Cementitious articles, such as gypsum board and cement board, are useful in a variety of applications, some of which require a degree of water resistance. Traditional paper-faced cementitious articles do not always perform well under high moisture conditions, or upon exposure to the outdoors. Thus, for such applications, it is often desirable to use a cementitious article that is faced with a glass or polymer-based fiber mat instead of paper. It also is advantageous to use additives in the cementitious core that improve the water resistance of the core material itself.
The manufacturing process of cementitious articles, such as gypsum board and cement board, typically involves depositing a cementitious slurry over a first facing material and covering the wet slurry with a second facing material of the same type, such that the cementitious slurry is sandwiched between the two facing materials. Thereafter, excess water is removed from the slurry by drying. The cementitious slurry is allowed to harden to produce a solid article prior to final drying.
The manufacturing process of cementitious articles, thus, often requires the facing material to be sufficiently permeable that excess water can be removed from the cementitious slurry in the drying process. For example, non-woven fiberglass mat is often used as a facing material, in which the space between the fibers provides permeability. The permeability of the fibrous facing materials, however, makes the manufacturing process more difficult because the cementitious slurry deposited on the fibrous mat facing material tends to penetrate the mat causing slurry build-up on the forming table and assembly line. The slurry build-up must be removed periodically. Increasing the viscosity of the slurry can reduce the amount of slurry that penetrates the fibrous mat facing material, but the required higher viscosity is not always optimum for use in existing plant production processes due, for instance, to changes in mixing, setting, drying, or hardening characteristics.
Furthermore, the permeability of the fibrous mat facing material also reduces the water-resistance of the cementitious article because it allows water to penetrate the mat and contact the cementitious core during use. In order to alleviate this problem, exterior coatings of hydrophobic resins are sometimes applied. However, this generally requires an additional post-manufacturing step to be employed, adding cost and inconvenience.
Another approach is to further increase the water resistance of the cementitious core material by including hydrophobic additives in the cementitious slurry. A preferred additive for this purpose is a siloxane oil. However, methods of employing such additives require further improvement in their implementation and effectiveness.
Thus, there remains a desire for new water resistant cementitious articles, as well as methods of preparing such articles.
In one aspect, the invention provides a fibrous mat-faced cementitious article comprising (a) a cementitious core, and (b) a first fibrous mat comprising polymer or mineral fibers and a hydrophobic finish on at least one surface thereof, wherein the hydrophobic finish is in contact with the cementitious core.
In another aspect, the invention provides a method of preparing a fibrous mat-faced cementitious article comprising (a) depositing a cementitious slurry on a first fibrous mat comprising polymer or mineral fibers and a hydrophobic finish on at least one surface thereof, wherein the cementitious slurry is deposited on the hydrophobic finish, and (b) allowing the cementitious slurry to harden, thereby providing a fibrous mat-faced cementitious article.
In another aspect, the invention provides a method of preparing a water-resistant cementitious article comprising (a) preparing an aqueous siloxane dispersion comprising about 4 wt. % to about 8 wt. % siloxane in water, (b) combining the siloxane dispersion with a cementitious mixture to provide a cementitious slurry, (c) depositing the cementitious slurry onto a substrate, and (d) allowing the cementitious slurry to harden, thereby providing a cementitious article.
These and other advantages of the present invention, as well as additional inventive features, will be apparent from the description of the invention provided herein.
Embodiments of a fibrous mat-faced cementitious article according to the invention comprise (a) a cementitious core, and (b) a first fibrous mat comprising polymer or mineral fibers and a hydrophobic finish on at least one surface thereof, wherein the hydrophobic finish is in contact with the cementitious core. Desirably, the hydrophobic finish prevents the cementitious core of the article from penetrating the first fibrous mat to any substantial degree during manufacture.
The first fibrous mat comprises any suitable type of polymer or mineral fiber, or combination thereof. Non-limiting examples of suitable fibers include glass fibers, polyamide fibers, polyaramide fibers, polypropylene fibers, polyester fibers (e.g., polyethylene teraphthalate (PET)), polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), cellulosic fibers (e.g., cotton, rayon, etc.), and the like, as well as combinations thereof. Furthermore, the fibers of the mat can be hydrophobic or hydrophilic, coated or uncoated. Of course, the choice of fibers will depend, in part, on the type of application in which the cementitious article is to be used. For example, when the cementitious article is used for applications that require heat or fire resistance, appropriate heat or fire resistant fibers should be used in the fibrous mat.
The first fibrous mat can be woven or non-woven; however, non-woven mats are preferred. Non-woven mats comprise fibers bound together by a binder. The binder can be any binder typically used in the mat industry. Suitable binders include, without limitation, urea formaldehyde, melamine formaldehyde, stearated melamine formaldehyde, polyester, acrylics, polyvinyl acetate, urea formaldehyde or melamine formaldehyde modified or blended with polyvinyl acetate or acrylic, styrene acrylic polymers, and the like, as well as combinations thereof. Suitable fibrous mats include commercially available mats used as facing materials for cementitious articles.
The first fibrous mat of the cementitious article comprises a hydrophobic finish on at least one surface thereof, which is in contact with the cementitious core. Any hydrophobic finish material can be used. Preferably, the hydrophobic finish provides a surface with a degree of hydrophobicity such that water applied to the surface exhibits a contact angle of about 70° or greater, such as about 70° to about 130° , or about 90° or greater, such as about 90° to about 120° . The contact angle can be measured by any suitable technique.
Examples of suitable hydrophobic finish materials include, without limitation, compositions comprising, consisting essentially of, or consisting of talc, wax, silicone-based compounds (e.g., silanes or siloxanes), hydrophobic resins, fatty acids (e.g., oleic acid) and salts (e.g., multivalent salts) thereof, polyethylene glycol (PEG), and long-chain hydrocarbon and fluorocarbon surfactants (e.g., having 12 or more carbon atoms), as well as combinations thereof.
The finish material can be applied to the first fibrous mat as a liquid or solid material (e.g., resin, wet-dispersed powder, dry powder, or film) by any of various methods known in the art. For instance, the hydrophobic finish materials can be applied by brushing, spraying, rolling, pouring, dipping, sifting, or overlaying the hydrophobic finish material. Solid materials, such as powders, can be dispersed prior to application using any common solvent (e.g, water, alcohols, etc.) or dispersant, provided the solvent or dispersant does not react adversely with the fibrous mat materials. Solvents that etch the surface fibers of the fibrous mat, and thereby enhance the ability of the finish material to adhere to the mat, also can be used. Preferably, any solvent or dispersant used is easily dried and does not leave a residue that prevents the finish from adhering to the fibrous mat. Liquid or dispersed finish materials can have any viscosity suitable for application to the fibrous mat. Typically, the viscosity of a liquid or dispersed finish material will be from about 50-200 Kreb's units (KU) (about 300-20,000 cP), such as about 80-150 KU (about 800-8,000 cP).
Recognizing that the surface of the fibrous mat is an irregular surface, the finish material need not provide a finish that is completely continuous. When a liquid or powder finish composition is used, for instance, the finish material may fall within the voids between the fibers of the mat leaving gaps or holes in the finish. However, the finish material preferably is applied in an amount sufficient to provide a finish that is continuous and, desirably, coextensive with the dimensions of the first fibrous mat.
The hydrophobic finish applied to the first fibrous mat is preferably in the form of a layer. The layer, desirably, is thick enough to slow or prevent the penetration of cementitious slurry through the first fibrous mat during production. Without wishing to be bound by any particular theory, it is believed that the hydrophobic layer slows or prevents slurry penetration due to the reduced surface tension of the cementitious slurry on the hydrophobic layer as compared to the fibrous mat in the absence of the hydrophobic layer and/or by physically blocking the pore space of the fibrous mat. Generally, the finish will provide a layer over the mat (and over any resinous binder used to bind the fibers of the mat) with an average thickness of at least about 25 microns (e.g., at least about 25 to about 500 microns), at least about 100 microns (e.g., about 100 to about 500 microns), or at least about 200 microns (e.g., about 200 to about 500 microns, or about 200 to about 400 microns), or even at least about 300 microns (e.g., about 300 to about 500 microns, or about 300 to about 400 microns).
According to a preferred aspect of the invention, the first fibrous mat is not substantially embedded in the cementitious core. Preferably, less than about 50% of the thickness of the mat is embedded in the cementitious core, more preferably less than about 30%, less than about 15%, less than about 10%, or even less than about 2% (e.g., less than about 1%) of the thickness of the mat is embedded in the cementitious core. Without wishing to be bound by any particular theory, it is believed that the hydrophobic finish of the first fibrous mat prevents, to at least some degree, the first fibrous mat from becoming embedded in the cementitious core during production. In a related and preferred aspect of the invention, the cementitious core adheres, at least in part, to the hydrophobic finish.
It will be appreciated that the first fibrous mat has two facing surfaces: an outwardly facing surface and a surface facing the cementitious core. In accordance with the invention, the surface of the first fibrous mat facing the cementitious core comprises a hydrophobic finish. The outwardly facing surface need not comprise a hydrophobic finish. However, according to one embodiment of the invention, the outwardly facing surface of the fibrous mat also can comprise a hydrophobic finish as described herein. Alternatively, the outwardly facing surface can be otherwise treated by any method known in the art, or can remain untreated.
The cementitious article optionally can comprise a second fibrous mat comprising polymer or mineral fibers, wherein the cementitious core is disposed between the first fibrous mat and the second fibrous mat. The second fibrous mat can be the same or different from the first fibrous mat. Furthermore, the second fibrous mat can comprise a hydrophobic finish as described herein, or can be free of such a finish. When the cementitious article is in the form of a board or panel (e.g., gypsum board, cement board, etc.), the second fibrous mat is preferably the same as the first fibrous mat, both in material and orientation relative to the cementitious core, or has sufficiently similar expansion and contraction properties to the first fibrous mat, such that warping of the cementitious article is reduced or eliminated. When the second fibrous mat is the same as the first fibrous mat, it should be understood that the first and second fibrous mats can be provided by a single continuous piece of material, for example, by folding a single piece of fibrous mat such that it wraps around the cementitious core.
The cementitious core can comprise any material, substance, or composition containing or derived from hydraulic cement, along with any suitable additives. Non-limiting examples of materials that can be used in the cementitious core include Portland cement, sorrel cement, slag cement, fly ash cement, calcium alumina cement, water-soluble calcium sulfate anhydrite, calcium sulfate α-hemihydrate, calcium sulfate β-hemihydrate, natural, synthetic or chemically modified calcium sulfate hemihydrates, calcium sulfate dihydrate (“gypsum,” “set gypsum,” or “hydrated gypsum”), and mixtures thereof. As used herein, the term “calcium sulfate material” refers to any of the forms of calcium sulfate referenced above.
The additives can be any additives commonly used to produce cementitious articles, such as gypsum board or cement board. Such additives include, without limitation, structural additives such as mineral wool, continuous or chopped glass fibers (also referred to as fiberglass), perlite, clay, vermiculite, calcium carbonate, polyester, and paper fiber, as well as chemical additives such as foaming agents, fillers, accelerators, sugar, enhancing agents such as phosphates, phosphonates, borates and the like, retarders, binders (e.g., starch and latex), colorants, fungicides, biocides, and the like. Examples of the use of some of these and other additives are described, for instance, in U.S. Pat. Nos. 6,342,284, 6,632,550, 6,800,131, 5,643,510, 5,714,001, and 6,774,146, and U.S. Patent Publications 2004/0231916 A1, 2002/0045074 A1 and 2005/0019618 A1.
Preferably, the cementitious core comprises a calcium sulfate material, Portland cement, or mixture thereof. Advantageously, the cementitious core also comprises a hydrophobic agent, such as a silicone-based material (e.g., a silane, siloxane, or silicone-resin matrix), in a suitable amount to improve the water resistance of the core material. It is also preferred that the cementitious core comprise a siloxane catalyst, such as magnesium oxide (e.g., dead burned magnesium oxide), fly ash (e.g., Class C fly ash), or a mixture thereof. The siloxane and siloxane catalyst can be added in any suitable amount, and by any suitable method as described herein with respect the method of preparing a water-resistant cementitious article of the invention, or as described, for example, in U.S. Patent Publications 2006/0035112 A1 or 2007/0022913 A1. Desirably, the cementitious core also comprises strength-improving additives, such as phosphates (e.g., polyphosphates as described in U.S. Pat. Nos. 6,342,284, 6,632,550, and 6,800,131 and U.S. Patent Publications 2002/0045074 A1, 2005/0019618 A1, and 2007/0022913 A1) and/or pre-blended unstable and stable soaps (e.g., as described in U.S. Pat. Nos. 5,683,635 and 5,643,510). The cementitious core can comprise paper or glass fibers, but is preferably substantially free of paper and/or glass fibers (e.g., comprises less than about 1 wt. %, less than about 0.5 wt. %, less than about 0.1 wt. %, or even less than about 0.05 wt. % of paper and/or glass fibers, or contains no such fibers).
The cementitious article can be any of any type or shape suitable for a desired application. Non-limiting examples of cementitious articles include gypsum panels and cement panels of any size and shape.
The cementitious article can be prepared by any suitable method including, but not limited to, the inventive methods described herein. Embodiments of a method of preparing a fibrous mat-faced cementitious article according to the invention comprise (a) depositing a cementitious slurry on a first fibrous mat comprising polymer or mineral fibers, wherein the first fibrous mat comprises a hydrophobic finish on at least one surface thereof, and the cementitious slurry is deposited on the hydrophobic finish, and (b) allowing the cementitious slurry to harden, thereby providing a fibrous mat-faced cementitious article.
The method of preparing a cementitious article in accordance with the invention can be conducted on existing gypsum board manufacturing lines used to make fibrous mat-faced cementitious articles known in the art. Briefly, the process typically involves discharging a fibrous mat material onto a conveyor, or onto a forming table that rests on a conveyer, which is then positioned under the discharge conduit (e.g., a gate-canister-boot arrangement as known in the art, or an arrangement as described in U.S. Pat. Nos. 6,494,609 and 6,874,930) of a mixer. The components of the cementitious slurry are fed to the mixer comprising the discharge conduit, where they are agitated to form the cementitious slurry. Foam can be added in the discharge conduit (e.g., in the gate as described, for example, in U.S. Pat. Nos. 5,683,635 and 6,494,609). The cementitious slurry is discharged onto the fibrous mat facing material. The slurry is spread, as necessary, over the fibrous mat facing material and optionally covered with a second facing material, which may be a fibrous mat or other type of facing material (e.g., paper, foil, plastic, etc.). The wet cementitious assembly thereby provided is conveyed to a forming station where the article is sized to a desired thickness, and to one or more knife sections where it is cut to a desired length to provide a cementitious article. The cementitious article is allowed to harden, and, optionally, excess water is removed using a drying process (e.g., by air-drying or transporting the cementitious article through a kiln). Each of the above steps, as well as processes and equipment for performing such steps, are known in the art. It also is common in the manufacture of cementitious articles such as gypsum and cement board to deposit a relatively dense layer of slurry onto a facing material before depositing the primary slurry, and to use vibration in order to eliminate large voids or air pockets from the deposited slurry. Also, hard edges, as known in the art, are sometimes used. These steps or elements (dense slurry layer, vibration, and/or hard edges) optionally can be used in conjunction with the invention.
All aspects of the first fibrous mat used in accordance with the method of preparing a cementitious article are as described herein with respect to the cementitious article of the invention.
Although the cementitious slurry is in contact with the hydrophobic finish of the first fibrous mat, the cementitious slurry preferably does not substantially penetrate the first fibrous mat, thereby preventing the first fibrous mat from embedding in the cementitious slurry to any substantial degree. Preferably, the cementitious slurry penetrates less than about 50% of the thickness of the mat, more preferably less than about 30%, less than about 15%, less than about 10%, or even less than about 2% (e.g., less than about 1%) of the thickness of the mat. Most preferably, the cementitious slurry does not penetrate at all beyond the hydrophobic finish on the mat. According to a related and preferred aspect of the invention, the cementitious slurry preferably adheres, at least in part, to the hydrophobic finish.
The hydrophobic finish can be applied to the first fibrous mat prior to delivering the first fibrous mat to the manufacturing line. Alternatively, the hydrophobic finish can be applied to the first fibrous mat on the manufacturing line. In this respect, the method of the invention can further comprise depositing a hydrophobic finish on the first fibrous mat before depositing the cementitious slurry on the first fibrous mat. Any suitable hydrophobic finish material can be used, as previously described herein. The hydrophobic finish can be deposited on the first fibrous mat by any of various techniques known in the art, such as by brushing, spraying, rolling, pouring, dipping, sifting, or overlaying the hydrophobic finish material.
The hydrophobic finish, when applied as a liquid, preferably is dried before depositing the cementitious slurry on the first fibrous mat. The hydrophobic finish can be dried by any suitable method, such as by applying heat to the finish or to the mat comprising the finish.
Optionally, the method of preparing a fibrous mat-faced cementitious article can further comprise contacting the cementitious slurry with a second fibrous mat prior to allowing the cementitious slurry to harden, wherein the cementitious slurry is disposed between the first fibrous mat and the second fibrous mat. All other aspects of the first and second fibrous mats are as described with respect to the cementitious article of the invention.
The cementitious slurry comprises any of the cementitious materials and additives previously described as suitable or preferred with respect to the cementitious core of the cementitious article, along with sufficient water to provide a suitable viscosity. When measured by the slump test, the cementitious slurry will typically produce a patty with a diameter of about 5″ to about 8″ (or about 10 cm to about 20 cm), such as about 6″ to about 7″ (or about 15 cm to about 18 cm). Procedures for measuring the viscosity of a slurry using the slump test are known in the art. Briefly, a 2″ (or 5 cm) diameter tube is filled with slurry to a height of 4″ (10 cm). Within 5 seconds from sampling the slurry from the manufacturing line, the slurry is released from the tube onto a flat, level surface and allowed to spread into a patty. When the slurry has stopped spreading, the widest diameter of the slurry patty is measured (in the case of non-circular (e.g., elliptical) slurry patty, the widest diameter of the slurry patty is averaged with the diameter of the slurry patty in the direction perpendicular to the widest diameter).
Other aspects of the method of preparing a fibrous mat-faced cementitious article are as described herein with respect to the cementitious article of the invention. Those aspects of the method of preparing a fibrous mat-faced cementitious article not specifically described herein can be supplied by the techniques known and used in the manufacture of conventional cementitious articles, especially fibrous mat-faced cementitious articles.
In a related aspect, the invention provides a method of preparing a water resistant cementitious article comprising (a) preparing an aqueous siloxane dispersion comprising about 4 wt. % to about 8 wt. % siloxane in water, (b) combining the siloxane dispersion with a cementitious mixture to provide a cementitious slurry, (c) depositing the cementitious slurry onto a facing or other type of substrate, and (d) allowing the cementitious slurry to harden, thereby providing a cementitious article.
Any siloxane suitable for conferring water-resistance to a cementitious mixture can be used. The siloxane can be a cyclic hydrogen-modified siloxane or, preferably, a linear hydrogen-modified siloxane. The siloxane is desirably a liquid (e.g., a siloxane oil). Typically, the linear hydrogen modified siloxanes useful in the practice of the present invention comprise those having a repeating unit of the general formula: —Si(H)(R)—O—, wherein R represents a saturated or unsaturated mono-valent hydrocarbon radical. In preferred embodiments, R represents an alkyl group and most preferably R is a methyl group. Preferred siloxanes are capable of forming highly cross-linked silicone resins. During polymerization, the terminal groups are removed by condensation and siloxane groups are linked together to form the silicone resin. Cross-linking of the chains also occurs. The resulting silicone resin imparts water resistance to the gypsum matrix as it forms. Suitable such siloxanes are commercially available and described in the patent literature (e.g., low solvent or solventless methyl hydrogen siloxane fluid sold under the name SILRES BS 94 by Wacker-Chemie GmbH (Munich, Germany)).
The siloxane dispersion preferably is prepared by introducing the siloxane and water into a mixer in an amount sufficient to provide a dispersion comprising about 4 wt. % to about 8 wt. % siloxane in water, preferably about 4 wt. % to about 5 wt. % siloxane in water, and processing the mixture to produce a dispersion. More preferably, the dispersion comprises more than 4 wt. % and/or less than 8 wt. % siloxane in water. By way of illustration, the dispersion can comprise from about 4.1 wt. %, 4.2 wt. %, 4.3 wt. %, 4.4 wt. % or 4.5 wt. % to about 5 wt. %, 6 wt. %, or 7 wt. % siloxane in water. Preferably, the dispersion comprises droplets of siloxane in water, wherein the droplets have an average particle size of about 50 microns or less, preferably about 30 microns or less, or even about 20 microns or less (e.g., about 10 microns or less). More preferably, the droplets have a particle size distribution such that about 75% or more, 80% or more, 85% or more, even 90% or more, or even 95% or more of the droplets have a particle size of about 50 microns or less, preferably about 30 microns or less, or even about 20 microns or less (e.g., about 10 microns or less).The particle size and particle size distribution of the siloxane droplets in the dispersion can be determined using routine techniques, such as by dynamic light scattering analysis.
According to a preferred aspect of the invention, the dispersion is stabilized, such that the siloxane droplets remain dispersed in the water (i.e., the siloxane phase does not substantially separate from the water phase) for a period of time sufficient to allow the dispersion to be combined with the other components of the cementitious core. For instance, according to a preferred aspect of the invention, the dispersion will have a stability such that a sample of the dispersion taken immediately after mixing and allowed to rest will exhibit no visible coalescing of droplets on the surface of the sample within one minute (e.g., within two minutes).
A high shear or ultra-high shear mixer is, desirably, used to disperse the siloxane in the water. The high shear or ultra-high shear mixer can be any mixer capable of producing a siloxane in water dispersion in which the siloxane droplets have the above-described particle size or particle size distribution characteristics. Suitable types of high shear mixers include mechanical-shear mixers, such as pin-type, blade-type, rotor-stator, and disc-type mixers, as well as hydraulic shear mixers. Preferred mixers are those capable of producing a tip-speed of about 9,000 to about 15,000 feet per minute (FPM) (or about 40 to about 80 meters per second (mps), such as about 10,000 to 12,000 FPM (or about 50 to about 60 mps). Non-limiting examples of high shear mixers that can be used include the 312/45 MS high shear mixer (20 hp, 3600 RPM) manufactured by Silverson Machines, Inc., East Longmeadow, Mass., and the X-Series Mixer emulsifiers (30 to 75 HP), such as ME-430XS-6, ME-440XS-9, ME-475XS-12, HSM709X-40, HMS712X-75 manufactured by Charles Ross & Son Company, Hauppauge, N.Y.
The siloxane and water can be introduced into the dispersing mixer, preferably high shear mixer, separately or together, simultaneously or sequentially in any order. When the dispersion is prepared by batch mixing, the water is preferably added prior to the siloxane. However, batch mixing generally is not convenient or economical for continuous production methods. Thus, an in-line dispersing mixer is preferably used so as to produce the dispersion in a continuous manner, in which case the siloxane and water can be supplied to the in-line dispersing mixer continuously and simultaneously in an appropriate ratio. The aqueous siloxane dispersion preferably does not comprise an emulsifier or dispersant.
The aqueous sitoxane dispersion is combined with a cementitious mixture to provide a cementitious slurry. Those of ordinary skill in the art will appreciate that the cementitious mixture comprises solid components and liquid components. By way of illustration, the siloxane dispersion comprising the above-described amount of siloxane in water can be introduced directly into the mixer (e.g., the board mixer) comprising the solid components and/or liquid components of the cementitious mixture. Preferably, however, the siloxane dispersion is first combined with a liquid component of the cementitious mixture (e.g., water), and subsequently combined with the solid components of the cementitious mixture (e.g., by adding the siloxane dispersion to the gauging water or other water that is subsequently delivered to the board mixer). The siloxane dispersion is preferably added to the cementitious mixture in an amount sufficient to provide a siloxane content in the final cementitious product of about 0.3 wt. % to about 2 wt. %, such as about 0.5 wt. % to about 1.5 wt. %, or about 0.6 wt. % to about 1 wt. % based on the weight of the final cementitious product (e.g., the hardened, dried cementitious product). For example, assuming a cementitious panel of 1500 lbs/msf (e.g., a standard ½″ gypsum panel), the siloxane dispersion can be added to the cementitious mixture in an amount sufficient to provide about 5 lbs siloxane/1000 sq. ft. to about 30 lbs siloxane/1000 sq. ft. (or about 20 g siloxane/m2 to about 150 g siloxane/m2), such as about 7 lbs siloxane/1000 sq. ft. to about 20 lbs siloxane/1000 sq. ft. (or about 30 g siloxane/m2 to about 100 g siloxane/m2), or even about 10 lbs siloxane/1000 sq. ft. to about 14 lbs siloxane/1000 sq. ft. (or about 50 g siloxane/m2 to about 70 g siloxane/m2) in the final cementitious product (e.g., the hardened, dried cementitious product).
The cementitious slurry optionally comprises a siloxane catalyst, such as fly ash, especially class C fly ash, magnesium oxide, especially dead burned magnesium oxide, or, most preferably, a combination thereof. The fly ash is preferably used in amounts of about 0.1% to about 5% based on the weight of the dry cementitious component (e.g., the dry weight of the stucco). The magnesium oxide is preferably used in amounts of about 0.1% to about 0.5% based on the weight of the dry cementitious component (e.g., the dry weight of the stucco). The ratio of fly ash to magnesium oxide is desirably from about 2:1 to about 3:1.
Other aspects of the cementitious slurry are as previously described with respect to the method of preparing a mat-faced cementitious article in accordance with the invention. Other aspects of preparing an aqueous siloxane emulsion and combining the emulsion with a cementitious slurry are as described in U.S. Patent Publication 2007/0022913 A1.
The cementitious slurry can be deposited onto a substrate in accordance with known methods and on existing manufacturing lines, as described herein with respect to the method of preparing a fibrous mat-faced cementitious article, provided that a fibrous mat facing material need not be used as a substrate. Rather, the substrate can be any suitable substrate, such as any facing material typically used to face cementitious articles (e.g., paper facing material). Preferably, however, the substrate is a fibrous mat facing material comprising polymer or mineral fibers.
It is especially advantageous, to employ as the substrate a first fibrous mat comprising polymer or mineral fibers, wherein the first fibrous mat comprises a hydrophobic finish on at least one surface thereof. It is further preferable, when such a substrate is used, to deposit the slurry on the hydrophobic finish of the fibrous mat. Furthermore, a first and second fibrous mats can advantageously be used, wherein the cementitious slurry is disposed between the fibrous mats. Suitable such fibrous mats, hydrophobic finishes, and methods for the use thereof to provide a cementitious article, are as described herein with respect to the fibrous mat-faced cementitious article and method for preparing a fibrous mat-faced cementitious article of the invention.
All other aspects of the method of preparing a water-resistant cementitious article are as described herein with respect to the fibrous mat-faced cementitious article or the method of preparing a mat-faced cementitious article. Aspects of the method of preparing water-resistant cementitious article not specifically described herein can be supplied by the techniques known and used in the manufacture of conventional cementitious articles, especially fibrous mat-faced cementitious articles.
The following example illustrates the preparation of a fibrous-mat faced cementitious article in accordance with the invention.
Two types of fibrous mats are prepared: a first mat comprising all glass fibers and a second mat comprising a blend of 85 wt. % glass fibers and 15 wt. % polyester fibers. Both mats are non-woven and comprised a 19 wt. % melamine formaldehyde/acrylic binder.
A cementitious slurry is prepared using the formulation provided in Table 1 in a board mixer. The siloxane component of the slurry is dispersed in water (e.g., 4.1-4.4 wt. % siloxane in water dispersion) using a high shear mixer (e.g., the 312/45 MS high shear mixer (20 hp, 3600 rpm) manufactured by Silverson Machines, Inc., East Longmeadow, Mass., and the X-Series Mixer emulsifiers (60 Hz, 3,600 rpm) manufactured by Charles Ross & Son Company, Hauppauge, N.Y.), and introduced into the gauging water used to prepare the slurry.
The fibrous mat is positioned for application to the face (formed down) and the back (formed up) of the cementitious panel. The mat is passed through a tensioning and alignment system, and the face mat is creased to form the desired thickness (e.g, ⅝″) and desired edge (e.g., square) at the desired board width (e.g., 48″). Preferably, a hydrophobic finish is applied to the face mat. The face mat is passed under the board mixer, and the cementitious slurry is deposited onto the face mat. A densified layer is not deposited prior to depositing the cementitious slurry, and any slurry vibration apparatuses are turned off to help reduce slurry penetration through the mat.
The creased face mat with the slurry in-place is formed into an envelope and passed under the forming plate. At the point where the formed face mat enteres the forming plate, the back mat is placed in contact with the edges of the face mat. A bead of synthetic adhesive is used to bond the face glass mat to the back glass mat at the point where the mats intersected. Slurry does not contact the face and back glass mats at this intersection.
The completed glass mat envelope, filled with slurry, exits the forming plate and is transferred to the board belt. Guides keep the edges in the proper position until the slurry hydrates at a point about 30 seconds down the board belt, at which point the edges are self-supporting. The board is moved further down the line until it becomes self supporting. Thereafter, the board is cut to slightly longer than its desired finished length with a board knife. The board is inverted and moved into the kiln to remove the excess water.
The resulting product is a fibrous mat-faced cementitious product with improved water resistance.
The following example illustrates the effectiveness of a hydrophobic finish material applied to a fibrous mat facing material in preventing the penetration of a cementitious slurry through the fibrous mat.
Talc powder (Talcron 40-26, particle size 5 microns) dispersed in water containing 0.05 wt. % tri-potassium polyphosphate (dispersant) at various solid loading levels and viscosities is applied to non-woven glass fiber mats to coat the mats at a thickness of 5 mil or 15 mil (based on wet film thickness). The solid loading level, viscosity, and thickness of the finishes are provided in Table 2. Finishes 5-7 also contain a hydroxyethylcellulose viscosity enhancer (0.05 wt. %). Finish 7 further includes 1 wt. % white wax. Thereafter, a cementitious slurry is deposited over the finish material.
The amount of slurry penetration is visually inspected and compared to a control, which is provided by applying the same slurry to a glass fiber mat that is identical to the mats used to test finishes 1-7, but comprises no finish material.
By comparison to the control mat, a lesser amount of slurry will penetrate the mats comprising a finishing material, showing that the application of a hydrophobic finish to a fibrous mat facing material reduces or eliminates slurry penetration through the fibrous mat.
The following example illustrates the preparation of a water-resistant cementitious article in accordance with the invention.
A cementitious slurry is prepared using the formulation provided in Table 1 in a board mixer. The siloxane component of the slurry is dispersed in water (e.g., 4.1-4.4 wt. % siloxane in water dispersion) using a 312/45 MS high shear mixer (20 hp, 3600 RPM) manufactured by Silverson Machines, Inc., East Longmeadow, Mass.), and introduced into the gauging water used to prepare the slurry. The siloxane dispersion is introduced into the board mixer in an amount sufficient to provide a final cementitious product comprising 11 lb. siloxane/msf board (about 0.43% wt./wt.). The slurry is used in conjunction with standard manufacturing processes to produce a paper-faced board product that passes the ASTM C1396/C 1396M-06 2-hour immersion target for sheathing without board defects of 10% and for water resistant gypsum backing board of 5% using ASTM Standard Test Method C 473.
A second cementitious slurry is prepared in the same manner, except that an X-Series High Shear Mixer ME-430XS-6 manufactured by Charles Ross & Son Company, Hauppauge, N.Y. instead of the Silverson mixer, and the siloxane dispersion is added to the board mixer in an amount sufficient to provide a final cementitious produce comprising 10 lb. siloxane/msf board (about 0.39% wt./wt.). The slurry is used in conjunction with standard manufacturing processes to produce a paper-faced board product that passes the C1396/C 1396M-06 2-hour immersion target for sheathing without board defects of 10% and for water resistant gypsum backing board of 5% using ASTM Standard Test Method C 473.
In order to produce a product that passes the ASTM C1396 standard using conventional processes, higher levels of siloxane typically are required (e.g., on the order of 12.5 lbs. siloxane/msf or about 0.5% wt./wt.). The foregoing example illustrates that preparing a water-resistant cementitious article in accordance with the invention can be advantageously be used with a lower siloxane loading level.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
Preferred embodiments of this invention are described herein. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description, without departing from the spirit and scope of the invention. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
This patent application claims the benefit of U.S. Provisional Patent Application No. 60/889,487, filed Feb. 12, 2007, the entire disclosure of which is hereby incorporated by reference.
Number | Name | Date | Kind |
---|---|---|---|
1870439 | Birdsey | Aug 1932 | A |
2127952 | Choate | Aug 1938 | A |
2198766 | Gallagher | Apr 1940 | A |
2198776 | King et al. | Apr 1940 | A |
2216207 | Menaul | Oct 1940 | A |
2413458 | Light | Dec 1946 | A |
2425883 | Jackson | Aug 1947 | A |
2560521 | Camp | Jul 1951 | A |
2681863 | Croce et al. | Jun 1954 | A |
2803575 | Riddell et al. | Aug 1957 | A |
2806811 | Hazmburg | Sep 1957 | A |
2907667 | Johnson | Oct 1959 | A |
2970127 | Slayter et al. | Jan 1961 | A |
3086953 | Nitzsche et al. | Apr 1963 | A |
3155567 | Harr | Nov 1964 | A |
3259536 | Gaeth et al. | Jul 1966 | A |
3297601 | Maynard et al. | Jan 1967 | A |
3298973 | Quarles et al. | Jan 1967 | A |
3359146 | Lane et al. | Dec 1967 | A |
3382083 | Marsden et al. | May 1968 | A |
3389042 | Bieri et al. | Jun 1968 | A |
3455710 | Nitzsche et al. | Jul 1969 | A |
3459571 | Shannon | Aug 1969 | A |
3462341 | Littin | Aug 1969 | A |
3490065 | Shannon et al. | Jan 1970 | A |
3503841 | Sterrett | Mar 1970 | A |
3516882 | Cummisford | Jun 1970 | A |
3615189 | Hayakawa et al. | Oct 1971 | A |
3616173 | Green et al. | Oct 1971 | A |
3623895 | Nitzsche et al. | Nov 1971 | A |
3645707 | Philipps | Feb 1972 | A |
3650785 | Ball et al. | Mar 1972 | A |
3660068 | Wilson | May 1972 | A |
3663168 | Rubin et al. | May 1972 | A |
3663355 | Shimizu et al. | May 1972 | A |
3676094 | Russell | Jul 1972 | A |
3699212 | Palm | Oct 1972 | A |
3770468 | Knauf et al. | Nov 1973 | A |
3781396 | Okuda et al. | Dec 1973 | A |
3788020 | Gregori | Jan 1974 | A |
3839059 | Rothfelder et al. | Oct 1974 | A |
3839239 | Godfried | Oct 1974 | A |
3839836 | Payne | Oct 1974 | A |
3841886 | Burr | Oct 1974 | A |
3847766 | Klaus | Nov 1974 | A |
3857934 | Bernstein et al. | Dec 1974 | A |
3874980 | Richards et al. | Apr 1975 | A |
3903879 | Riley et al. | Sep 1975 | A |
3908062 | Roberts | Sep 1975 | A |
3915919 | Nishioka et al. | Oct 1975 | A |
3922413 | Reineman | Nov 1975 | A |
3922459 | Franz et al. | Nov 1975 | A |
3934066 | Murch | Jan 1976 | A |
3935021 | Greve et al. | Jan 1976 | A |
3935343 | Nuttall | Jan 1976 | A |
3936414 | Wright et al. | Feb 1976 | A |
3944698 | Dierks et al. | Mar 1976 | A |
3949144 | Duff | Apr 1976 | A |
3951675 | Krempff | Apr 1976 | A |
3951735 | Kondo et al. | Apr 1976 | A |
3955031 | Jones et al. | May 1976 | A |
3957501 | Matsuda et al. | May 1976 | A |
3964256 | Plantif et al. | Jun 1976 | A |
3967016 | Schneller et al. | Jun 1976 | A |
3977888 | Sano et al. | Aug 1976 | A |
3980487 | Akabayashi et al. | Sep 1976 | A |
3987600 | Baehr | Oct 1976 | A |
3993822 | Knauf et al. | Nov 1976 | A |
3994110 | Ropella | Nov 1976 | A |
3998023 | Anderson | Dec 1976 | A |
4005959 | Kautz | Feb 1977 | A |
4009062 | Long | Feb 1977 | A |
4010134 | Braunisch et al. | Mar 1977 | A |
4015386 | Cook | Apr 1977 | A |
4027043 | Schroeder et al. | May 1977 | A |
4028125 | Martin | Jun 1977 | A |
4028158 | Hipchen et al. | Jun 1977 | A |
4036658 | Pühringer et al. | Jul 1977 | A |
4036659 | Stude | Jul 1977 | A |
4040950 | Zipperian et al. | Aug 1977 | A |
4042536 | Dieterich et al. | Aug 1977 | A |
4043862 | Roberts | Aug 1977 | A |
4043950 | Wilmsen et al. | Aug 1977 | A |
4044520 | Barrows | Aug 1977 | A |
4049778 | Hodgson | Sep 1977 | A |
4054461 | Martin | Oct 1977 | A |
4054462 | Stude | Oct 1977 | A |
4063976 | Wain et al. | Dec 1977 | A |
4065413 | MacInnis et al. | Dec 1977 | A |
4065597 | Gillespie | Dec 1977 | A |
4070311 | Cominassi et al. | Jan 1978 | A |
4075804 | Zimmerman | Feb 1978 | A |
4076580 | Panusch et al. | Feb 1978 | A |
4081598 | Morgan et al. | Mar 1978 | A |
4088738 | Hauge | May 1978 | A |
4094694 | Long | Jun 1978 | A |
4097423 | Dieterich | Jun 1978 | A |
4101335 | Barrable | Jul 1978 | A |
4101475 | Stalego | Jul 1978 | A |
4102697 | Fukuba et al. | Jul 1978 | A |
4107376 | Ishikawa | Aug 1978 | A |
4112174 | Hannes et al. | Sep 1978 | A |
4113913 | Smiley | Sep 1978 | A |
4125498 | Blount | Nov 1978 | A |
4136215 | den Otter et al. | Jan 1979 | A |
4148781 | Narukawa et al. | Apr 1979 | A |
4154593 | Brown et al. | May 1979 | A |
4165413 | Sefton et al. | Aug 1979 | A |
4169907 | Barker et al. | Oct 1979 | A |
4174230 | Hashimoto et al. | Nov 1979 | A |
4183908 | Rolfe | Jan 1980 | A |
4184022 | Lawyer | Jan 1980 | A |
4186236 | Heitmann | Jan 1980 | A |
4187130 | Kautz | Feb 1980 | A |
4195110 | Dierks et al. | Mar 1980 | A |
4197225 | Emmons et al. | Apr 1980 | A |
4203788 | Clear | May 1980 | A |
4204030 | Takamizawa et al. | May 1980 | A |
4205136 | Ohashi et al. | May 1980 | A |
4210725 | Redfarn | Jul 1980 | A |
4214027 | Knuaf et al. | Jul 1980 | A |
4217333 | Löblich | Aug 1980 | A |
4221697 | Osborn et al. | Sep 1980 | A |
4230616 | Godfried | Oct 1980 | A |
4233343 | Barker et al. | Nov 1980 | A |
4233368 | Baehr et al. | Nov 1980 | A |
4236911 | McCullough et al. | Dec 1980 | A |
4242406 | El Bouhnini et al. | Dec 1980 | A |
4242407 | Bijen | Dec 1980 | A |
4245029 | Crivello | Jan 1981 | A |
4255483 | Byrd et al. | Mar 1981 | A |
4256799 | Ohashi et al. | Mar 1981 | A |
4258102 | Traver et al. | Mar 1981 | A |
4265964 | Burkhart | May 1981 | A |
4265979 | Baehr et al. | May 1981 | A |
4292353 | Ohashi et al. | Sep 1981 | A |
4296015 | Aotani et al. | Oct 1981 | A |
4296169 | Shannon | Oct 1981 | A |
4297311 | Sherman et al. | Oct 1981 | A |
4304877 | Blount | Dec 1981 | A |
4306395 | Carpenter | Dec 1981 | A |
4311767 | Kennedy | Jan 1982 | A |
4315967 | Prior et al. | Feb 1982 | A |
4322301 | Blackmore | Mar 1982 | A |
4324775 | Tung | Apr 1982 | A |
4327143 | Alvino et al. | Apr 1982 | A |
4327146 | White | Apr 1982 | A |
4341560 | Saito et al. | Jul 1982 | A |
4343127 | Greve et al. | Aug 1982 | A |
4344804 | Bijen et al. | Aug 1982 | A |
4350533 | Galer et al. | Sep 1982 | A |
4360386 | Bounini | Nov 1982 | A |
4361616 | Bömers | Nov 1982 | A |
4361995 | Buck et al. | Dec 1982 | A |
4364991 | Byrd et al. | Dec 1982 | A |
4372814 | Johnstone et al. | Feb 1983 | A |
4372997 | Fritze et al. | Feb 1983 | A |
4376674 | Ali | Mar 1983 | A |
4378405 | Pilgrim | Mar 1983 | A |
4380592 | Blount | Apr 1983 | A |
4381716 | Hastings et al. | May 1983 | A |
4388366 | Rosato et al. | Jun 1983 | A |
4392896 | Sakakibara | Jul 1983 | A |
4393015 | Kaneda et al. | Jul 1983 | A |
4394411 | Krüll et al. | Jul 1983 | A |
4399046 | Okamura et al. | Aug 1983 | A |
4399110 | Kurandt | Aug 1983 | A |
4403006 | Bruce et al. | Sep 1983 | A |
4406738 | Fink et al. | Sep 1983 | A |
4407884 | Witt | Oct 1983 | A |
4411701 | Saito et al. | Oct 1983 | A |
4411702 | Makino et al. | Oct 1983 | A |
4421704 | Reily | Dec 1983 | A |
4433020 | Narukawa et al. | Feb 1984 | A |
4433069 | Harper | Feb 1984 | A |
4436645 | Ceaser | Mar 1984 | A |
4441944 | Massey | Apr 1984 | A |
4447254 | Hughes et al. | May 1984 | A |
4447498 | Fink et al. | May 1984 | A |
4450022 | Galer | May 1984 | A |
4462831 | Raevsky et al. | Jul 1984 | A |
4463043 | Reeves et al. | Jul 1984 | A |
4477300 | Pilgrim | Oct 1984 | A |
4477533 | Phillips | Oct 1984 | A |
4486476 | Fritsch et al. | Dec 1984 | A |
4489176 | Kluth et al. | Dec 1984 | A |
4501787 | Marchetti et al. | Feb 1985 | A |
4502901 | Burkard | Mar 1985 | A |
4504533 | Altenhöfer et al. | Mar 1985 | A |
4508774 | Grabhoefer et al. | Apr 1985 | A |
4517095 | Ceaser | May 1985 | A |
4518508 | Conner | May 1985 | A |
4518652 | Willoughby | May 1985 | A |
4529705 | Larsen | Jul 1985 | A |
4543281 | Pedersen et al. | Sep 1985 | A |
4544424 | Take et al. | Oct 1985 | A |
4557961 | Gorges | Dec 1985 | A |
4557973 | Ali | Dec 1985 | A |
4563285 | Nair et al. | Jan 1986 | A |
4564544 | Burkard et al. | Jan 1986 | A |
4572865 | Gluck et al. | Feb 1986 | A |
4578301 | Currie et al. | Mar 1986 | A |
4613627 | Sherman et al. | Sep 1986 | A |
4618642 | Schoenherr | Oct 1986 | A |
4619655 | Hanker et al. | Oct 1986 | A |
4619701 | Angrick et al. | Oct 1986 | A |
4636538 | Malcolm-Brown | Jan 1987 | A |
4637951 | Gill et al. | Jan 1987 | A |
4643771 | Steinbach et al. | Feb 1987 | A |
4645548 | Take et al. | Feb 1987 | A |
4646494 | Saarinen et al. | Mar 1987 | A |
4647496 | Lehnert et al. | Mar 1987 | A |
4664707 | Wilson et al. | May 1987 | A |
4681798 | Gill et al. | Jul 1987 | A |
4684567 | Okamoto et al. | Aug 1987 | A |
4704263 | Berry et al. | Nov 1987 | A |
4729853 | von Bonin | Mar 1988 | A |
4746365 | Babcock et al. | May 1988 | A |
4748051 | Songer et al. | May 1988 | A |
4748771 | Lehnert et al. | Jun 1988 | A |
4759964 | Fischer et al. | Jul 1988 | A |
4767656 | Chee et al. | Aug 1988 | A |
4772326 | Heinen et al. | Sep 1988 | A |
4784897 | Brands et al. | Nov 1988 | A |
4810552 | Meyer | Mar 1989 | A |
4810569 | Lehnert et al. | Mar 1989 | A |
4849018 | Babcock et al. | Jul 1989 | A |
4857211 | Nineuil et al. | Aug 1989 | A |
4861397 | Hillstrom | Aug 1989 | A |
4879173 | Randall | Nov 1989 | A |
4904694 | Matsuoka et al. | Feb 1990 | A |
4916004 | Ensminger et al. | Apr 1990 | A |
4927463 | Kloetzer et al. | May 1990 | A |
4948647 | Burkard | Aug 1990 | A |
4975122 | Parkinson et al. | Dec 1990 | A |
4992481 | von Bonin et al. | Feb 1991 | A |
4999066 | Sherif | Mar 1991 | A |
5062235 | Cook, Jr. et al. | Nov 1991 | A |
5068103 | Kawazi et al. | Nov 1991 | A |
5073198 | Kurz | Dec 1991 | A |
5079078 | Jutte, Jr. et al. | Jan 1992 | A |
5082501 | Kurz | Jan 1992 | A |
5091441 | Omura | Feb 1992 | A |
5100948 | Aydin et al. | Mar 1992 | A |
5112678 | Gay et al. | May 1992 | A |
5118336 | Biez | Jun 1992 | A |
5120355 | Imai | Jun 1992 | A |
5135805 | Sellers et al. | Aug 1992 | A |
5141561 | Ledard et al. | Aug 1992 | A |
5148645 | Lehnert et al. | Sep 1992 | A |
5149368 | Liu et al. | Sep 1992 | A |
5155959 | Richards et al. | Oct 1992 | A |
5160639 | McCollum | Nov 1992 | A |
5171366 | Richards et al. | Dec 1992 | A |
5198052 | Ali | Mar 1993 | A |
5220762 | Lehnert et al. | Jun 1993 | A |
5258069 | Knechtel et al. | Nov 1993 | A |
5281265 | Liu | Jan 1994 | A |
5284700 | Strauss et al. | Feb 1994 | A |
5292781 | Floyd | Mar 1994 | A |
5296026 | Monroe et al. | Mar 1994 | A |
5304239 | Schwabe et al. | Apr 1994 | A |
5308692 | Kennedy et al. | May 1994 | A |
5319900 | Lehnert et al. | Jun 1994 | A |
5320677 | Baig | Jun 1994 | A |
5336316 | Dawson et al. | Aug 1994 | A |
5340392 | Westbrook et al. | Aug 1994 | A |
5342680 | Randall | Aug 1994 | A |
5366507 | Sottosanti | Nov 1994 | A |
5366810 | Merrifield et al. | Nov 1994 | A |
5371989 | Lehnert et al. | Dec 1994 | A |
5389716 | Graves | Feb 1995 | A |
5395685 | Seth et al. | Mar 1995 | A |
5397631 | Green et al. | Mar 1995 | A |
5401310 | Ture | Mar 1995 | A |
5401588 | Garvey et al. | Mar 1995 | A |
5411941 | Grinna et al. | May 1995 | A |
5437722 | Borenstein | Aug 1995 | A |
5462722 | Liu et al. | Oct 1995 | A |
5466273 | Connell | Nov 1995 | A |
5468282 | Yugami et al. | Nov 1995 | A |
5484653 | Kennedy et al. | Jan 1996 | A |
5496914 | Wood et al. | Mar 1996 | A |
5500668 | Malhotra et al. | Mar 1996 | A |
5508263 | Grinna et al. | Apr 1996 | A |
5520926 | Ferguson | May 1996 | A |
5527982 | Pal et al. | Jun 1996 | A |
5545297 | Andersen et al. | Aug 1996 | A |
5549859 | Andersen et al. | Aug 1996 | A |
5552187 | Green et al. | Sep 1996 | A |
5614307 | Andersen et al. | Mar 1997 | A |
5618627 | Merrifield et al. | Apr 1997 | A |
5624481 | Gerhardinger et al. | Apr 1997 | A |
5626668 | Gerhardinger et al. | May 1997 | A |
5626954 | Andersen et al. | May 1997 | A |
5631097 | Andersen et al. | May 1997 | A |
5637362 | Chase et al. | Jun 1997 | A |
5643510 | Sucech | Jul 1997 | A |
5644880 | Lehnert et al. | Jul 1997 | A |
5648097 | Nuwayser | Jul 1997 | A |
5654048 | Andersen et al. | Aug 1997 | A |
5658624 | Andersen et al. | Aug 1997 | A |
5683635 | Sucech et al. | Nov 1997 | A |
5695811 | Andersen et al. | Dec 1997 | A |
5704179 | Lehnert et al. | Jan 1998 | A |
5705237 | Andersen et al. | Jan 1998 | A |
5705242 | Andersen et al. | Jan 1998 | A |
5714001 | Savoly et al. | Feb 1998 | A |
5714032 | Ainsley et al. | Feb 1998 | A |
5718785 | Randall | Feb 1998 | A |
5718797 | Phillips et al. | Feb 1998 | A |
5744199 | Joffre et al. | Apr 1998 | A |
5746822 | Espinoza et al. | May 1998 | A |
5749936 | Humphries et al. | May 1998 | A |
5753163 | Sekhar et al. | May 1998 | A |
5759037 | Fischer | Jun 1998 | A |
5772846 | Jaffee | Jun 1998 | A |
5776245 | Thomas | Jul 1998 | A |
5791109 | Lehnert et al. | Aug 1998 | A |
5797988 | Linde et al. | Aug 1998 | A |
5798151 | Andersen et al. | Aug 1998 | A |
5807567 | Randolph et al. | Sep 1998 | A |
5817262 | Englert | Oct 1998 | A |
5830319 | Landin | Nov 1998 | A |
5830548 | Andersen et al. | Nov 1998 | A |
5837752 | Shastri et al. | Nov 1998 | A |
5855667 | Thomas | Jan 1999 | A |
5879498 | Lemons | Mar 1999 | A |
5882395 | Linde et al. | Mar 1999 | A |
5883024 | O'Haver-Smith et al. | Mar 1999 | A |
5908521 | Ainsley et al. | Jun 1999 | A |
5945044 | Kawai et al. | Aug 1999 | A |
5981406 | Randall | Nov 1999 | A |
6001496 | O'Haver-Smith | Dec 1999 | A |
6106607 | Be et al. | Aug 2000 | A |
6110575 | Haga | Aug 2000 | A |
6182407 | Turpin et al. | Feb 2001 | B1 |
6187697 | Jaffee et al. | Feb 2001 | B1 |
6319312 | Luongo | Nov 2001 | B1 |
6340388 | Luongo | Jan 2002 | B1 |
6342284 | Yu et al. | Jan 2002 | B1 |
6355099 | Immordino et al. | Mar 2002 | B1 |
6365533 | Horner, Jr. et al. | Apr 2002 | B1 |
6409824 | Veeramasuneni et al. | Jun 2002 | B1 |
6432482 | Jaffee et al. | Aug 2002 | B1 |
6435369 | Poursayadi | Aug 2002 | B1 |
6443258 | Putt et al. | Sep 2002 | B1 |
6465165 | Landry-Coltrain et al. | Oct 2002 | B2 |
6492450 | Hsu | Dec 2002 | B1 |
6494609 | Wittbold et al. | Dec 2002 | B1 |
6524679 | Hauber et al. | Feb 2003 | B2 |
6547874 | Eck et al. | Apr 2003 | B2 |
6566434 | Mayer et al. | May 2003 | B1 |
6569541 | Martin et al. | May 2003 | B1 |
6632550 | Yu et al. | Oct 2003 | B1 |
6723670 | Kajander et al. | Apr 2004 | B2 |
6737156 | Koval et al. | May 2004 | B2 |
6746781 | Francis et al. | Jun 2004 | B2 |
6747922 | Kamiyama | Jun 2004 | B2 |
6770354 | Randall et al. | Aug 2004 | B2 |
6774146 | Savoly et al. | Aug 2004 | B2 |
6800131 | Yu et al. | Oct 2004 | B2 |
6800361 | Bruce et al. | Oct 2004 | B2 |
6808793 | Randall et al. | Oct 2004 | B2 |
6822033 | Yu et al. | Nov 2004 | B2 |
6838163 | Smith et al. | Jan 2005 | B2 |
6866492 | Hauber et al. | Mar 2005 | B2 |
6874930 | Wittbold et al. | Apr 2005 | B2 |
6875308 | Kajander et al. | Apr 2005 | B2 |
6878321 | Hauber et al. | Apr 2005 | B2 |
6902615 | Shoshany | Jun 2005 | B2 |
6932863 | Shoshany | Aug 2005 | B2 |
6946504 | Sinnige | Sep 2005 | B2 |
7056582 | Carbo et al. | Jun 2006 | B2 |
7244304 | Yu et al. | Jul 2007 | B2 |
7338702 | Swales | Mar 2008 | B2 |
7364676 | Sucech et al. | Apr 2008 | B2 |
7413603 | Miller et al. | Aug 2008 | B2 |
7435369 | Hennis et al. | Oct 2008 | B2 |
7803226 | Wang et al. | Sep 2010 | B2 |
7811685 | Wang et al. | Oct 2010 | B2 |
7815730 | Wang et al. | Oct 2010 | B2 |
7892472 | Veeramasuneni et al. | Feb 2011 | B2 |
20010009834 | Peng et al. | Jul 2001 | A1 |
20020045074 | Yu et al. | Apr 2002 | A1 |
20020151240 | Smith et al. | Oct 2002 | A1 |
20020155282 | Randall et al. | Oct 2002 | A1 |
20030031854 | Kajander et al. | Feb 2003 | A1 |
20030032350 | Kajander et al. | Feb 2003 | A1 |
20030054714 | Peng et al. | Mar 2003 | A1 |
20030114065 | Peng et al. | Jun 2003 | A1 |
20030119408 | Choi | Jun 2003 | A1 |
20030129903 | Moes | Jul 2003 | A1 |
20030134079 | Bush et al. | Jul 2003 | A1 |
20030134554 | Halm et al. | Jul 2003 | A1 |
20030139111 | Kajander et al. | Jul 2003 | A1 |
20030175478 | Leclercq | Sep 2003 | A1 |
20030203191 | Randall et al. | Oct 2003 | A1 |
20030211305 | Koval et al. | Nov 2003 | A1 |
20040033749 | Smith et al. | Feb 2004 | A1 |
20040043682 | Taylor et al. | Mar 2004 | A1 |
20040083927 | Shoshany | May 2004 | A1 |
20040083928 | Shoshany | May 2004 | A1 |
20040142618 | Porter | Jul 2004 | A1 |
20040166751 | Peng et al. | Aug 2004 | A1 |
20040198116 | Peng et al. | Oct 2004 | A1 |
20040209074 | Randall et al. | Oct 2004 | A1 |
20040231916 | Englert et al. | Nov 2004 | A1 |
20040266303 | Jaffee | Dec 2004 | A1 |
20040266304 | Jaffee | Dec 2004 | A1 |
20050019618 | Yu et al. | Jan 2005 | A1 |
20050070186 | Shoemake et al. | Mar 2005 | A1 |
20050103262 | Bush et al. | May 2005 | A1 |
20050112977 | Choi | May 2005 | A1 |
20050136241 | Kajander et al. | Jun 2005 | A1 |
20050142348 | Kajander et al. | Jun 2005 | A1 |
20050181693 | Kajander | Aug 2005 | A1 |
20050202223 | Harima et al. | Sep 2005 | A1 |
20050202258 | Swales et al. | Sep 2005 | A1 |
20050202742 | Smith et al. | Sep 2005 | A1 |
20050221705 | Hitch | Oct 2005 | A1 |
20050233657 | Grove et al. | Oct 2005 | A1 |
20050266225 | Currier et al. | Dec 2005 | A1 |
20060010786 | Rogers | Jan 2006 | A1 |
20060035112 | Veeramasuneni et al. | Feb 2006 | A1 |
20060272764 | Smith | Dec 2006 | A1 |
20070022913 | Wang et al. | Feb 2007 | A1 |
20070026578 | Kim et al. | Feb 2007 | A1 |
20070056478 | Miller et al. | Mar 2007 | A1 |
20070148430 | Agrawal | Jun 2007 | A1 |
20080003903 | Nandi | Jan 2008 | A1 |
20080057318 | Adzima et al. | Mar 2008 | A1 |
20080176050 | Lintz et al. | Jul 2008 | A1 |
20080190062 | Engbrecht et al. | Aug 2008 | A1 |
20090011207 | Dubey | Jan 2009 | A1 |
20090186549 | Bennett | Jul 2009 | A1 |
20090239087 | Wang et al. | Sep 2009 | A1 |
20100055477 | Wang et al. | Mar 2010 | A1 |
Number | Date | Country |
---|---|---|
69055-74 | Nov 1975 | AU |
993779 | Jul 1976 | CA |
2116443 | Mar 1993 | CA |
7806114 | Mar 1978 | DE |
2808723 | Sep 1979 | DE |
3135865 | Mar 1983 | DE |
3508933 | Oct 1986 | DE |
198 53 450 | May 2000 | DE |
0154094 | Sep 1985 | EP |
0 681 998 | Nov 1995 | EP |
1 801 278 | Jun 2007 | EP |
1801278 | Jun 2007 | EP |
585627 | Feb 1947 | GB |
672829 | May 1952 | GB |
735405 | Aug 1955 | GB |
736257 | Sep 1955 | GB |
772581 | Apr 1957 | GB |
833800 | Apr 1960 | GB |
873805 | Jul 1961 | GB |
1064462 | Apr 1967 | GB |
1170079 | Nov 1969 | GB |
1197221 | Jul 1970 | GB |
1250713 | Oct 1971 | GB |
1498030 | Jan 1978 | GB |
2004807 | Apr 1979 | GB |
2007153 | May 1979 | GB |
2013563 | Aug 1979 | GB |
2023687 | Jan 1980 | GB |
1581396 | Dec 1980 | GB |
2053779 | Feb 1981 | GB |
2141456 | Dec 1984 | GB |
2142674 | Jan 1985 | GB |
2433497 | Jun 2007 | GB |
53-135125 | Nov 1978 | JP |
07-330410 | Dec 1995 | JP |
07-330411 | Dec 1995 | JP |
08-232442 | Sep 1996 | JP |
11-300882 | Nov 1999 | JP |
155679 | Dec 1971 | NZ |
2044714 | Sep 1995 | RU |
2058955 | Apr 1996 | RU |
94030472 | Jun 1996 | RU |
09-142915 D1 | Mar 1997 | RU |
2210553 | Aug 2003 | RU |
967984 | Oct 1982 | SU |
1052492 | Nov 1983 | SU |
WO 8002086 | Oct 1980 | WO |
93004009 | Mar 1993 | WO |
WO9304009 | Mar 1993 | WO |
WO 9908979 | Feb 1999 | WO |
WO 0006518 | Feb 2000 | WO |
WO 0145932 | Jun 2001 | WO |
WO0153075 | Jul 2001 | WO |
WO 2007005041 | Jan 2007 | WO |
WO 2007009935 | Jan 2007 | WO |
WO 2008066746 | Jun 2008 | WO |
Number | Date | Country | |
---|---|---|---|
20080190062 A1 | Aug 2008 | US |
Number | Date | Country | |
---|---|---|---|
60889487 | Feb 2007 | US |