Colloid systems and wetting agents; subcombinations thereof; pro – Continuous liquid or supercritical phase: colloid systems;... – Primarily organic continuous liquid phase
Reexamination Certificate
1999-10-14
2001-04-24
Lovering, Richard D. (Department: 1712)
Colloid systems and wetting agents; subcombinations thereof; pro
Continuous liquid or supercritical phase: colloid systems;...
Primarily organic continuous liquid phase
C516S199000, C516S034000, C106S287110, C501S097100
Reexamination Certificate
active
06221921
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to dispersant systems and methods for formulating non-aqueous siliceous particulate slurries. More particularly, the present invention relates to new ceramic slurries for use in a wide variety of green (i.e., “undried”) ceramic forming processes, including slip casting and gel casting. Numerous ceramic products can be made using the present invention include, but are not limited to, turbine engine components, wear resistant tooling and other structural engineering ceramic components, as well as traditional whitewares.
BACKGROUND OF THE INVENTION
In conventional slip casting, a suspension of ceramic particles dispersed in a liquid vehicle (i.e., a “slip”) is poured into a porous plaster of Paris mold. The interior surfaces of the mold conform to the exterior surface of the desired ceramic piece. As the plaster absorbs the liquid vehicle from the slip via capillary action, solid particles are deposited on the interior surface of the mold. The process may be continued until the walls of the ceramic piece meet the center, as in solid casting, or the slip may be drained from the mold when the walls reach the desired thickness, as in drain casting. Conventional slips are prepared in several ways. Slurries are typically prepared by ball milling ceramic particles. For example, filter cake may be blunged or raw materials may be ball-milled in the vehicle. A dispersant is usually added to the liquid vehicle prior to milling to keep the solid particles in suspension in the liquid vehicle. Otherwise, the particles would settle, forming thicker walls at the bottom of the mold. Furthermore, addition of a dispersant to the slurry increases its fluidity by inhibiting interparticle coalescence and flocculation. The mold can be made in two or more parts to facilitate removal of the ceramic piece.
The principal advantage of slip casting is that it permits formation of complex shapes. It is widely used throughout the ceramic industry. Another advantage of slip casting is that the molds are relatively inexpensive and they are reusable. In some cases, pieces of ware are cast separately and joined, using the slip as an adhesive (e.g., handles for whiteware cups and vases).
Gel casting differs from slip casting in that the former entails pouring a slurry into a nonporous mold which is subsequently heated to gel the slurry and form the green ceramic part. Gel casting therefore relies upon a slurry gelation mechanism for green part consolidation rather than through a capillary wicking effect encountered during slip cast molding. Gelation is typically accomplished by in-situ free radical polymerization of acrylate or vinyl monomers present as solutes within the gel casting slurry vehicle. (See e.g. U.S. Pat. Nos. 4,894,194 and 5,028,362.) The resulting polymer forms a binder phase in the gel cast green ceramic part after molding.
In order to minimize the amount of shrinkage and possible distortion of the ceramic part during drying, binder removal, and sintering operations, green ceramic parts, regardless of forming technique, should exhibit high green densities (e.g. green density should be at least 50% that of the sintered ceramic part density). This requires that ceramic slurries should have high solids loadings. Slip casting slurries typically do not require as high a solids loading compared to those used for gel casting for the reason that the porous molds used in the former continually remove the liquid vehicle from the slurry during casting and raises green ceramic part density. Gel casting slurries, on the other hand, require at least 50 volume % solids since no liquid vehicle is removed during casting and gelation.
In order to achieve a high ceramic solids loading and maintain slurry fluidity, a dispersant is often added to the gel casting formulation. The dispersant is a low molecular weight polymer or oligomer which has a polar end group having a strong affinity for the ceramic particulate surface while the tail end of the molecule becomes solvated within the vehicle. Suitable dispersants have tail ends that are highly solvated within the vehicle liquid. These dispersants form a steric barrier toward ceramic interparticle coalescence and ultimately slurry flocculation. In essence, the attractive force between the vehicle molecules and the dispersant tail overrides the interchain attractive effects present within the dispersant molecule.
Numerous slurries containing siliceous ceramic particulate (i.e., silicon nitride, silicon carbide, silica, and silicon metal powder partially oxidized by air exposure) have been formulated in aqueous vehicles previously. Unfortunately, most of these slurries suffer from the drawback that water present in its vehicle causes hydrolytic degradation of the particulate surfaces and forms soluble ionic silicate species within the vehicle. A number of variables magnify this problematic hydrolysis effect including, allowing the slurry to stand for prolonged time periods and exposure to elevated temperatures, or formulating the slurry under alkaline pH conditions.
Slurry particle hydrolysis is undesirable for several reasons. First, the formation of soluble silicate hydrolysis by-products often changes slurry rheology by increasing its viscosity when subjected to low shear (as encountered when pouring the slurry). This is undesirable since many green ceramic forming methods rely upon slurries that have predictable and controllable viscosities that do not change upon aging. Second, the soluble silicates may polymerize and induce slurry gelation. Further, particulate hydrolysis may change the overall slurry chemical composition by increasing the amount of oxygen (in the form of silica) within the ceramic formulation. This is particularly undesirable for silicon carbide (SiC) and silicon nitride (Si
3
N
4
) slurries since the properties of sintered ceramics made from these materials are highly sensitive to small changes in chemical composition. An increased amount of silica in an ages SiC and Si
3
N
4
slurry may manifest itself as a change in the composition and properties of the intergranular glass phase responsible for binding the individual SiC or Si
3
N
4
grains together within the sintered ceramic body. Elevated silica levels in intergranular glasses, for example, have been shown to decrease the high temperature creep resistance of sintered Si
3
N
4
ceramics.
Consequently, there is a significant need for methods and formulations for siliceous ceramic slurries that do not have the disadvantages of conventional methods and formulations.
SUMMARY OF THE INVENTION
The present invention overcomes the problems encountered in conventional methods and formulations by providing a non-aqueous vehicle that does not undergo significant changes in rheology compared to conventional formulations.
More specifically, the present invention provides methods and formulations that use a vehicle and dispersant composition as well as a formulating process for preparing stable, non-aqueous slurries containing a high siliceous ceramic solids composition (greater than 25 volume percent, and preferably, greater than 50 volume percent solids). Siliceous ceramic particles that can be dispersed in the vehicles of the present invention include oxidized silicon metal, and more preferably silicon nitride or silicon carbide.
The slurry formulation of the present invention comprises an organic liquid ester that serves as the major component of the vehicle, and a mixture of alkoxylated aminoalcohol (alkanolamine) and organophosphate ester, which collectively constitute the dispersant. A wide variety of linear and cyclic organic esters can be used as a vehicle component, with lactones (e.g., gamma-butyrolactone, referred hereafter as “BLO”) being a preferred ester. The alkoxylated aminoalcohol is typically an ethoxylated aminoethanol oligomer (sold under the tradename of HYPERMER™ PS-2 or ZEPHRYM™ PD-7000, made by I.C.I. Specialty Chemicals of Wilmington, Del.). A wide variety of aromatic and nonaromatic organophosphate ester compounds can be used for the
Dent David Zackery
Johnston Kevin Haines
Lombardi John Lang
Advanced Ceramics Research, Inc.
Banner & Witcoff , Ltd.
Lovering Richard D.
Metzmaier Daniel S.
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