Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B11/00—Calcium sulfate cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
  • C04B2111/0062—Gypsum-paper board like materials

Definitions

• the strength of gypsum products made from full density slurries is inversely proportional to the amount of water used in their manufacture.
• Some of the water that is added to the gypsum slurry is used to hydrate the calcined gypsum, also known as calcium sulfate hemihydrate, to form an interlocking matrix of calcium sulfate dihydrate crystals.
• Excess water evaporates or is driven off in a kiln, leaving voids in the matrix once occupied by the water. Where large amounts of water were used to fluidize the gypsum slurry, more and larger voids remain in the product when it is completely dry. These voids decrease the product density and strength in the finished product.
• the gypsum slurry of this invention is made using water, calcined gypsum, a polycarboxylate dispersant and a modifier. Although the benefits of this invention are most clear when used in a slurry for a high strength product, it can be used with any slurry using a polycarboxylate, even those that already utilize low doses of polycarboxylate dispersant.
• any calcined gypsum or stucco is useful in this slurry. It has unexpectedly been discovered that some gypsum sources are more responsive to the dispersant and the modifier than other sources. Laboratory tests indicate that gypsums from different geographical areas contain different salts and impurities. While not wishing to be bound by theory, it is believed that the salts present in the gypsum influence to the fluidity in the slurry.
• the polyether group of Formula Il contains multiple C 2 - C 4 alkyl groups, including at least two different alkyl groups, connected by oxygen atoms.
• M and n are integers from 2 to 4, inclusive, preferably, at least one of m and n is 2.
• X and y are integers from 55 to 350, inclusive.
• the value of z is from 0 to 200, inclusive.
• R 3 is a non-substituted or substituted aryl group and preferably phenyl.
• R 4 is hydrogen or an aliphatic Ci to C 2 o hydrocarbon group, a cycloaliphatic C 5 to C 8 hydrocarbon group, a substituted C ⁇ to C 14 aryl group or a group conforming at least one of Formula lll(a), lll(b) and lll(c).
• R 5 and R 7 independently of each other, represent an alkyl, aryl, aralkyl or alkylaryl group.
• R 6 is a bivalent alkyl, aryl, aralkyl or alkylaryl group.
• PCE211 A particularly useful dispersant of the PCE211-Type Dispersants is designated PCE211 (hereafter "211").
• Other polymers in this series known to be useful in wallboard include PCE111.
• PCE211-Type dispersants are described more fully in U.S. Serial No. 11 /xxx.xxx, by Degussa Construction Polymers (Attorney Ref. DCP3) entitled “Polyether-Containing Copolymer", and U.S. Serial No. 11/152,678 entitled “Polyether-Containing Copolymer", filed June 14, 2005, both of which are herein incorporated by reference.
• R 1 preferably makes up from about 300 to about 99 mole % of the total repeating units, more preferably from about 40 to about 80%. From about 1 to about 70 mole % of the repeating units are R 2 , more preferably from about 10 to about 60 mole %.
• the dispersant includes at least three repeating units shown in Formula IV(a), IV(b) and IV(c).
• R 1 represents a hydrogen atom or an aliphatic hydrocarbon radical having from 1 to 20 carbon atoms.
• X represents OM, where M is a hydrogen atom, a monovalent metal cation, an ammonium ion or an organic amine radical.
• R 2 can be hydrogen, an aliphatic hydrocarbon radical having from 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having from 6 to 14 carbon atoms, which may be substituted.
• R 3 is hydrogen or an aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, which are optionally linear or branched, saturated or unsaturated.
• R 4 is hydrogen or a methyl group, depending on whether the structural units are acrylic or methacrylic.
• P can be from 0 to 3.
• M is an integer from 2 to 4, inclusive, and n is an integer from 0 to 200, inclusive.
• PCE211-Type and 2641-Type dispersants are manufactured by Degussa Construction Polymers, GmbH (Tr ⁇ stberg, Germany) and marketed in the United States by Degussa Corp. (Kennesaw, GA).
• Preferred 2641-Type Dispersants are sold by Degussa as MELFLUX 2641 F, MELFLUX 2651 F and MELFLUX 2500L dispersants.
• 2641-Type dispersants (MELFLUX is a registered trademark of Degussa Construction Polymers, Gm bH) are described for use in wallboard and gypsum slurries in U.S. Serial No. 11/152,661 (Attorney Ref. No. 2033.72380), entitled “Fast Drying Wallboard", previously incorporated by reference.
• polycarboxylate dispersants are relatively expensive components, it is preferred to use a small dose, preferably less than 2% or more preferably less than 1 % by weight based on the weight of the dry stucco.
• the dispersant is used in amounts of about 0.05% to about 0.5% based on the dry weight of the stucco. More preferably, the dispersant is used in amounts of about 0.01% to about 0.2% on the same basis. In measuring a liquid dispersant, only the polymer solids are considered in calculating the dosage of the dispersant, and the water from the dispersant is considered when a water/stucco ratio is calculated.
• the ratio of the acid- containing repeating units to the polyether-containing repeating unit is directly related to the charge density.
• the charge density of the co-polymer is in the range of about 300 to about 3000 ⁇ equiv. charges/g co-polymer. It has been found that the most effective dispersant tested for water reduction in this class of dispersants, MELFLUX 2651 F, has the highest charge density.
• the increase in charge density further results in an increase in the retardive effect of the dispersant.
• Dispersants with a low charge density such as MELFLUX 2500L, retard the set times less than the MELFLUX 2651 F dispersant that has a high charge density. Since retardation in set times increases with the increase in efficacy obtained with dispersants of high charge density, making a slurry with low water, good flowability and reasonable set times requires keeping of the charge density in a mid-range. More preferably, the charge density of the co-polymer is in the range of about 600 to about 2000 ⁇ equiv. charges/g co-polymer.
• the modifier can be any substance, liquid or solid, which when combined with a polycarboxylate dispersant in a gypsum slurry, leads to an improvement the efficacy of the dispersant.
• Modifiers are not intended to be dispersants in themselves, but serve to allow the dispersant to be more effective. For example, at constant concentrations of dispersant, better fluidity is obtained when the modifier is used compared to the same slurry without the modifier.
• Preferred modifiers include cement, lime, also known as quicklime or calcium oxide, slaked lime, also known as calcium hydroxide, soda ash, also known as sodium carbonate, potassium carbonate, also known as potash, and other carbonates, silicates, hydroxides, phosphonates and phosphates.
• Preferred carbonates include sodium and potassium carbonate.
• Sodium silicate is a preferred silicate.
• lime or slaked lime When lime or slaked lime is used as the modifier, it is used in concentrations of about 0.15% to about 1.0% based on the weight of the dry calcium sulfate hemihydrate.
• lime In the presence of water, lime is quickly converted to calcium hydroxide, or slaked lime, and the pH of the slurry becomes alkaline. The sharp rise in pH can cause a number of changes in the slurry chemistry.
• Certain additives, including trimetaphosphate break down as the pH increases. There can also be problems with hydration and, where the slurry is used to make wallboard or gypsum panels, there are problems with paper bond at high pH.
• modifiers include carbonates, phosphonates, phosphates and silicates.
• the modifiers are used in amounts less than 0.25% based on the weight of the dry calcium sulfate hemihydrate. Above these concentrations, increases in the amount of modifier causes a decrease in the dispersant efficacy. These modifiers are preferably used in amounts of from about 0.05 to about 0.2 weight %.
• the charge density of the dispersant has also been found to affect the ability of the modifier to interact with the dispersant. Given a family of dispersants with the same repeating units, the modifier causes a greater increase in efficacy in the dispersant having the higher charge density. It is important to note that although the general trend is to obtain a higher efficacy boost with higher charge density, when comparing the effectiveness of dispersants having different repeating units, the effectiveness of the dispersants may be considerably different at the same charge density. Thus, adjustment of the charge density may not be able to overcome poor fluidity with a particular family of dispersants for that application.
• Modifiers appear to be less effective if the calcium sulfate hemihydrate is wetted with the dispersant before the modifier is added to the mixture. It is, therefore, preferred that the dispersant and the modifier be combined prior to mixture with the stucco. If either the modifier or the dispersant is in a liquid form, the liquid is preferably added to the process water. The other of the modifier or the dispersant is then added to the water prior to addition of the calcium sulfate hemihydrate. Only a few seconds of mixing is needed to blend the modifier and the dispersant together. If both the modifier and the dispersant are in dry form, they can be mixed together and added simultaneously with the stucco.
• Dispersants are best utilized with a low salt stucco.
• Other dispersants such as the 2641 -Type Dispersants are suitable for use with high-salt stuccos.
• the amount of water used to fluidize the slurry can be reduced compared to slurries made without these additives.
• the stucco source, the calcining technique, the dispersant family, the charge density and the modifier all work together to produce a slurry of a given fluidity. In the laboratory, it is possible to reduce the water level close to that theoretically required to fully hydrate the calcium sulfate hemihydrate. When used in a commercial setting, process considerations may not allow water reduction to this degree.
• any amount of water may be used to make the slurry of this invention as long as the slurry has sufficient fluidity for the application being considered.
• the amount of water varies greatly, depending on the source of the stucco, how it is calcined, the additives and the product being made.
• WSR water to stucco ratio
• Pourable flooring utilizes a WSR of from about 0.17 to about 0.45, preferably from 0.17 to about 0.34. Flooring compositions using this dispersant are revealed in U.S. Serial No. 11/152,324 (Attorney Ref.
• Castable products utilize a WSR from about 0.1 to about 0.3, preferably from about 0.16 to about 0.25.
• water to stucco ratios of less than 0.1 are attainable, however, commercially, the water to stucco ratio is typically from 0.5 to 0.7.
• water to stucco ratios of about 0.2 to about 0.6 are preferred. The amount of water can be diminished compared to other slurries, resulting in fuel savings and higher product strength.
• the slurry is used to make gypsum panels or wallboard having increased strength.
• the slurry is poured onto at least one sheet of facing material. Facing materials are well known to an artisan of gypsum panels. Multi-ply paper is the preferred facing material, however, single-ply paper, cardboard, plastic sheeting and other facing materials may be used.
• CSA is a set accelerator comprising 95% calcium sulfate dihydrate co-ground with 5% sugar and heated to 250°F (121°C) to caramelize the sugar.
• CSA is available from USG Corporation, Southard, OK plant, and is made according to U.S. Patent No. 3,573,947, herein incorporated by reference.
• Potassium sulfate is another preferred accelerator.
• HRA is calcium sulfate dihydrate freshly ground with sugar at a ratio of about 5 to 25 pounds of sugar per 100 pounds of calcium sulfate dihydrate. It is further described in U.S. Patent No. 2,078,199, herein incorporated by reference. Both of these are preferred accelerators.
• wet gypsum accelerator WGA
• WGA wet gypsum accelerator
• a description of the use of and a method for making wet gypsum accelerator are disclosed in U.S. Patent No. 6,409,825, herein incorporated by reference.
• This accelerator includes at least one additive selected from the group consisting of an organic phosphonic compound, a phosphate- containing compound or mixtures thereof.
• This particular accelerator exhibits substantial longevity and maintains its effectiveness over time such that the wet gypsum accelerator can be made, stored, and even transported over long distances prior to use.
• the wet gypsum accelerator is used in amounts ranging from about 5 to about 80 pounds per thousand square feet (24.3 to 390 g/m 2 ) of board product.
• additives are included in the gypsum slurry to modify one or more properties of the final product.
• Additives are used in the manner and amounts as are known in the art. Concentrations are reported in amounts per 1000 square feet of finished board panels ("MSF"). Starches are used in amounts from about 3 to about 20 Ibs./MSF (14.6 to 97.6 g/m 2 ) to increase the density and strengthen the product. Glass fibers are optionally added to the slurry in amounts of at least 11 Ib./MSF (54 g/m 2 ). Up to 15 Ib./MSF (73.2 g/m 2 ) of paper fibers are also added to the slurry. Wax emulsions are added to the gypsum slurry in amounts up to 90 Ibs./MSF (0.4 kg/m 2 ) to improve the water-resistency of the finished gypsum board panel.
• any of the conventional foaming agents known to be useful in preparing foamed set gypsum products can be employed.
• Many such foaming agents are well known and readily available commercially, e.g. from GEO Specialty Chemicals, Ambler, PA.
• Foams and a preferred method for preparing foamed gypsum products are disclosed in U.S. Patent No. 5,683,635, herein incorporated by reference. If foam is added to the product, the polycarboxylate dispersant can be divided between the process water and the foam water prior to its addition to the calcium sulfate hemihydrate.
• a trimetphosphate compound is added to the gypsum slurry in some embodiments to enhance the strength of the product and to reduce sag resistance of the set gypsum.
• concentration of the trimetaphosphate compound is from about 0.07% to about 2.0% based on the weight of the calcined gypsum.
• Gypsum compositions including trimetaphosphate compounds are disclosed in U.S. Patent No. 6,342,284 and 6,632,550, both herein incorporated by reference.
• Exemplary trimetaphosphate salts include sodium, potassium or lithium salts of trimetaphosphate, such as those available from Astaris, LLC, St. Louis, MO.
• trimetaphosphate with lime or other modifiers that raise the alkalinity of the slurry. Above a pH of about 9.5, the trimetaphosphate loses its ability to strengthen the product and the slurry becomes severely retardive.
• biocides to reduce growth of mold, mildew or fungi are biocides to reduce growth of mold, mildew or fungi.
• the biocide can be added to the covering, the gypsum core or both.
• examples of biocides include boric acid, pyrithione salts and copper salts.
• Biocides can be added to either the facing or the gypsum core. When used, biocides are used in the facings in amounts of less than about 500 ppm.
• the gypsum composition optionally can include a starch, such as a pregelatinized starch and/or an acid- modified starch.
• a starch such as a pregelatinized starch and/or an acid- modified starch.
• the inclusion of the pregelatinized starch increases the strength of the set and dried gypsum cast and minimizes or avoids the risk of paper delamination under conditions of increased moisture (e.g., with regard to elevated ratios of water to calcined gypsum).
• a starch such as a pregelatinized starch and/or an acid- modified starch.
• pregelatinized starch increases the strength of the set and dried gypsum cast and minimizes or avoids the risk of paper delamination under conditions of increased moisture (e.g., with regard to elevated ratios of water to calcined gypsum).
• methods of pregelatinizing raw starch such as, for example, cooking raw starch in water at temperatures of at least about 185°
• gypsum board is made in a continuous process formed into a long panel and cut into panels of desired lengths.
• the formed facing material is obtained and put into place to receive the gypsum slurry.
• the facing material is of a width to form a continuous length of panel that requires no more than two cuts to make a panel with the desired finished dimensions.
• Any known facing material is useful in making the wallboard panels, including paper, glass mat and plastic sheeting. Facing material is continuously fed to the board line.
• the slurry is formed by mixing the dry components and the wet components together in any order.
• liquid additives are added to the water, and the mixer is activated for a short time to blend them. Water is measured directly into the mixer. If modifiers are used, preferably the modifiers and dispersants are predissolved in the mixer water prior to introduction of the stucco. Dry components of the slurry, the calcined gypsum and any dry additives, are preferablyblended together prior to entering the mixer. The dry components are added to the liquid in the mixer, and blended until the dry components are moistened.
• the slurry is then mixed to achieve a homogeneous slurry.
• an aqueous foam is mixed into the slurry to control the density of the resultant core material.
• Such an aqueous foam is usually generated by high shear mixing of an appropriate foaming agent, water and air to prior to the introduction of the resultant foam into the slurry.
• the foam can be inserted into the slurry in the mixer, or preferably, into the slurry as it exits the mixer in a discharge conduit. See, for example, U.S. Patent No. 5,683,635, herein incorporated by reference.
• frequently solids and liquids are continuously added to a mixer, while the resultant slurry is continuously discharged from the mixer, and has an average residence time in the mixer of less than 30 seconds.
• the slurry is continuously dispensed through one or more outlets from the mixer through a discharge conduit and deposited onto a moving conveyor carrying the facing material and formed into a panel.
• Another paper cover sheet is optionally placed on top of the slurry, so that the slurry is sandwiched between two moving cover sheets which become the facings of the resultant gypsum panel.
• the thickness of the resultant board is controlled by a forming plate, and the edges of the board are formed by appropriate mechanical devices which continuously score, fold and glue the overlapping edges of the paper. Additional guides maintain thickness and width as the setting slurry travels on a moving belt. While the shape is maintained, the calcined gypsum is kept under conditions sufficient (i.e. temperature of less than about 120°F) to react with a portion of the water to set and form an interlocking matrix of gypsum crystals. The board panels are then cut, trimmed and passed to dryers to dry the set but still somewhat wet boards.
• a two-stage drying process is employed.
• the panels are first subjected to a high temperature kiln to rapidly heat up the board and begin to drive off excess water.
• the temperature of the kiln and the residence time of the board vary with the thickness of the panel.
• a 1/2-inch board (12.7mm) is preferably dried at temperatures in excess of 300°F (149°C) for approximately 20 to 50 minutes.
• 149°C 300°F
• a second-stage oven has temperatures less than 300 0 F (149°C) to limit calcination of the board.
• EXAMPLE I Tests were conducted to determine the effect of the addition of potassium carbonate on two different dispersants.
• a gypsum slurry was made from 400 grams of stucco from Southard, OK, 180 grams of water and 0.2% dispersant based on the dry weight of the stucco.
• the dispersant type and amount of potassium carbonate are shown in Table I below, together with the results of the patty size and the stiffening rate tests.
• Sodium carbonate was added at the concentrations shown in Table III, ranging from none to 0.6% by weight based on the weight of the dry stucco.
• the water demand and the set time are shown in Table III.
• Hydroxides act as modifiers, allowing less water to be used to obtain a standard fluidity which produces a standard patty size. Although the efficacy is good, hydroxides are not suitable for some products, such as wallboard, because the slurry becomes very alkaline, causing loss of efficacy of some preferred additives, including trimetaphosphate. Even at 0.05% CaMg(OH) 4 , the pH was above 10. For products where pH of the product is not a problem, hydroxides can be used effectively as modifiers.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Mechanical Engineering (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

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• 2006
  • 2006-06-13 AU AU2006259585A patent/AU2006259585B2/en not_active Ceased
  • 2006-06-13 KR KR1020087001090A patent/KR20080016960A/ko not_active Ceased
  • 2006-06-13 EP EP06773002A patent/EP1896376A4/de not_active Withdrawn
  • 2006-06-13 CA CA002607973A patent/CA2607973A1/en not_active Abandoned
  • 2006-06-13 WO PCT/US2006/022936 patent/WO2006138277A2/en not_active Ceased
  • 2006-06-14 AR ARP060102521A patent/AR053628A1/es unknown
• 2007
  • 2007-11-09 NO NO20075725A patent/NO20075725L/no not_active Application Discontinuation

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