Patent Grant
8696962
The disclosure relates generally to methods of reducing defects in ceramic articles and precursors and more particularly to methods of reducing defects in ceramic articles and precursors that are made using a batch composition containing an oil phase material.
In the production of ceramic articles, such as honeycomb-shaped articles used as substrates and filters in mobile emissions applications, it is desirable to minimize the presence of defects in ware that rise to the level of causing failure to meet ever increasingly stringent customer specifications. Such defects can include not only those observed post-firing but also those observed in post-extrusion and post-drying stages, such as green fissure. Rejection of such ware results in reduced material utilization, which is undesirable.
Defects, such as green fissures, can result from a number of causes. In the production of certain ceramic articles, such as thin walled substrates for mobile emission control, a hydrophobic material such as a fatty acid or oil is often added to the batch as a lubricant. However, because typically applied binder materials, such as methylcellulose, are frequently generally insoluble in the oil phase, this phase often has substantially lower cohesive strength than the aqueous phase. This lack of cohesive strength in the oil phase can result in a type of green fissure often referred to as an oil fissure, characterized by locally concentrated oil streaks that migrate from the bulk of the batch to the skin area during extrusion. If defects caused by such fissures are severe enough, substantial losses in material utilization can occur as well as significant down time in production facilities in order to attempt to address the problem.
One embodiment of the disclosure relates to a method of reducing the presence of defects in ceramic articles and precursors. The method includes determining the incidence of a defect in a plurality of ceramic articles or precursors. The method also includes increasing a concentration of a water insoluble soap in a precursor batch composition. In addition, the method includes determining the incidence of a defect in a plurality of ceramic articles or precursors made from the precursor batch composition.
Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from the description or recognized by practicing the embodiments as described in the written description and claims hereof, as well as the appended drawings.
It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework to understand the nature and character of the claims.
The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s), and together with the description serve to explain principles and operation of the various embodiments.
Various embodiments of the disclosure will be described in detail with reference to the drawings, if any.
As used herein, the term “precursors” when used in the context of “ceramic articles and precursors”, refers to shaped or extruded material, such as that in the wet or green state, which can be subsequently fired to result in a ceramic article.
As used herein, “water insoluble soap” refers to a species of the general formula RCOOX, wherein R represents a generally organic constituent imparting oil phase solubility and X represents a metal, wherein the soap has a solubility limit in water at 25° C. of less than 0.001 mole per liter.
As used herein, “salt of a water insoluble soap” refers to a salt containing a metal ion of a water insoluble soap.
As used herein, “alkaline earth soap” refers to a species of the general formula RCOOX, wherein R represents a generally organic constituent imparting oil phase solubility and X represents an alkaline earth metal (beryllium, magnesium, calcium, strontium, barium, or radium).
As used herein, the term “precursor batch composition” refers to a composition of materials used to make ceramic articles and precursors.
In the production of ceramic articles, particularly those made from precursor batch compositions containing an oil phase material, certain defects such as green fissures, including oil fissures, are often caused by lack of cohesive strength in the oil phase. Applicant has surprisingly found that the oil phase cohesive strength can be increased by increasing the batch concentration of certain water insoluble soaps that are generally soluble in the oil phase. By thus increasing the cohesive strength of the oil phase, the incidence of certain defects such as green fissures, including oil fissures, may be significantly reduced.
Specifically, the incidence of one or more defects may be reduced by determining the incidence of the defect or defects in a plurality of ceramic articles or precursors, for example, by determining the percentage or fraction of ceramic articles or precursors having a certain defect or defects within a group of ceramic articles or precursors being produced. Depending on the level of defects found in the ceramic articles, the concentration of a water insoluble soap in a precursor batch composition may be increased. The incidence of the defect or defects in a plurality of ceramic articles made from the precursor batch composition in which the concentration of the water insoluble soap has been increased can then be determined. If necessary, the concentration of the water insoluble soap can be adjusted or increased at least a second time, depending, for example, on the incidence of defects (and other considerations) in ceramic articles or precursors made from the precursor batch composition in which the concentration of the water insoluble soap has been increased.
The concentration of water insoluble soap in the precursor batch composition can be increased by at least one of a number of different approaches. For example, the concentration of water insoluble soap can be increased by adding an amount of common metal ion salt of water insoluble soap to the precursor batch composition. The concentration of water insoluble soap can also be increased by adding an amount of water insoluble soap to the precursor batch composition. The concentration of water insoluble soap can additionally be increased by lowering the overall solubility product of fatty acid and water insoluble soap metal ion in the precursor batch composition.
The water insoluble soap can be selected to comprise chelateable inorganic ions that are capable of forming generally water insoluble inorganic-fatty acid complexes having at least some amount of solubility in oil. The inorganic ions can include those selected from alkaline earth elements, rare earth elements, group VIIIB elements, and group IIB elements that produce salts of organic fatty acids with solubility products (Ksp) of between 10−16 and 10−12 at 67° C.
In certain exemplary embodiments, the water insoluble soap is selected from at least one alkaline earth soap. In certain exemplary embodiments, the alkaline earth soap is at least one of a calcium soap and a magnesium soap. Exemplary calcium and magnesium soaps include calcium oleate, calcium laurate, magnesium oleate, magnesium laurate, calcium stearate, calcium palmitate, magnesium stearate, and magnesium palmitate.
In certain exemplary embodiments, the concentration of water insoluble soap in the precursor batch composition can be increased by adding an amount of a common metal ion salt of a water insoluble soap to the precursor batch composition. For example, the concentration of water insoluble soap in the precursor batch composition may be increased by adding an amount of at least one suitable alkaline earth salt to the precursor batch composition. Exemplary alkaline earth salts include calcium carbonate, calcium oxide, and calcium chloride, magnesium carbonate, magnesium oxide, and magnesium chloride.
The salt of a water insoluble soap can be added in an amount that is effective to increase the concentration of water insoluble soap according to the equilibrium relationship:
[RCOOX][RCOO−]N[X+N]
wherein [RCOOX] represents the concentration of the water insoluble soap, [RCOO−] represents anionic fatty acid concentration, [X+N] represents concentration of a metal ion of a water insoluble soap, and N represents the net positive charge of the metal ion.
In certain exemplary embodiments, the amount of common metal ion salt of a water insoluble soap, such as a suitable alkaline earth salt, added to the precursor batch composition can be at least 0.05%, such as at least 0.10%, and further such as at least 0.15%, and still further such as at least 0.20% of the weight of the dry ingredients of the precursor batch composition.
In certain exemplary embodiments, care should be taken to ensure that the amount of common metal ion salt of a water insoluble soap added to the precursor batch composition does not substantially adversely affect other properties of ceramic articles made from the composition, such as, for example, coefficient of thermal expansion (CTE). Accordingly, in certain exemplary embodiments, the common metal ion salt of a water insoluble soap, such as a suitable alkaline earth salt, is added to the precursor batch composition in an amount ranging from 0.05 to 0.40%, such as from 0.10 to 0.35%, and further such as from 0.15 to 0.30% of the weight of the dry ingredients of the precursor batch composition.
In certain exemplary embodiments, the concentration of water insoluble soap in the precursor batch composition can be increased by adding an amount of water insoluble soap to the precursor batch composition. For example, the concentration of water insoluble soap in the precursor batch composition may be increased by adding an amount of at least one suitable alkaline earth soap to the precursor batch composition. Exemplary alkaline earth soaps include calcium oleate, calcium laurate, magnesium oleate, and magnesium laurate, calcium stearate, calcium palmitate, magnesium stearate, and magnesium palmitate.
In certain exemplary embodiments, the amount of water insoluble soap, such as a suitable alkaline earth soap, added to the precursor batch composition can be at least 0.05%, such as at least 0.10%, and further such as at least 0.15%, and still further such as at least 0.20% of the weight of the dry ingredients of the precursor batch composition.
In certain exemplary embodiments, the concentration of water insoluble soap in the precursor batch composition can be increased by lowering the overall solubility product (Ksp) of fatty acid and metal ion of a water insoluble soap, wherein:
Ksp=[RCOO−]N[X+N]
wherein [RCOO−] represents anionic fatty acid concentration, [X+N] represents concentration of a metal ion of a water insoluble soap, and N represents the net positive charge of the metal ion. This can be done by selecting a suitable combination of fatty acid and metal ion and/or by adding a suitable fatty acid to the precursor batch composition and/or wholly or partially substituting a suitable fatty acid for another fatty acid in the precursor batch composition.
For example the concentration of water insoluble soap in the precursor batch composition may be increased by lowering the overall solubility product (Ksp) of fatty acid and a suitable alkaline earth metal ion in the precursor batch composition.
In certain exemplary embodiments, the overall solubility product (Ksp) of fatty acid and alkaline earth metal ion at 67° C. in the precursor batch composition can be lowered to be below 10−11, such as below 10−12, and further such as below 10−13, and yet further such as below 10−14, such as between 10−11 and 10−16.
By adding a suitable fatty acid to the precursor batch composition and/or wholly or partially substituting a suitable fatty acid for another fatty acid in the precursor batch composition, the overall solubility product of fatty acid and metal ion, such as alkaline earth metal ion, can be lowered by at least 50%, such as by at least 90%, and further such as by at least 95%, and yet further such as by at least 99%.
In certain exemplary embodiments, the alkaline earth metal ion is calcium and the overall solubility product of fatty acid and calcium ion is lowered by adding a fatty acid having a solubility product at 67° C. with calcium ion of equal to or less than 10−12.
In certain exemplary embodiments, the alkaline earth metal ion is magnesium and the overall solubility product of fatty acid and calcium ion is lowered by adding a fatty acid having a solubility product at 67° C. with magnesium ion of equal to or less than 10−12.
In certain exemplary embodiments, the overall solubility product of fatty acid and metal ion, such as alkaline earth metal ion is lowered by adding at least one of oleic acid, stearic acid, palmitic acid, and lauric acid to the precursor batch composition and/or by substituting at least one of these acids for another fatty acid in the precursor batch composition.
The disclosure and scope of the appended claims will be further clarified by the following examples. In all of the examples below, the talc contained about 0.1 to 0.2 wt % of calcium salt as an impurity.
Four different experimental runs were conducted from cordierite precursor batch compositions having the ingredients set forth in Table 1.
The compositions were identical except for the amount of calcium carbonate, which on a weight percentage basis, was superadded in certain experimental runs in differing amounts as a dry component. Specifically, in Runs 2 and 3, calcium carbonate was added to the composition in amounts of 0.16 and 0.32 weight percent respectively. Addition of calcium carbonate to the composition results in an increased amount of calcium soap in the oil phase of the composition.
Honeycomb-shaped ware was extruded from the compositions set forth in Table 1 and evaluated for skin defects such as air checks and fissures, with skin quality results set forth in Table 1, showing that the addition of calcium carbonate improved the skin quality.
Four additional experimental runs were conducted from cordierite precursor batch compositions having the ingredients set forth in Table 2.
The compositions were identical to each other and to those set forth in Example 1 except calcium chloride (instead of calcium carbonate), was superadded in certain experimental runs in differing amounts as a dry component. Specifically, in Runs 6 and 7, calcium chloride was added to the composition in amounts of 0.08 and 0.16 weight percent respectively. Addition of calcium chloride to the composition results in an increased amount of calcium soap in the oil phase of the composition.
Honeycomb-shaped ware was extruded from the compositions set forth in Table 2 and evaluated for skin defects such as air checks and fissures, with skin quality results set forth in Table 2, showing that the addition of calcium chloride improved the skin quality.
Four additional experimental runs were conducted from cordierite precursor batch compositions having the ingredients set forth in Table 3.
The compositions were identical to each other except oleic and linoleic acid were substituted for tall oil in certain experimental runs. Specifically, in Run 10, oleic acid was substituted for tall oil and in Run 11, linoleic acid was substituted for tall oil. Oleic acid is known to have a Ksp of about 10−10 at 67° C. and linoleic acid is known to have a Ksp of about 10−12 at 67° C. Tall oil is expected to have a Ksp between these two values as it is known as being a mixture of oleic and linoleic acid. Therefore, substitution of oleic acid for tall oil results in an increased amount of calcium soap in the oil phase of the composition, whereas substitution of linoleic acid for tall oil results in a decreased amount of calcium soap in the oil phase of the composition.
Honeycomb-shaped ware was extruded from the compositions set forth in Table 3.
Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that any particular order be inferred.
It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the invention as set forth in the appended claims. Since modifications combinations, sub-combinations and variations of the disclosed embodiments incorporating the spirit and substance of the disclosure may occur to persons skilled in the art, the disclosure should be construed to include everything within the scope of the appended claims and their equivalents.
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| 20130072370 A1 | Mar 2013 | US |
