids has a largest length dimension of greater than or equal to 0.5 mm.

    [0008] The present invention provides a method for manufacturing a porous ceramic wall flow filter according to claim 1.

    [0009] Further, the present invention provides a composition for applying to a honeycomb body according to claim 7.

    Brief Description of the Drawings



    [0010] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate certain embodiments of the instant invention and together with the description, serve to explain, without limitation, the principles of the invention.

    FIG. 1 is a perspective view of an exemplary end plugged wall flow filter according to one embodiment of the present invention.

    FIG. 2 is a schematic diagram of an inclined plane testing apparatus used to determine incline plane rate of flow according to one embodiment of the present invention.

    FIG. 3 is a photographic top view image of an aluminum titanate honeycomb substrate end plugged with a plugging mixture without a rheology modifier.

    FIG. 4 is a photographic side view image of an aluminum titanate honeycomb substrate end plugged without a rheology modifier.

    FIG. 5 is a photographic top view image of an aluminum titanate honeycomb substrate end plugged with an inventive plugging mixture according to one embodiment of the present invention.

    FIG. 6 is a photographic side view image of an aluminum titanate honeycomb substrate end plugged with an inventive plugging mixture according to one embodiment of the present invention.


    Detailed Description



    [0011] As used herein, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a "rheology modifier" includes embodiments having two or more such rheology modifiers unless the context clearly indicates otherwise.

    [0012] As used herein, a "wt. %" or "weight percent" or "percent by weight" of an inorganic component, unless specifically stated to the contrary, is based on the total weight of the inorganic powder batch composition in which the component is included.

    [0013] As used herein, a "superaddition" refers to a weight percent of a component, such as for example, an organic binder, liquid vehicle, or pore former, based upon and relative to 100 weight percent of the ceramic forming inorganic powder batch component.

    [0014] As used herein, the term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

    [0015] As briefly summarized above, the present invention provides compositions suitable for use as plugging mixtures for forming ceramic wall flow filters. Among several advantages, the compositions exhibit increased yield strengths. When used as a plugging mixture, this increased yield strength can result in reduced levels of undesired slumping or dimpling during the drying and firing process. Further, the inventive compositions also exhibit reduced viscosities under shear compared to the viscosities of conventional compositions. When used as a plugging mixture, this reduction in the viscosity under shear can also lead to an improved ability to control the depth of a desired plug within a channel.

    [0016] The inventive compositions are generally comprised of an inorganic powder batch composition; an organic binder; a liquid vehicle; and a rheology modifier. As used herein, a rheology modifier refers to a plugging mixture component that is capable of altering one or more rheological properties of a plugging mixture, including for example the viscosity and yield strength of a plugging mixture, without adversely affecting the performance properties of the plugging mixture. According to one embodiment of the present invention, the rheology modifier can be a polyethylene glycol dioleate.

    [0017] In an alternative embodiment, the rheology modifier can be an oil, such as for example a natural or synthetic oil. Specific examples of commercially available oils suitable for use a rheology modifier in the plugging mixtures of the present invention include peanut oil, soybean oil, vegetable oil, and synthetic mono- and poly-esters such as alkyl (butyl, hexyl, octyl, decyl, dodecyl, etc.) oleates, adipates, azelates, sebacates, dodecanedioates, phthalates, dimerates, neopentylglycol, trimethyol propane, pentaerythitol (C3 thru C20 acid esters, e.g., proprionate, octonate, 2-ethylhexanoate, oleate, etc.), mixtures thereof and the like; poly-alpha olefin liquids, poly-internal olefin liquids and poly butene liquids; mineral oils; silicone oils. Lists of various commercially available natural and synthetic oils and can be found in Rudnick, L.S., Shubkin, R.L. (1999), Synthetic Lubricants and High-Performance Functional Fluids, 2nd ed., Marcel and Dekker, NY, ISBN 0-8247-0194-1. In still another embodiment, a suitable rheology modifier for use in the plugging mixtures of the present invention is fumed silica.

    [0018] The rheology modifier is present as a super addition, and in an amount in the range of from approximately 0.1 weight percent to approximately 15 weight percent, preferably in the range of from approximately 0.1 weight percent to approximately 10 weight percent, of the inorganic powder batch composition, including exemplary amounts of 1.0 weight %, 2.0, weight % 3.0 weight %, 4.0 weight %, 5.0 weight %, 6.0 weight %, 7.0 weight %, 8.0 weight %, and 9.0 weight %, and an amount in any range derived from these values. For example, in another embodiment it is desirable for the rheology modifier to be present as a super addition in an amount in the range of from 4.0 weight percent to 8.0 weight percent of the inorganic powder batch composition. In some embodiments, the rheology modifier is fumed silica and is present as a super addition in an amount in the range of 0.1 weight percent to 2 weight percent of the inorganic powder batch composition. In other embodiments, the rheology modifier is an organic rheology modifier, such as oil or non-ionic surfactant, and is present as a super addition in an amount greater than 2 weight percent of the inorganic powder batch composition.

    [0019] The inorganic powder batch composition can be comprised of a combination of inorganic batch components sufficient to form a desired sintered phase ceramic composition, including for example a predominant sintered phase composition comprised of ceramic, glass-ceramic, glass, and combinations thereof. It should be understood that, as used herein, combinations of glass, ceramic, and/or glass-ceramic compositions includes both physical and/or chemical combinations, e.g., mixtures or composites. To this end, exemplary and non-limiting inorganic powder materials suitable for use in these inorganic ceramic powder batch mixtures can include cordierite, aluminum titanate, mullite, clay, kaolin, magnesium oxide sources, talc, zircon, zirconia, spinel, alumina forming sources, including aluminas and their precursors, silica forming sources, including silicas and their precursors, silicates, aluminates, lithium aluminosilicates, alumina silica, feldspar, titania, fused silica, nitrides, carbides, borides, e.g., silicon carbide, silicon nitride or mixtures of these.

    [0020] For example, in one embodiment, the inorganic powder batch composition can comprise a mixture of aluminum-titanate forming components that can be heated under conditions effective to provide a sintered phase aluminum titanate composition. In accordance with this embodiment, the inorganic powder batch composition can comprise powdered raw materials, including an alumina source, a silica source, and a titania source. These inorganic powdered raw materials can for example be selected in amounts suitable to provided a sintered phase aluminum titanate ceramic composition comprising, as characterized in an oxide weight percent basis, from about 8 to about 15 percent by weight SiO2, from about 45 to about 53 percent by weight Al2O3, and from about 27 to about 33 percent by weight TiO2. An exemplary inorganic aluminum titanate precursor powder batch composition can comprises approximately 10% quartz; approximately 47% alumina; approximately 30% titania; and approximately 13% additional inorganic additives. Additional exemplary non-limiting inorganic batch component mixtures suitable for forming aluminum titanate include those disclosed in U.S. Pat. Nos. 4,483,944; 4,855,265; 5,290,739; 6,620,751; 6,942,713; 6,849,181; U.S. Patent Application Publication Nos.:2004/0020846; 2004/0092381; and in PCT Application Publication Nos.: WO 2006/015240; WO 2005/046840; and WO 2004/011386.

    [0021] In an alternative embodiment, the inorganic powder batch composition can comprise a mixture of cordierite forming components that can be heated under conditions effective to provide a sintered phase cordierite composition. According to this embodiment, the ceramic forming inorganic powder batch composition can comprise a magnesium oxide source; an alumina source; and a silica source. For example, and without limitation, the inorganic ceramic powder batch composition can be selected to provide a cordierite composition consisting essentially of from about 49 to about 53 percent by weight SiO2, from about 33 to about 38 percent by weight Al2O3, and from about 12 to about 16 percent by weight MgO. To this end, an exemplary inorganic cordierite precursor powder batch composition can comprise about 33 to about 41 weight percent aluminum oxide source, about 46 to about 53 weight percent of a silica source, and about 11 to about 17 weight percent of a magnesium oxide source. Exemplary non-limiting inorganic batch component mixtures suitable for forming cordierite include those disclosed in U.S. Pat. Nos. 3,885,977; RE 38,888; 6,368,992; 6,319,870; 6,24,437; 6,210,626; 5,183,608; 5,258,150; 6,432,856; 6,773,657; 6,864,198; and U.S. Patent Application Publication Nos.: 2004/0029707; 2004/0261384.

    [0022] Exemplary and non-limiting examples of alumina forming sources include corundum or alpha-alumina, gamma-alumina, transitional aluminas, aluminum hydroxide such as gibbsite and bayerite, boehmite, diaspore, aluminum isopropoxide and the like. The median particle size of the alumina source is preferably greater than 5 µm, including for example, median particle sizes up to 10 µm, 15 µm, 20 µm, or even 25 µm. Commercially available alumina sources can include relatively coarse aluminas, such as the Alcan C-700 series, having a particle size of about 4-6 microns, and a specific surface area of about 0.5-1 m2 /g, e.g., C-701™ and relatively fine aluminas having a particle size of about 0.5-2 microns, and a specific surface area of about 8-11 m2 /g, such as A-16SG available from Alcoa.

    [0023] If desired, the alumina source can comprise a dispersible alumina forming source. As used herein, a dispersible alumina forming source is an alumina forming source that is at least substantially dispersible in a solvent or liquid medium and that can be used to provide a colloidal suspension in a solvent or liquid medium. In one embodiment, a dispersible alumina source can be a relatively high surface area alumina source having a specific surface area of at least 20 m2/g. Alternatively, a dispersible alumina source can have a specific surface area of at least 50 m2/g. In an exemplary embodiment, a suitable dispersible alumina source for use in the methods of the instant invention comprises alpha aluminum oxide hydroxide (AlOOH·H2O) commonly referred to as boehmite, pseudoboehmite, and as aluminum monohydrate. In another exemplary embodiment, the dispersible alumina source can comprise the so-called transition or activated aluminas (i.e., aluminum oxyhydroxide and chi, eta, rho, iota, kappa, gamma, delta, and theta alumina) which can contain various amounts of chemically bound water or hydroxyl functionalities. Specific examples of commercially available dispersible alumina sources that can be used in the present invention include, without limitation, Dispal Boehmite, commercially available from CONDEA Vista Company of Houston, Texas, and Alpha Alumina A1000, commercially available from Almatis, Inc.

    [0024] Suitable silica sources can in one embodiment comprise clay or mixtures, such as for example, raw kaolin, calcined kaolin, and/or mixtures thereof. Exemplary and non-limiting clays include non-delaminated kaolinite raw clay, having a particle size of about 7-9 microns, and a surface area of about 5-7 m2 /g, such as Hydrite MP™, those having a particle size of about 2-5 microns, and a surface area of about 10-14 m2 /g, such as Hydrite PX™ and K-10 raw clay, delaminated kaolinite having a particle size of about 1-3 microns, and a surface area of about 13-17 m2 /g, such as KAOPAQUE-10™, calcined clay, having a particle size of about 1-3 microns, and a surface area of about 6-8 m2 /g, such as Glomax LL. All of the above named materials are available from Dry Branch Kaolin, Dry Branch, Ga.

    [0025] In a further embodiment, it should also be understood that the silica forming source can further comprise crystalline silica such as quartz or cristobalite, non-crystalline silica such as fused silica or sol-gel silica, silicone resin, zeolite, and diatomaceous silica. To this end, a commercially available quartz silica forming source includes, without limitation, Imsil A25 Silica available from Laguna Clay Co. of Byesville, Ohio. In still another embodiment, the silica forming source can comprise a compound that forms free silica when heated, such as for example, silicic acid or a silicon organo-metallic compound.

    [0026] The titania source is preferably selected from, but not limited to, the group consisting of rutile and anatase titania. In one embodiment, optimization of the median particle size of the titania source can be used to avoid entrapment of unreacted oxide by the rapidly growing nuclei in the sintered ceramic body. Accordingly, in one embodiment, the median particle size of the titania is up to 20 microns.

    [0027] Exemplary and non-limiting magnesium oxide sources can include talc. In a further embodiment, suitable talcs can comprise talc having a mean particle size of at least about 5 µm, at least about 8 µm, at least about 12 µm, or even at least about 15 µm. Particle size is measured by a particle size distribution (PSD) technique, preferably by a Sedigraph by Micrometrics. In some embodiments, talc has particle sizes between 15 and 25 µm. In still a further embodiment, the talc can be a platy talc. As used herein, a platy talc refers to talc that exhibits a platelet particle morphology, i.e., particles having two long dimensions and one short dimension, or, for example, a length and width of the platelet that is much larger than its thickness. In one embodiment, the talc possesses a morphology index (Ml) of greater than about 0.50, 0.60, 0.70, or 80. To this end, the morphology index, as disclosed in U.S. Pat. No. 5,141,686, is a measure of the degree of platiness of the talc. One typical procedure for measuring the morphology index is to place the sample in a holder so that the orientation of the platy talc is maximized within the plane of the sample holder. The x-ray diffraction (XRD) pattern can then be determined for the oriented talc. The morphology index semi-quantitatively relates the platy character of the talc to its XRD peak intensities using the following equation:

    where Ix is the intensity of the peak and Iy is that of the reflection. To that end, examples of commercially available magnesium oxide sources suitable for use in the present invention include, without limitation, Mistron 002 and F-Cor (100 mesh), available from Luzenac, Inc. of Oakville, Ontario, Canada, and 96-67 Talc available from Barrett's Minerals, Inc. of Dillon, Montana.

    [0028] In another embodiment, the inorganic powder batch composition comprises powders of one or more already fired, i.e., ceramed, inorganic refractory ceramic compositions. Exemplary ceramed inorganic refractory compositions suitable for use in the inorganic powder batch composition include silicon carbide, silicon nitride, aluminum titanate, mullite, calcium aluminate, and cordierite. In one embodiment, the inorganic powder batch composition comprises a fired cordierite composition. Suitable ceramed cordierite compositions for use in the inorganic powder batch can be obtained commercially from known sources, including for example, Corning Incorporated, Corning, NY, USA. Alternatively, a suitable cordierite composition can also be manufactured by heating a cordierite forming batch composition, as described above, under conditions effective to convert the batch composition into a sintered phase cordierite. In one embodiment, a suitable ceramed cordierite consists essentially of from about 49 to about 53 percent by weight SiO2, from about 33 to about 38 percent by weight Al2O3, and from about 12 to about 16 percent by weight MgO.

    [0029] Powdered cordierite preferably has a median particle size d50 in the range of from about 10µm to about 45µm. In another embodiment, the powdered cordierite component can comprise a blend of two or more cordierite compositions, each having differing median particle sizes. For example, in one embodiment, the powdered cordierite can comprise a blend of a relatively coarse powdered cordierite and a relatively fine powdered cordierite. As used herein, a relatively coarse cordierite can, for example, be a powdered cordierite having a median particle size in the range of from about 35µm to about 45µm. Further, as used herein, a relatively fine powdered cordierite can, for example, be a powdered cordierite having a median particle size in the range of from about 10µm to about 20µm. When the powdered cordierite composition is present as a blend of two or more cordierite components having different particles sizes, the inorganic powder batch composition can comprise, for example, from about 40 weight% to about 70% of a relatively coarse powdered cordierite and from about 30 weight% to about 60 weight % of a relatively fine powdered cordierite.

    [0030] Still further, it should be understood that the inorganic batch composition can further comprise one or more additive components. For example, in one embodiment, the inorganic powder batch composition can comprise an inorganic binder, such as for example, a borosilicate glass. When present in the inorganic powder batch composition, the additive component can, for example, be used in an amount up to and including 25 weight % of the inorganic batch composition, including exemplary amounts as 1 weight%, 5 weight %, 10 weight%, 15 weight%, 20 weight%, and any range of weight percentages derived from these values.

    [0031] To provide the compositions of the present invention, the inorganic ceramic powder batch composition, comprising the aforementioned powdered ceramic materials and any optional inorganic additive components, can be mixed together with the rheology modifier, a binder, and a liquid vehicle.

    [0032] The binder component can include organic binders, inorganic binders, or a combination of both. Suitable organic binders include water soluble cellulose ether binders such as methylcellulose, hydroxypropyl methylcellulose, methylcellulose derivatives, hydroxyethyl acrylate, polyvinylalcohol, and/or any combinations thereof. Preferably, the organic binder can be present in the composition as a super addition in an amount in the range of from 0.1 weight percent to 5.0 weight percent of the inorganic powder batch composition, and more preferably, in an amount in the range of from 0.5 weight percent to 2.0 weight percent of the inorganic powder batch composition. To this end, the incorporation of the organic binder into the batch composition can further contribute to the cohesion and plasticity of the composition. The improved cohesion and plasticity can, for example, improve the ability to shape the mixture and plugging selected ends of a honeycomb body. Exemplary inorganic binders that can be used include colloidal silica and colloidal alumina.

    [0033] One liquid vehicle for providing a flowable or paste-like consistency to the inventive compositions is water, although it should be understood that other liquid vehicles exhibiting solvent action with respect to suitable temporary organic binders can be used. The amount of the liquid vehicle component can vary in order to impart optimum handling properties and compatibility with the other components in the ceramic batch mixture. In some embodiments, the liquid vehicle content is present as a super addition in an amount in the range of from 8 to 60%, and in other embodiments in the range of from 8 to 40%, and in other embodiments in the range from 15% to 60%, by weight of the inorganic powder batch composition, and in some embodiments in the range of from 20% to 40% by weight of the inorganic powder batch composition. However, it should also be understood that in another embodiment, it is desirable to minimize the amount of liquid vehicle component while still obtaining a paste like consistency capable of being forced into selected ends of a honeycomb substrate. Minimization of liquid components in the inventive compositions can lead to further reductions in undesired drying shrinkage and crack formation during the drying process.

    [0034] In addition to the rheology modifier, liquid vehicle and binder, the compositions of the present invention can also comprise one or more optional forming or processing aids. Exemplary processing aids or additives can include lubricants, ionic surfactants, plasticizers, and sintering aids. Exemplary lubricants can include tall oil, or sodium stearate. An exemplary plasticizer for use in the composition can include glycerine. Still further, suitable sintering aids can generally include an oxide source of one or more metals such as strontium, barium, iron, magnesium, zinc, calcium, aluminum, lanthanum, yttrium, titanium, bismuth, or tungsten. In one embodiment, the optional sintering aid comprise a mixture of a strontium oxide source, a calcium oxide source and an iron oxide source. In another embodiment, the optional sintering aid comprise at least one rare earth metal. It should be understood that the sintering aid can be added to the batch composition in a powder and/or a liquid form.

    [0035] As summarized above, the compositions of the present invention can be used as plugging mixtures to provide end plugged porous ceramic wall flow filters. In particular, these plugging mixtures are well suited for providing end plugged ceramic honeycomb bodies. For example, in one embodiment, an end plugged ceramic wall flow filter can be formed from a honeycomb substrate that defines a plurality of cell channels bounded by porous channel walls that extend longitudinally from an upstream inlet end to a downstream outlet end. A first portion of the plurality of cell channels can comprise an end plug, formed from a plugging mixture as described herein, and sealed to the respective channel walls at the downstream outlet end to form inlet cell channels. A second portion of the plurality of cell channels can also comprise an end plug, formed from a plugging mixture as described herein, and sealed to the respective channel walls at the upstream inlet end to form outlet cell channels.

    [0036] Accordingly, the present invention further provides a method for manufacturing a porous ceramic wall flow filter having a ceramic honeycomb body and a plurality of channels bounded by porous ceramic walls, with selected channels each incorporating a plug sealed to the channel wall. The method generally comprises the steps of providing a honeycomb body defining a plurality of cell channels bounded by porous channel walls that extend longitudinally from an upstream inlet end to a downstream outlet end and selectively plugging an end of at least one predetermined channel with a plugging mixture as described herein. The selectively plugged honeycomb body can then be fired under conditions effective to form a sintered phase ceramic plug in the at least one selectively plugged channel.

    [0037] In one embodiment, the honeycomb substrate to be plugged can be a green substrate. According to this embodiment, if the plugging mixture used to plug the selected cell channels of the green substrate is comprised of a ceramic forming powder batch composition as described herein, the plugging mixture can be fired simultaneously with the green honeycomb substrate in a "single fire" process. In another embodiment, the honeycomb substrate to be plugged can be an already fired or ceramed honeycomb substrate. According to this embodiment, the firing temperature used to fire the end plugs will depend, at least in part, on the composition of the plugging material. For example, if the plugging mixture used to plug the selected cell channels of the ceramed substrate is again comprised of a ceramic forming powder batch composition as described herein, the plugging mixture can be fired for the first time in what is called a "second fire" process. Alternatively, if the plugging mixture used to plug the selected cell channels of the ceramed substrate is comprised of already fired or ceramed inorganic powder batch components, the plugging mixture can be heated at a lower temperature than firing, also referred to as a "cold set" plugging procedure.

    [0038] With reference to FIG. 2, an exemplary end plugged wall flow filter 100 is shown. As illustrated, the wall flow filter 100 has an upstream inlet end 102 and a downstream outlet end 104, and a multiplicity of cells 108 (inlet), 110 (outlet) extending longitudinally from the inlet end to the outlet end. The multiplicity of cells is formed from intersecting porous cell walls 106. A first portion of the plurality of cell channels are plugged with end plugs 112 at the downstream outlet end (not shown) to form inlet cell channels and a second portion of the plurality of cell channels are plugged at the upstream inlet end with end plugs 112 to form outlet cell channels. The exemplified plugging configuration forms alternating inlet and outlet channels such that a fluid stream flowing into the reactor through the open cells at the inlet end 102, then through the porous cell walls 106, and out of the reactor through the open cells at the outlet end 104. The exemplified end plugged cell configuration can be referred to herein as a "wall flow" configuration since the flow paths resulting from alternate channel plugging direct a fluid stream being treated to flow through the porous ceramic cell walls prior to exiting the filter.

    [0039] The honeycomb substrate can be formed from any conventional material suitable for forming a porous monolithic honeycomb body. For example, in one embodiment, the substrate can be formed from a plasticized ceramic forming composition. Exemplary ceramic forming compositions can include those conventionally known for forming cordierite, aluminum titanate, silicon carbide, aluminum oxide, zirconium oxide, zirconia, magnesium stabilized zirconia, zirconia stabilized alumina, yttrium stabilized zirconia, calcium stabilized zirconia, alumina, magnesium stabilized alumina, calcium stabilized alumina, titania, silica, magnesia, niobia, ceria, vanadia, silicon nitride, or any combination thereof.

    [0040] The honeycomb substrate can be formed according to any conventional process suitable for forming honeycomb monolith bodies. For example, in one embodiment a plasticized ceramic forming batch composition can be shaped into a green body by any known conventional ceramic forming process, such as, e.g., extrusion, injection molding, slip casting, centrifugal casting, pressure casting, dry pressing, and the like. Preferably, the ceramic precursor batch composition comprises inorganic ceramic forming batch component(s) capable of forming, for example, one or more of the sintered phase ceramic compositions set forth above, a liquid vehicle, a binder, and one or more optional processing aids and additives including, for example, lubricants, and/or a pore former. In an exemplary embodiment, extrusion can be done using a hydraulic ram extrusion press, or a two stage de-airing single auger extruder, or a twin screw mixer with a die assembly attached to the discharge end. In the latter, the proper screw elements are chosen according to material and other process conditions in order to build up sufficient pressure to force the batch material through the die.

    [0041] The formed monolithic honeycomb 100 can have an exemplary cell density of from about 70 cells/in2 (10.9 cells/cm2) to about 400 cells/in2 (62 cells/cm2). Still further, as described above, a portion of the cells 110 at the inlet end 102 are plugged with a paste having the same or similar composition to that of the body 101. The plugging is preferably performed only at the ends of the cells and form plugs 112 having a depth of about 5 to 20 mm, although this can vary. A portion of the cells on the outlet end 104 but not corresponding to those on the inlet end 102 may also be plugged in a similar pattern. Therefore, each cell is preferably plugged only at one end. The preferred arrangement is to therefore have every other cell on a given face plugged as in a checkered pattern as shown in FIG. 1. Further, the inlet and outlet channels can be any desired shape. However, in the exemplified embodiment shown in FIG. 1, the cell channels are square in cross-sectional shape. Once formed, the green body can then be fired to form a sintered phase ceramic composition.

    [0042] The inorganic batch components can be selected so as to yield a ceramic honeycomb article comprising cordierite, mullite, spinel, aluminum titanate, or a mixture thereof upon firing. For example, and without limitation, in one embodiment, the inorganic batch components can be selected to provide a cordierite composition consisting essentially of, as characterized in an oxide weight percent basis, from about 49 to about 53 percent by weight SiO2, from about 33 to about 38 percent by weight Al2O3, and from about 12 to about 16 percent by weight MgO. To this end, an exemplary inorganic cordierite precursor powder batch composition preferably comprises about 33 to about 41 weight percent aluminum oxide source, about 46 to about 53 weight percent of a silica source, and about 11 to about 17 weight percent of a magnesium oxide source. Exemplary non-limiting inorganic batch component mixtures suitable for forming cordierite include those disclosed in U.S. Pat. Nos. 3,885,977; RE 38,888; 6,368,992; 6,319,870; 6,24,437; 6,210,626; 5,183,608; 5,258,150; 6,432,856; 6,773,657; 6,864,198; and U.S. Patent Application Publication Nos.: 2004/0029707; 2004/0261384.

    [0043] Alternatively, in another embodiment, the honeycomb body can be formed from inorganic batch components selected to provide, upon firing, a mullite composition consisting essentially of, as characterized in an oxide weight percent basis, from 27 to 30 percent by weight SiO2, and from about 68 to 72 percent by weight Al2O3. An exemplary inorganic mullite precursor powder batch composition can comprise approximately 76% mullite refractory aggregate; approximately 9.0% fine clay; and approximately 15% alpha alumina. Additional exemplary non-limiting inorganic batch component mixtures suitable for forming mullite include those disclosed in U.S. Pat. Nos.: 6,254,822 and 6,238,618.

    [0044] Still further, the honeycomb body can be formed from inorganic batch components selected to provide, upon firing, an aluminum-titanate composition consisting essentially of, as characterized in an oxide weight percent basis, from about 8 to about 15 percent by weight SiO2, from about 45 to about 53 percent by weight Al2O3, and from about 27 to about 33 percent by weight TiO2. An exemplary inorganic aluminum titanate precursor powder batch composition can comprises approximately 10% quartz; approximately 47% alumina; approximately 30% titania; and approximately 13% additional inorganic additives. Additional exemplary non-limiting inorganic batch component mixtures suitable for forming aluminum titanate include those disclosed in U.S. Pat. Nos. 4,483,944; 4,855,265; 5,290,739; 6,620,751; 6,942,713; 6,849,181; U.S. Patent Application Publication Nos.:2004/0020846; 2004/0092381; and in PCT Application Publication Nos.: WO 2006/015240; WO 2005/046840; and WO 2004/011386.

    [0045] Once the honeycomb substrate is formed, a plugging mixture as described herein can then be forced into selected open cells of either a green honeycomb substrate or an already fired honeycomb substrate in the desired plugging pattern and to the desired depth, by one of several conventionally known plugging process methods. For example, selected channels can be end plugged as shown in FIG. 3 to provide a "wall flow" configuration whereby the flow paths resulting from alternate channel plugging direct a fluid or gas stream entering the upstream inlet end of the exemplified honeycomb substrate, through the porous ceramic cell walls prior to exiting the filter at the downstream outlet end. The plugging can be effectuated by, for example, using a conventional masking apparatus and process such as that disclosed and described in U.S. Patent No, 6,673,300.

    [0046] The resulting plugged honeycomb body can then be dried, and subsequently fired under conditions effective to convert the plugging mixture into a primary sintered phase ceramic composition. Conditions effective for drying the plugging material functionally include those conditions capable of removing at least substantially all of the liquid vehicle present within the plugging mixture. As used herein, at least substantially all include the removal of at least 95%, at least 98%, at least 99%, or even at least 99.9 % of the liquid vehicle present in the plugging mixture. Exemplary and non-limiting drying conditions suitable for removing the liquid vehicle include heating the end plugged honeycomb substrate at a temperature of at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 110°C, at least 120°C, at least 130°C, at least 140°C, or even at least 150°C for a period of time sufficient to at least substantially remove the liquid vehicle from the plugging mixture. In one embodiment, the conditions effective to at least substantially remove the liquid vehicle comprise heating the plugging mixture at a temperature of at least about 60°C. Further, the heating can be provided by any conventionally known method, including for example, hot air drying, or RF and/or microwave drying.

    [0047] After drying, the plugging mixtures as described herein can be fired under conditions effective to convert the plugging material into a primary sintered phase ceramic composition. In one embodiment, the step of firing the plugging material can be a "single fire" process as described above. According to this embodiment, the selectively end plugged honeycomb substrate is a green body or unfired honeycomb body comprised of a dried plasticized ceramic forming precursor composition. The conditions effective to fire the plugging mixture are also effective to convert the dried ceramic precursor composition of the green body into a sintered phase ceramic composition. Further according to this embodiment, the unfired honeycomb green body can be selectively plugged with a plugging mixture having a composition that is substantially equivalent to the inorganic composition of the honeycomb green body. Thus, the plugging material can for example comprise either the same raw material sources or alternative raw material sources chosen to at least substantially match the drying and firing shrinkage of the green honeycomb. Exemplary conditions effective to simultaneously single fire the plugging mixture and the green body can comprise firing the selectively plugged honeycomb body at a maximum firing temperature in the range of from 1350°C to 1500°C, and more preferably at a maximum firing temperature in the range of from 1375°C to 1425°C.

    [0048] In an alternative embodiment, the step of firing the plugging material can be a "second fire" process. According to this embodiment, the provided honeycomb substrate has already been fired to provide a ceramic honeycomb body prior to selectively end plugging the honeycomb substrate with the plugging mixture of the present invention. Accordingly, the conditions effective to fire the plugging mixture are those effective to convert the plugging mixture into the ceramic composition. To this end, it can be desirable to selectively plug one or more channels of the honeycomb body with a plugging mixture that will result in a plug with physical properties similar to the honeycomb, but which can be fired without altering the properties of the ceramed honeycomb substrate. For example, a plugging mixture according to this embodiment can be chosen to lower the peak firing temperature required for firing of the plugs to a temperature below the peak firing temperature of the fired ceramic honeycomb body.

    [0049] The conditions effective to set or cure the plugging mixture in a second heating process will again depend in part on the particular composition of the plugging material. However, effective heating conditions can comprise heating the plugging material at a maximum temperature of, at least 400°C, at least 700°C, at least 800°C, at least 900°C, or even at least 1000°C. Preferably, organic materials are removed from the body as a result of such heating.

    Examples



    [0050] To further illustrate the principles of the present invention, the following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the plugging mixtures and methods claimed herein are made and evaluated. They are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention. Unless indicated otherwise, parts are parts by weight, temperature is °C or is at ambient temperature, and pressure is at or near atmospheric.

    [0051] In the following Examples, a number of plugging mixtures were prepared and evaluated for rheological properties including yield strength, as indicated by a resistance to slumping and deformation, and capillary viscosity. Additionally, the plugging mixtures were also evaluated for their performance properties when used to form end plugs in both cordierite and aluminum titanate honeycomb articles. In particular, the evaluated performance properties included the plugging materials ability to achieve a uniform and desired plugging depth and to provide a dried and fired plug exhibiting little or no dimple formation.

    [0052] Examples 1-27 were evaluated for the performance of plugging mixtures comprising already fired or ceramed cordierite. A listing of the materials used to prepare the plugging mixtures utilized in Examples 1-27 is set forth in Table 1 below.
    TABLE 1 - Materials Used
    ComponentProduct NameSupplierSupplier AddressRheology Modifier Code
    Methylcellulose Methocel® A4M Dow Chemical Midland, MI -
    Colloidal Silica Ludox® HS40 W.R. Grace Columbia MD -
    Borosilicate Glass (-325 mesh) Pyrex® 7761 Corning, Inc. Corning, NY -
    Powdered cordierite d50 40.4 Coarse Cordierite Corning, Inc. Corning, NY -
    Powdered Cordierite d50 14.5 Fine Cordierite Corning, Inc. Corning, NY -
    Deionized water Deionized Water - - -
    Sorbitan monolaurate Span® 20 Croda, Inc. Edison NJ RM-1
    Polyoxyethylene (2) oleyl ether Brij® 93 Croda, Inc. Edison NJ RM-2
    Polyethylene glycol 400 dioleate PEG 400 DO BASF Florham Park NJ RM-3
    Polyethylene glycol 200 dioleate PEG 200 DO Stepan, Inc. Northfield IL. RM-4
    Fumed Silica Cabosil® EH5 Cabot Corp. Billerica MA RM-5
    Peanut Oil Peanut Oil Wegmans, Inc. Rochester NY RM-6
    Soybean Oil Soybean Oil Cargill, Inc. Chicago IL RM-7
    Glycerol Monoleate GMO Emery Cincinnati OH RM-8
    Vegetable Oil Agri-Pure™ 60 Cargill, Inc. Chicago IL RM-9
    Oleyl alcohol Oleyl Alcohol Sigma-Aldrich Milwaukee WI RM-10
    Polyoxyethylene (20) cetyl ether Brij® 58 Croda Inc. Edison, NJ RM-11
    Polyoxyethylene (4) sorbitan monolaurate Tween® 21 Croda Inc. Edison, NJ RM-12
    Polyoxyethylene (6) Nonylphenol Igepal® CO530 Rhodia Inc. Cranbury, NJ RM-13


    [0053] Examples 28-30 evaluated the performance of plugging mixtures comprised of a cordierite forming ceramic batch composition. In addition to the materials set forth above in Table 1, the formulation for the cordierite forming ceramic batch composition used in Examples 28-30 is set forth in Table 2 below:
    TABLE 2 - Cordierite Forming Composition
    ComponentProduct NameSupplierSupplier AddressWeight %
    Talc F-Cor Luzenac Greenwood Village, CO 35.03
    Clay K-10 Imerys Roswell, GA 13.76
    Silica Cerasil 300 4 Unimin Corp. New Canaan, CT 10.76
    Alumina A3000 Almatis GmbH Frankfurt-am main, Germany 12.73
    Alumina Micral 6000 (AC714) Aluchem, Inc. Reading, OH 13.76
    Graphite Asbury 4740 Asbury Carbon Asbury, NJ 12.91
    Ionic Lubricant SAN Liga Peter Greven Bad Munstereifel, Germany 0.45
    Organic Binder Methocel BD06 (F240) Dow Chemical Midland, MI 0.60


    [0054] The plugging mixture formulations prepared using the materials from Tables 1 and 2 are set forth in Table 3 below.
    TABLE 3 - Plugging Mixture Formulations
    ExampleCordierite Forming CompositionCoarse Cordierite (grams)Fine Cordierite (grams)Pyrex (grams)Methocel (grams)Ludox (grams)Water (grams)(Rheology Modifier) grams
    1 - 50 30 20 1 25 24 (RM-3) 6
    2 - 50 30 20 1 25 26 (RM-3) 6
    3 - 50 30 20 1 25 28 (RM-3 6
    4 - 50 30 20 1 25 32 (RM-3) 6
    5 - 50 30 20 1 25 36 (RM-3 6
    6 - 50 30 20 1 25 26 (RM-3) 3
    7 - 50 30 20 1 25 26 (RM-4) 6
    8 - 50 30 19.5 1 25 26 (RM-5) 0.5
    9 - 50 30 20 1 25 26 (RM-1) 6
    10 - 50 30 20 1 25 22 (RM-2) 6
    11 - 50 30 20 1 25 26 (RM-2) 6
    12 - 50 30 20 1 25 28 (RM-2) 6
    13 - 50 30 20 1 25 19 (RM-7) 6
    14 - 50 30 20 1 25 19 (RM-6) 6
    15 - 50 30 20 1 - 40 (RM-7) 6
    16 - 50 30 20 1 - 40 (RM-6) 6
    17 - 50 30 20 1 - 40 (RM-8) 6
    18 - 50 30 20 1 - 40 (RM-10) 6
    19 - 50 30 20 1 - 37 (RM-10) 6
    20 - 50 30 20 1 - 40 (RM-2) 6
    21 - 50 30 20 1 - 38 (RM-9) 6
    22 - 50 30 20 1 - 40 (RM-9) 6
    23 - 62.5 37.5 - 1 25 20 (RM-2) 6
    24 - 62.5 37.5 - 1 25 20 (RM-9) 6
    25 - 62.5 37.5 - 1 25 22 (RM-9) 6
    26 - 62.5 37.5 - 1 25 26 (RM-12) 6
    27 - 62.5 37.5 - 1 25 26 (RM-13) 6
    28 100 - - - - - 31.6 (RM-11)6
    29 100 - - - - - 31.6 (RM-13) 6
    30 100 - - - - 25 10.6 (RM-3) 12


    [0055] To prepare the plugging formulations set forth in Table 3 above, the dry components for each formulation were weighed into a 250 ml plastic container and sealed with a lid. The dry components were then shaken for one minute to ensure good mixing. The liquid components of each formulation were then added and mixed using a metal spatula to provide the resulting plugging mixture. The inclined plane test, capillary viscosity test, and substrate plugging tests required approximate batch sizes of 75 grams, 150 grams, and 225 grams, respectively. Larger batch quantities (e.g., 10 Kg or larger) of these formulations were also made for scale-up to a pilot and manufacturing lines. The rheological tests and plugging of parts was carried out immediately after mixing of the plugging mixtures was complete.

    [0056] An inclined plane test was developed to evaluate the plugging mixture paste formulation's resistance to deformation and slumping. This is a measurement of a material's ability to maintain shape and not yield as well as also to provide insight for a material to not form dimples. This test used a 60 degree inclined plane to measure the rate of mixture flow. A schematic of the inclined plane test apparatus is shown in FIG. 2. As shown, the test apparatus comprised a clear plastic plate 301 that was formed from Lexan® brand polycarbonate and having a ruler 302 attached to the underside of the plate. The plate was positioned at a 60 degree angle with respect to level. A 32 mm inside diameter by 36 mm outside diameter silica glass tube 303 having a 50mm length was used as a holding container for the plugging mixture to be tested at the 60 degree angle 304. The tube, which was open at both ends, was fully packed with the plugging mixture to be tested 306 and to that end held approximately 75 grams of mixture paste. To ensure the tube was fully packed and absent of any internal voids, the tube was filled with excess plugging mixture, after which both ends of the tube were scraped flush to remove any excess. The filled tube was held horizontal with the ends blocked by wax paper until it was inserted into a holder 305 attached to the plastic inclined plane plate so that the inside diameter of the tube 303 was even with the surface of the plate. The beginning of flow was defined as and calculated from the time at which the plugging mixture within the tube began touching the surface of the plate 301.

    [0057] All inclined plane flow experiments were preformed at room temperature of approximately 22-24 degrees Celsius and relative humidity of approximately 50%. Mixture paste formulations were made immediately prior to inclined plane testing. Measurements of the mixture paste flow verses time were recorded over an 8 minute period wherein the test was completed. The results of the inclined plane test for the plugging formulations are set forth in Table 5 below and reported in units of mm flow after 8 minutes. In some cases the inclined plane test was terminated early due to a mixture paste flowing rapidly past the end of the plate 301; this was observed with some ceramic paste formulations without the current inventive rheology modifier additions.

    [0058] A capillary viscosity test was used to determine and compare the viscosity of the plugging mixtures over the range of shear rates of from 1/s to 50/s. This characterization method was used to determine a material's ability to flow under applied shear, i.e., shear experienced while pumping the mixture paste and plugging a substrate. The capillary viscosity test was conducted using a Rosand RH-7 capillary viscometer (Malvern Instruments Inc. 10 Southville Road, Southborough MA 01772). The viscometer had a barrel/plunger diameter of 15 mm, and a sample chamber within the barrel of approximately 250 mm, and utilized a capillary die (Part #DA-1.0-0.25-90-15), having a length of 0.25mm, a diameter of 1mm, and entry angle of 90 degrees, and an outside diameter of 15mm. A 250 psi pressure transducer was used. The plunger speeds with corresponding shear rates is shown below in Table 4.
    TABLE 4
    Shear rate (/s)Speed (mm/min)
    1 0.03
    1.63 0.05
    2.66 0.09
    4.34 0.14
    7.07 0.24
    11.53 0.38
    18.8 0.63
    30.66 1.02
    50 1.67


    [0059] The apparent viscosity, without correction, was recorded as a function of shear rate. Based on the typical cell geometry of a honeycomb article to be end plugged, and the typical time required to push the plugging paste into the selected honeycomb cells, it was estimated that the shear rate was approximately 10/s for plugging the honeycomb ceramic substrates used in the following examples. Accordingly, the apparent viscosities of the plugging mixtures of Examples 1 through 24, for a shear rate of 10/s, are reported in Table 5 below.

    [0060] Following the inclined plane and capillary viscosity tests described above, the plugging mixtures of Examples 1 through 30 were used to plug exemplary aluminum titanate and cordierite honeycomb substrates. The plugged substrates were then evaluated for the plugging depth, existence of dimple formation and the existence of voids or pinhole formation. The Aluminum-Titanate substrates comprised cell geometries of 300 cells per square inch and 13 mil wall thickness. The overall dimension of the aluminum titanate honeycomb bodies were a 4" x 7.8" x 6.8" oval and had porosity %P of about 50 to 51%. Further, the median pore size of the porosity %P was in the range of from 12µm to 16µm. Similarly, the Cordierite substrates used had cell geometries of 275 cells per square inch with a 15 mil wall thickness. The overall part size was 5.66" diameter x 6" length and porosity of approximately 50%.

    [0061] To plug the honeycomb bodies, a polymer mask with a checkerboard pattern was placed on both ends of the ceramic substrate to be plugged with the mixture paste. The mask had holes which opened to alternating cells on the substrate ends. A roll of 1 inch wide masking tape was used to wrap the end of the substrate thus creating an approximately 5 mm tall dam for the plugging mixture. Plugging mixture formulations were prepared just prior to plugging and placed on the ceramic substrate to the top of the tape dam. This assembly was placed in a hydraulic press (parallel ends pushing on the mixture paste) where it took approximately 5-10 seconds to push the paste into the masked ceramic substrate. As stated above, based on the cell geometry and time to push the plugging paste into the cells, it was estimated that the capillary viscosity shear rate is approximately 10/s for plugging the honeycomb ceramic substrates used in these examples. Following pressing, the polymer mask was removed; the sample was placed in an oven set at 60 degrees Celsius and dried for 6-24 hours. Parts were then cut open to measure the depth the plugging mixture filled the ceramic substrate. Parts were also fired for 1-6 hours at approximately 1000 degrees Celsius.

    [0062] The results from the inclined plane, capillary viscometer and substrate plugging tests are shown below in Table 5. In some embodiments, it is desirable to obtain plug depths of 5-10 mm to assure that the parts are plugged (and the plugs don't fall out) and that the plug lasts over the lifetime of the honeycomb body, e.g. diesel filter. The inventive plugging mixture pastes comprised of the rheology modifiers, exhibited excellent plugging depths, low capillary viscosity, no dimples or large internal voids after drying or firing, and had excellent slumping resistance.
    TABLE 5
    Example #Capillary Viscosity (Pa.s)Inclined PlanePlug Depth AT (mm)Dimples in plugged AT*Plug Depth Cordierite (mm)Dimples in plugged cordierite*
    1 6000 0 10 No NA NA
    2 4100 0 10 No NA NA
    3 3000 0 10 No 12 Some
    4 1500 0 10 No NA NA
    5 700 23 10 Some NA NA
    6 1500 0 10 No NA NA
    7 6000 0 10 No NA NA
    8 1800 26 5 No NA NA
    9 3200 0 10 No NA NA
    10 2100 0 10 Some 12 Some
    11 820 0 10 No 12 Some
    12 140 45 10 No NA NA
    13 2200 0 10 Some NA NA
    14 2400 0 10 No NA NA
    15 1400 0 10 No NA NA
    16 1600 0 10 No NA NA
    17 900 0 10 No NA NA
    18 550 26 10 No NA NA
    19 1300 0 8 No NA NA
    20 1200 0 10 Some NA NA
    21 1400 0 8 No 5 NA
    22 850 20 10 No NA NA
    23 2350 15 7 No NA NA
    24 2200 5 7 No NA NA
    25 3800 0 10 No 7 no
    * "Some" means some cells dimpled at depths of about 1 mm, but no large internal voids; "No" means no dimples or large internal voids were observed.


    [0063] The data set forth in Table 5 indicates that the plugging mixtures of Examples 1-25 exhibit several improved rheological properties and performance properties. For example, the inventive plugging mixtures exhibited a capillary viscosity less than 8000 Pa·s when measured at a shear rate of 10/sec. In still further embodiments, certain inventive plugging mixtures also exhibited capillary viscosity less than 6000 Pa·s, less than 4000 Pa·s, and even less than 2000 Pa·s, when measured at a shear rate of 10/sec. Additionally, the inventive plugging mixtures also exhibited an inclined plane flow rate less than 60mm/8min when measured at an angle of 60 degrees. In still further embodiments, certain inventive plugging mixtures also exhibited inclined plane flow rates less than 50mm/8min, less than 40mm/8min, and even less than 30mm/8min.

    [0064] Further, the inventive plugging mixtures were able to achieve relatively uniform plugging depths in the range of from 5 to 10 mm and resulted in a reduction in surface dimples and void formations. For example, a top and side view of the Aluminum-Titanate substrate plugged with a plugging formulation similar to Example 2 but with no rheology modifier and 1 g less water is shown in FIG. 3 and FIG. 4, respectively. As shown in FIG. 3, the ruler in the top of the photo indicates the existence of approximately 1 mm diameter dimples, 1 mm length voids, or pinholes in the ends of the dried plugs. Similarly, as shown in FIG. 4, the ruler at the side of the photo indicates the existence of 4-5 mm deep dimples and 1 mm spacings or voids, and the results looked similar after firing to 1000 °C. In contrast, the top and side view of an aluminum titanate substrate plugged with the inventive plugging mixture of Example 2 is shown in FIG. 5 and FIG. 6, respectively, and the results looked similar after firing to 1000 °C. These images indicate that the pinhole holes and dimples illustrated in FIG. 3 and FIG. 4 did not exist when using an inventive plugging mixture comprised of a rheology modifier as described herein.

    [0065] The plugging mixtures of Examples 25-30 were next evaluated for their use in plugging green honeycomb bodies formed from an unfired cordierite forming ceramic precursor composition. In particular, the green honeycomb bodies were formed from a water plasticized precursor batch composition (which was extruded to form a honeycomb body and then dried) as set forth in Table 6 below:
    TABLE 6
    ComponentProduct NameSupplierSupplier AddressParts by wt.
    Talc Luzenac F-Cor Luzenac Greenwood Village, CO 39.5
    Silica Silverbond 200 Unimim Corp. New Canaan, CT 13.5
    Alumina C701 Alumina Alcan Chicago, IL 12
    Aluminum Trihvdrate AC400 Aluminum Aluchem, Inc. Reading . OH 16
    Clav K-10 Imervs Roswell, GA 17.2
    Starch Potato Starch T.J. Harkins Wood Dale, IL 10
    Organic Binder Methocel F240 Dow Chemical Midland, Ml 4
    Crosslinker Berset 2506/Water Bercen, Inc. Cranston, RI 2.5
    Lubricant Emulsia T/water* Corning, Inc. Corning, NY 8
    Organic Binder Klardaid PC1195 GE Betz Trevose, PA .45
    Inorganic Binder AL-20 SD Nvacol, Inc. Ashland, MA 9
    * a combination of triethanol amine and tall oil in a 1:1 mole ratio and diluted to 10 wt% in water


    [0066] Using the plasticized batch composition as set forth in TABLE 6, honeycomb bodies were prepared by an extrusion technique having a diameter of approximately 6 inches, a length of approximately 6.5 inches, a cell density of approximately 196 cells per square inch and channel wall thicknesses of approximately 17 mils. The formed green bodies were then dried to at least substantially remove any liquids from the extruded parts. To plug and dry the green honeycomb bodies of Examples 25-30, the procedures used to plug and dry the honeycomb bodies of Examples 1-25 were used. The plugged and dried green honeycomb bodies were then evaluated for the plugging depth and the existence of dimple formation. The results of this evaluation are set forth in TABLE 7 below:
    TABLE 7
    Example #Capillary Viscosity (Pa.s)Plug Depth in Green Body (mm)Dimple Formation
    25 3800 11 None
    26 550 10 None
    27 500 10 None
    28 1400 12 None
    29 2050 10 Slight
    30 7800 10 None


    [0067] The data set forth in Table 7 again illustrates that the inventive compositions of the present invention can exhibit several improved performance properties, and even when used as plugging mixtures for plugging green unfired honeycomb bodies. In particular, Table 7 indicates that uniform plugging depths of at least 10mm were again achieved without any significant formation of dimples during the drying process.


    Claims

    1. A method for manufacturing a porous ceramic wall flow filter, comprising the steps of:

    providing a honeycomb structure defining a plurality of cell channels bounded by porous channel walls that extend longitudinally from an upstream inlet end to a downstream outlet end;

    providing a plugging mixture, the plugging mixture comprising an inorganic powder batch composition;

    a binder; a liquid vehicle; and a rheology modifier selected from the group consisting of a polyethylene glycol dioleate, an oil, and fumed silica, the rheology modifier being present as a super addition in an amount in the range of from 0.1 weight percent to 15 weight percent relative to the inorganic powder batch composition;
    the plugging mixture exhibiting an inclined plane flow rate less than 60mm/8 min when measured at an angle of 60 degrees;

    selectively plugging an end of at least one predetermined channel with the plugging mixture which exhibits a capillary viscosity less than 8000 Pa·s when measured at a shear rate of 10/sec;

    firing the selectively plugged honeycomb body under conditions effective to form a sintered phase ceramic plug in the at least one selectively plugged channel by converting the plugging material into a primary sintered phase ceramic composition, wherein the firing comprises heating the plugging material at a maximum temperature of at least 400°C.


     
    2. The method of Claim 1, wherein the rheology modifier comprises an oil.
     
    3. The method of Claim 1, wherein the rheology modifier comprises peanut oil, soybean oil, vegetable oil, or oleyl alcohol.
     
    4. The method of Claim 1, wherein the rheology modifier comprises fumed silica.
     
    5. The method of Claim 1, wherein the rheology modifier comprises polyoxyethylene (2) oleyl ether, sorbitan monolaurate, or glycerol mono-oleate.
     
    6. The method of Claim 1, wherein the inorganic powder batch composition comprises cordierite; and
    wherein the cordierite comprises a blend of a first powdered cordierite having a median particle size in the range of from 35µm to 45µm and a second powdered cordierite having a median particle size in the range of from 10µm to 20µm.
     
    7. A plugging composition for applying to a honeycomb body defining cell channels bounded by porous channel walls that extend longitudinally from an upstream inlet end to a downstream outlet end, the plugging composition comprising:

    an inorganic powder batch composition;

    a binder;

    a liquid vehicle; and

    a rheology modifier selected from the group consisting of a polyethylene glycol dioleate, an oil, and fumed silica,
    the rheology modifier being present as a super addition in an amount in the range of from 0.1 weight percent to 15 weight percent relative to the inorganic powder batch composition;

    wherein the composition (i) exhibits a capillary viscosity less than 8000 Pa·s when measured at a shear rate of 10/sec, and (ii) exhibits an inclined plane flow rate less than 60mm/8min when measured at an angle of 60 degrees.
     
    8. The plugging composition of Claim 7, wherein the rheology modifier comprises an oil.
     
    9. The plugging composition of Claim 7, wherein the rheology modifier comprises peanut oil, soybean oil, vegetable oil, or oleyl alcohol.
     
    10. The plugging composition of Claim 7, wherein the rheology modifier comprises fumed silica.
     
    11. The plugging composition of Claim 7, wherein the rheology modifier comprises polyoxyethylene (2) oleyl ether, sorbitan monolaurate, or glycerol mono-oleate.
     
    12. The plugging composition of Claim 7, wherein the inorganic batch composition comprises fired cordierite; and
    wherein the cordierite comprises a blend of a first powdered cordierite having a median particle size in the range of from 35µm to 45µm and a second powdered cordierite having a median particle size in the range of from 10µm to 20µm.
     


    Ansprüche

    1. Verfahren zur Herstellung eines porösen keramischen Wandstromfilters, umfassend die folgenden Schritte:

    Bereitstellen einer Wabenstruktur, die mehrere Zellkanäle definiert, die durch sich in Längsrichtung von einem stromaufwärtigen Einlassende zu einem stromabwärtigen Auslassende erstreckende poröse Kanalwände begrenzt sind;

    Bereitstellen einer zusetzenden Mischung, wobei die zusetzende Mischung eine Chargenzuammensetzung eines anorganischen Pulvers; ein Bindemittel; ein flüssiges Vehikel und einen aus der Gruppe bestehend aus einem Polyethylenglykoldioleat, einem Öl und pyrogener Kieselsäure ausgewählten Rheologiemodifikator umfasst, wobei der Rheologiemodifikator als zusätzliche Zugabe in einer Menge im Bereich von 0,1 Gewichtsprozent bis 15 Gewichtsprozent, bezogen auf das Gewicht der Chargenzuammensetzung des anorganischen Pulvers, vorliegt;
    wobei die zusetzende Mischung eine auf einer schiefen Ebene mit einem Winkel von 60 Grad gemessene Fließrate von weniger als 60 mm/8 min aufweist;

    selektives Zusetzen von einem Ende von mindestens einem vorgegebenen Kanal mit der zusetzenden Mischung, die eine bei einer Scherrate von 10/sek gemessene Kapillarviskosität von weniger als 8000 Pa·s aufweist;

    Brennen des selektiv zugesetzten Wabenkörpers unter Bedingungen, unter denen sich durch Umwandeln des zusetzenden Materials in eine Keramikzusammensetzung mit einer hauptsächlich gesinterten Phase ein Sinterphasen-Keramikpropfen in dem mindestens einen selektiv zugesetzten Kanal bildet,
    wobei das Brennen das Erhitzen des zusetzenden Materials bei einer Höchsttemperatur von mindestens 400°C umfasst.


     
    2. Verfahren nach Anspruch 1, wobei der Rheologiemodifikator ein Öl umfasst.
     
    3. Verfahren nach Anspruch 1, wobei der Rheologiemodifikator Erdnussöl, Sojaöl, Pflanzenöl oder Oleylalkohol umfasst.
     
    4. Verfahren nach Anspruch 1, wobei der Rheologiemodifikator pyrogene Kieselsäure umfasst.
     
    5. Verfahren nach Anspruch 1, wobei der Rheologiemodifikator Polyoxyethylen(2)-oleylether, Sorbitanmonolaurat oder Glycerolmonooleat umfasst.
     
    6. Verfahren nach Anspruch 1, wobei die Chargenzuammensetzung eines anorganischen Pulvers Cordierit umfasst, und
    wobei der Cordierit eine Abmischung eines ersten fein gemahlenen Cordierits mit einer mittleren Teilchengröße im Bereich von 35 µm bis 45 µm und eines zweiten fein gemahlenen Cordierits mit einer mittleren Teilchengröße im Bereich von 10 µm bis 20 µm umfasst.
     
    7. Zusetzende Zusammensetzung zum Anwenden auf einen Wabenkörper, der mehrere Zellkanäle definiert, die durch sich in Längsrichtung von einem stromaufwärtigen Einlassende zu einem stromabwärtigen Auslassende erstreckende poröse Kanalwände begrenzt sind, wobei die zusetzende Zusammensetzung Folgendes umfasst:
    eine Chargenzuammensetzung eines anorganischen Pulvers;

    ein Bindemittel;

    ein flüssiges Vehikel; und

    einen aus der Gruppe bestehend aus einem Polyethylenglykoldioleat, einem Öl und pyrogener Kieselsäure ausgewählten Rheologiemodifikator,
    wobei der Rheologiemodifikator als zusätzliche Zugabe in einer Menge im Bereich von 0,1 Gewichtsprozent bis 15 Gewichtsprozent, bezogen auf das Gewicht der Chargenzuammensetzung des anorganischen Pulvers, vorliegt;

    wobei die Zusammensetzung (i) eine bei einer Scherrate von 10/sek gemessene Kapillarviskosität von weniger als 8000 Pa·s aufweist, und (ii) eine auf einer schiefen Ebene mit einem Winkel von 60 Grad gemessene Fließrate von weniger als 60 mm/8 min aufweist.


     
    8. Zusetzende Zusammensetzung nach Anspruch 7, wobei der Rheologiemodifikator ein Öl umfasst.
     
    9. Zusetzende Zusammensetzung nach Anspruch 7, wobei der Rheologiemodifikator Erdnussöl, Sojaöl, Pflanzenöl oder Oleylalkohol umfasst.
     
    10. Zusetzende Zusammensetzung nach Anspruch 7, wobei der Rheologiemodifikator pyrogene Kieselsäure umfasst.
     
    11. Zusetzende Zusammensetzung nach Anspruch 7, wobei der Rheologiemodifikator Polyoxyethylen(2)-oleylether, Sorbitanmonolaurat oder Glycerolmonooleat umfasst.
     
    12. Zusetzende Zusammensetzung nach Anspruch 7, wobei die anorganische Chargenzuammensetzung gebrannten Cordierit umfasst; und
    wobei der Cordierit eine Abmischung eines ersten fein gemahlenen Cordierits mit einer mittleren Teilchengröße im Bereich von 35 µm bis 45 µm und eines zweiten fein gemahlenen Cordierits mit einer mittleren Teilchengröße im Bereich von 10 µm bis 20 µm umfasst.
     


    Revendications

    1. Procédé de fabrication d'un filtre à parois poreuses en céramique poreuse, comprenant les étapes qui consistent à :

    fournir une structure en nid d'abeilles délimitant une pluralité de canaux cellulaires délimités par des parois de canaux poreuses qui s'étendent longitudinalement d'une extrémité d'entrée en amont à une extrémité de sortie en aval ;

    fournir un mélange de fermeture, le mélange de fermeture comprenant : un mélange de poudres inorganiques ; un liant ; un véhicule liquide ; et un modificateur de rhéologie sélectionné dans le groupe constitué d'un dioléate de polyéthylène glycol, d'une huile, et d'une silice pyrogénée, le modificateur de rhéologie étant présent en suraddition dans une quantité de 0,1 % en poids à 15 % en poids relativement au mélange de poudres inorganiques ;
    le mélange de fermeture présentant une vitesse d'écoulement sur un plan incliné inférieure à 60 mm/8 min lorsqu'elle est mesurée à un angle de 60 degrés ;

    fermer sélectivement une extrémité d'au moins un canal prédéterminé avec le mélange de fermeture qui présente une viscosité capillaire inférieure à 8 000 Pa·s lorsqu'elle est mesurée à une vitesse de cisaillement de 10/s ;

    cuire le corps en nid d'abeilles fermé sélectivement dans des conditions efficaces pour former un bouchon de céramique en phase frittée dans ledit au moins un canal fermé sélectivement en convertissant le matériau de fermeture en une composition céramique en phase frittée primaire,
    dans lequel la cuisson comprend un chauffage du matériau de fermeture à une température maximale d'au moins 400°C.


     
    2. Procédé selon la revendication 1, dans lequel le modificateur de rhéologie comprend une huile.
     
    3. Procédé selon la revendication 1, dans lequel le modificateur de rhéologie comprend l'huile d'arachide, l'huile de soja, une huile végétale, ou l'alcool oléylique.
     
    4. Procédé selon la revendication 1, dans lequel le modificateur de rhéologie comprend la silice pyrogénée.
     
    5. Procédé selon la revendication 1, dans lequel le modificateur de rhéologie comprend l'éther oléylique de polyoxyéthylène (2), le monolaurate de sorbitane ou le monooléate de glycérol.
     
    6. Procédé selon la revendication 1, dans lequel le mélange de poudres inorganiques comprend de la cordiérite ; et
    dans lequel la cordiérite comprend un mélange d'une première cordiérite en poudre ayant une taille de particule médiane de 35 µm à 45 µm et d'une deuxième cordiérite en poudre ayant une taille médiane de particule de 10 µm à 20 µm.
     
    7. Composition de fermeture destinée à une application sur un corps en nid d'abeilles délimitant des canaux cellulaires délimités par des parois de canaux poreuses qui s'étendent longitudinalement d'une extrémité d'entrée en amont à une extrémité de sortie en aval, la composition de fermeture comprenant :

    un mélange de poudres inorganiques ;

    un liant ;

    un véhicule liquide ; et

    un modificateur de rhéologie sélectionné dans le groupe constitué d'un dioléate de polyéthylène glycol, d'une huile, et d'une silice pyrogénée,
    le modificateur de rhéologie étant présent en suraddition dans une quantité de 0,1 % en poids à 15 % en poids relativement au mélange de poudres inorganiques ;

    la composition (i) présentant une viscosité capillaire inférieure à 8 000 Pa·s lorsqu'elle est mesurée à une vitesse de cisaillement de 10/s, et (ii) présentant une vitesse d'écoulement sur un plan incliné inférieure à 60 mm/8 min lorsqu'elle est mesurée à un angle de 60 degrés.


     
    8. Composition de fermeture selon la revendication 7, dans laquelle le modificateur de rhéologie comprend une huile.
     
    9. Composition de fermeture selon la revendication 7, dans laquelle le modificateur de rhéologie comprend l'huile d'arachide, l'huile de soja, une huile végétale, ou l'alcool oléylique.
     
    10. Composition de fermeture selon la revendication 7, dans laquelle le modificateur de rhéologie comprend la silice pyrogénée.
     
    11. Composition de fermeture selon la revendication 7, dans laquelle le modificateur de rhéologie comprend l'éther oléylique de polyoxyéthylène (2), le monolaurate de sorbitane ou le monooléate de glycérol.
     
    12. Composition de fermeture selon la revendication 7, dans laquelle le mélange de poudres inorganiques comprend de la cordiérite cuite ; et
    dans laquelle la cordiérite comprend un mélange d'une première cordiérite en poudre ayant une taille de particule médiane de 35 µm à 45 µm et d'une deuxième cordiérite en poudre ayant une taille médiane de particule de 10 µm à 20 µm.
     




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    Cited references

    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description




    Non-patent literature cited in the description