Bonding of ceramic fibers

Compositions: coating or plastic – Coating or plastic compositions – Carbohydrate or derivative containing

Reexamination Certificate

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Details

C106S217010, C106S217300, C162S145000, C162S152000, C162S175000, C264S086000, C264S087000, C501S095200

Reexamination Certificate

active

06214102

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to methods of vacuum forming of ceramic fibrous slurries into shaped products.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 3,224,927 shows the use of cationic starch to precipitate silica binders onto refractory fibers for forming refractory papers and mats. Although the teachings of this patent are useful for manufacture of shaped ceramic fiber products, the amount of silica binder which can be flocked onto the ceramic fibers is limited by the flocking capacity of the cationic starch; namely, to about 1.5 units silica per unit of starch. In addition, the amount of starch which can be used cannot exceed about 8%. Otherwise, forming times are high and shapes stick to molds. Binder content and formulations therefore are restricted to levels that produce only moderately strong pieces, i.e., 80-120 PSI modulus of rupture. A need therefore exists for improved methods of vacuum forming shaped ceramic fiber products
SUMMARY OF THE INVENTION
The invention relates to an aqueous ceramic slurry comprising ceramic fibers, cationic starch, and colloidal silica, a method of vacuum forming the slurry, and ceramic products formed by that method. The slurry typically has a solids content of about 0.5% to about 3% based on total weight of the slurry, about 0.5% to about 2% ceramic fiber based on the total weight of the slurry, about 0.01% to about 0.7% silica based on the total weight of the slurry, about 0.005% to about 0.2% cationic starch based on the total weight of the slurry, remainder water. The silica sol has, based on the weight of the sol, about 50% silica having a particle size range of from about 7 nm to about 200 nm and a specific surface area of about 100 m
2
/gm to about 10 m
2
/gm, remainder water.
The method of vacuum forming the slurry entails passing the slurry through a porous screen under a vacuum pressure deposit the solids content of the slurry onto the screen to produce a shaped product. The ceramic products produce typically include ceramic fiber in an amount of about 62% to about 96% by weight based on total weight of the ceramic product, about 2% to about 30% silica by weight based on total weight of the product, and about 1% to about 8% of cationic starch by weight based on the total weight of the product.
Having summarized the invention, the invention will now be described in detail by reference to the following detailed description and non-limiting examples.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the invention, an aqueous slurry having ceramic fiber, silica sol having a large particle size and broad particle size distribution, and starch is vacuum formed to provide shaped products. The aqueous slurry of ceramic fiber, starch and silica sol has a solids content of about 0.5% to about 3% by weight based on the total weight of the slurry, preferably about 0.7% to about 1% solids by weight based on total weight of the slurry, about 0.5% to about 2% ceramic fiber by weight based on total weight of the slurry, preferably about 0.7% ceramic fiber by weight based on total weight of the slurry, about 0.01% to about 0.7% silica by weight based on total weight of the slurry, preferably about 0.02% to about 0.21% silica by weight based on the total weight of the slurry, about 0.005% to about 0.2% cationic starch by weight based on total weight of the slurry, preferably about 0.01% to about 0.07% cationic starch by weight based on total weight of the slurry, remainder water.
Optionally, a filler material such as ceramic fillers and organic fillers, preferably ceramic fillers, may be included in the aqueous slurry of ceramic fiber, silica sol, and starch to provide a modified slurry that also may be vacuum formed. The filler may be included in an amount of up to about 1% by weight based on the total weight of the modified slurry. The modified slurry having ceramic fiber, silica sol, starch, and ceramic filler has about 0.5% to about 3% solids by weight based on the total weight of the modified slurry, preferably about 0.07% to about 1.7% by weight of solids by weight based on the total weight of the modified slurry. Ceramic fibers are present in the modified slurry an amount of about 0.5% to about 2% by weight based on total weight of the modified slurry, preferably about 0.7% by weight based on the total weight of the modified slurry, silica is present in an amount of about 0.01% to about 0.7% by weight based on total weight of the modified slurry, preferably about 0.02% to about 0.21% based on the total weight of the modified slurry, cationic starch is present in an amount of about 0.005% to about 0.2% by weight based on total weight of the modified slurry, preferably about 0.01% to about 0.07% by weight based on the total weight of the modified slurry remainder water. Preferably the filler is a ceramic filler present in an amount of up to about 1.0% by weight based on the total weight of the modified slurry. The preferred silica sols employed in the aqueous slurries which are vacuum formed into dried ceramic products in accordance with the invention are aqueous, colloidal dispersions of discrete amorphous silicon dioxide particles in slightly alkaline water that includes, based on the total weight of the sol, about 50% silica, remainder water. These sols are available from Wesbond Corporation, Wilmington, Del. under the name Megasol™. The sols may be used at a pH of about 8.0 to about 10.0, preferably at a pH of about 9.0 to about 9.5. The sols may be used in particle size ranges of about 7 nm to about 200 nm, preferably in particle size ranges of about 8 nm to about 190 nm, most preferably at a particle size range of about 10 nm to about 180 nm. The sols may be used with specific surface areas varying from about 100 m
2
/gm to about 10 m
2
/gm, preferably 80 m
2
/gm to about 20 m
2
/gm, most preferably about 60 m
2
/gm to about 27 m
2
/gm. The sols may be used at titratable Na
2
O contents of about 0.02% to about 0.35%, preferably about 0.1% to about 0.25%, most preferably about 0.20% to about 0.22%.
Silica sols such as Megasol™ which may be employed in the invention have larger particle size ranges and lower specific surface areas than prior art colloidal silica sols. These characteristics advantageously enables the use of much lower amounts of cationic starch to floc silica onto ceramic fibers, and to floc much larger amounts of silica onto the ceramic fibers. This enables manufacture of dried ceramic products such as ceramic fiberboard which have much lower organic content and higher strengths, and to produce products which sinter more slowly so that less shrinkage is experienced at elevated use temperatures.
The cationic starches which may be employed in the aqueous slurries which are vacuum formed in accordance with the invention preferably are pregelationized cationic corn starches that have been treated with a cationic amine, cooked and flaked. These cationic starches are available under the tradename WESTAR+ from Wesbond Corporation, Wilmington, Del. These cationic starches have a cationic charge of about 0. 18% N
2
to about 0.22% N
2
, and a pH of about 4 to 8. Higher cationic charge starches (0.30%N) such as WESTAR+3 corn starch from Wesbond Corp. also may be employed. Other starches which can be used in the compositions and process disclosed herein include, but are not limited to SOLVATOSE Potato Starch, EMPRESOL Potato Starch, and STA-LOK potato starch. SOLVATOSE Potato Starch, available from American Key Products, Inc. Kearney, N.J., is a pregelationized cationic potato starch that has been treated with a cationic amine, cooked and flaked. This starch has a cationic charge, as measured by Nitrogen content, of about 0.30%N
2
.
EMPRESOL Potato Starch, available from American Key Products, Inc. Kearney, NJ, also is a pregelationized cationic potato starch that has been treated with a cationic amine, cooked and flaked. This starch has a cationic charge, as measured by Nitrogen content, of about 0.30%N
2
. STA-LOK potato starch, available from Staley industrial Products, Decatur, Ill., is a pre

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