WO2023154662A1 - Panneau de gypse contenant de la vermiculite à échange d'ammonium et procédés associés - Google Patents

Panneau de gypse contenant de la vermiculite à échange d'ammonium et procédés associés Download PDF

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Publication number
WO2023154662A1
WO2023154662A1 PCT/US2023/061945 US2023061945W WO2023154662A1 WO 2023154662 A1 WO2023154662 A1 WO 2023154662A1 US 2023061945 W US2023061945 W US 2023061945W WO 2023154662 A1 WO2023154662 A1 WO 2023154662A1
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WIPO (PCT)
Prior art keywords
gypsum
ammonium
vermiculite
core
slurry
Prior art date
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PCT/US2023/061945
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English (en)
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WO2023154662A4 (fr
Inventor
Qinghua Li
Mark Hemphill
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United States Gypsum Company
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Filing date
Publication date
Priority claimed from US17/948,710 external-priority patent/US20230250019A1/en
Application filed by United States Gypsum Company filed Critical United States Gypsum Company
Publication of WO2023154662A1 publication Critical patent/WO2023154662A1/fr
Publication of WO2023154662A4 publication Critical patent/WO2023154662A4/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/42—Micas ; Interstratified clay-mica products
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/20—Mica; Vermiculite
    • C04B14/206—Mica or vermiculite modified by cation-exchange; chemically exfoliated vermiculate
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0004—Compounds chosen for the nature of their cations
    • C04B2103/0005—Organic ammonium compounds
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0004—Compounds chosen for the nature of their cations
    • C04B2103/0006—Alkali metal or inorganic ammonium compounds
    • C04B2103/0009—Inorganic ammonium compounds
    • 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

  • This disclosure relates to products suitable as construction materials and containing set gypsum and ammonium-exchanged vermiculite, including gypsum panels characterized by decreased heat shrinkage and increased resistance to fire damage, especially wallboard and acoustical ceiling tiles, and building assemblies with the gypsum panels as well as methods.
  • Products that contain a gypsum core composed of set gypsum, preferably intermixed with one or more additives, are commonly used in construction, including as panels in walls and ceilings.
  • Exemplary gypsum panels include an acoustical tile, a fiberboard, a glass-mat gypsum panel, a gypsum core which may be further coated with one or more coatings and/or paints, and a wallboard in which a gypsum core is typically sandwiched between two paper cover sheets, a face cover sheet and a back cover sheet.
  • Vermiculite is a hydrated magnesium aluminum silicate mineral commercially available in several different basic particle sizes, referred in the U.S. as grades 1 through 5. When subjected to heat, vermiculite expands into incombustible and highly absorbent particles.
  • U.S. patent 8,323,785 discloses a fire-resistant gypsum panel comprising a gypsum core disposed between two cover sheets, the gypsum core comprising high expansion particles having a volume expansion of about 300% or more of their original volume for Grade 4 vermiculite after being heated for about one hour at about 1560°F.
  • U.S. patent publication 2021/0238096 notes that using vermiculite in amounts necessary for supporting sufficient fire-resistance may not be an environmentally sustainable practice because of the limited supply of vermiculite ore in nature. This patent publication proposes reducing an amount of vermiculite by replacing a portion of vermiculite with graphite, perlite, or any combination thereof.
  • This disclosure addresses the need for producing fire-resistant gypsum panels in an environmentally sustainable manner by formulating a gypsum core comprising ammonium-exchanged vermiculite, resulting in production of fire-resistant gypsum panels with a lesser amount of vermiculite.
  • Gypsum panels according to this disclosure may be formed with ammonium-exchange vermiculite. These gypsum panels are characterized by a decreased heat shrinkage and increased resistance to fire damage when compared to gypsum panels having the same amount of vermiculite which is not ammonium-exchanged.
  • this disclosure relates to a gypsum panel having a gypsum core comprising set gypsum and ammonium-exchanged vermiculite, wherein the gypsum core has a width (x), a length (y) and a thickness (z), wherein the length (y) and the width (x) are greater than the thickness (z), wherein the length (y) is greater than the width (x), wherein the gypsum core has two long surfaces, a first long surface of a widthlength (x-y) area and an opposite second long surface of the width-length (x-y) area, and wherein each of the two long surfaces has four edges, including a first long edge of the length (y) and a second long edge of the length (y), the second long edge being opposite to the first long edge.
  • the gypsum core may be formed from at least one gypsum slurry, wherein the gypsum slurry comprises water, calcined gypsum in an amount from 40% to 70% by weight of the slurry, ammonium-exchanged vermiculite in an amount from 2% to 10% by weight of calcined gypsum, and one or more additives, or wherein the gypsum slurry comprises water, calcined gypsum in an amount from 40% to 70% by weight of the slurry, vermiculite in an amount from 2% to 10% by weight of calcined gypsum, one or more additives, and one or more of ammonium salt, ammonium hydroxide and/or urea in a weight ratio to vermiculite ranging from 1:5 to 1:50; and wherein a water-to-stucco ratio in the gypsum slurry is from 0.5 to 1.5.
  • the gypsum core may contain ammonium-exchanged vermiculite of Grade 4, Grade 5, or any combination thereof.
  • the gypsum core may be covered on at least one of the two long surfaces with a cover sheet, preferably the cover sheet being a paper cover sheet or a fiberglass mat.
  • a cover sheet preferably the cover sheet being a paper cover sheet or a fiberglass mat.
  • Some preferred embodiments of the gypsum panel according to this disclosure include those wherein the gypsum core is covered on the first long surface with a first paper cover sheet and the gypsum core is covered on the second long surface with a second paper cover sheet, and wherein the first paper cover sheet and the second paper cover sheet are attached to the gypsum core.
  • the gypsum panels according to this disclosure include those wherein the gypsum core has the thickness (z) of 5/8 inch, and wherein the gypsum core has less than 5% thermal shrinkage in the z-direction, as measured in a thermal shrinkage test conducted in accordance with ASTM C 1795-15 at 850 °C for one hour.
  • the gypsum panels according to this disclosure also include those gypsum panels which are fire rated.
  • the gypsum core may have a density in the range from 30 pounds per cubic foot (pcf) to 40 pounds per cubic foot (pcf).
  • At least two long edges of the gypsum core may be tapered.
  • the gypsum panels according to this disclosure may have the thickness (z) in range from 1 ⁇ 4 inch to 1 inch.
  • Particularly preferred gypsum panels of this disclosure include fire-resistant wallboard with a thermal insulation index (TI) of at least 20 minutes, as measured in accordance with ASTM C 1795-15.
  • TI thermal insulation index
  • the additives in the gypsum panel may include starch, fibers, a dispersant, a foaming agent, a set accelerating agent, a phosphate compound, a set retarding agent or any combination thereof.
  • the gypsum slurry may include a foaming agent, water repellant or any combination thereof.
  • Particularly preferred gypsum panels include those, wherein the gypsum core contains air voids.
  • this disclosure relates to methods for making a gypsum panel having a gypsum core comprising set gypsum and ammonium-exchanged vermiculite. These methods comprise: a) mixing a gypsum slurry with calcined gypsum, water and additives; b) adding to the gypsum slurry ammonium-exchanged vermiculite or adding to the gypsum slurry vermiculite and one or more of ammonium salt, ammonium hydroxide and/or urea; c) depositing the gypsum slurry on a first cover sheet; and d) covering the deposited gypsum slurry with a second cover sheet.
  • the methods further comprise before step b), ion-exchanging vermiculite in a solution comprising one or more of ammonium salt, ammonium hydroxide and/or urea and thereby obtaining ammonium-exchanged vermiculite. More preferably, after the ion-exchanging reaction is completed, the method may further comprise one or more of the following steps: separating ammonium exchanged vermiculite from the solution and/or drying ammonium-exchanged vermiculite.
  • the additives may include one or more of the following: starch, foam, fibers, a dispersant, a phosphate compound, a set retarding agent, a set accelerating agent, or any combination thereof.
  • Some preferred embodiments of the methods include those, wherein the first cover sheet and/or the second cover sheet are paper cover sheets.
  • this disclosure relates to a wall or ceiling assembly comprising at least one gypsum panel according to this disclosure, wherein the gypsum panel is attached to a substrate.
  • Fig. 1 is a perspective view of one embodiment of a gypsum panel according to this disclosure. This illustration is not drawn to scale.
  • FIG. 2 is a schematic representation of one embodiment for a method according to this disclosure for manufacturing a gypsum panel having a gypsum core comprising set gypsum and ammonium-exchanged vermiculite.
  • Fig. 3 is a perspective view of one embodiment of a building assembly according to this disclosure. This illustration is not drawn to scale.
  • this disclosure relates to a gypsum panel having a gypsum core comprising set gypsum intermixed with ammonium (NH4+)-exchanged vermiculite.
  • Particularly preferred embodiments include gypsum panels having a gypsum core containing ammonium-exchanged vermiculite in an amount from 2% to 10% by weight of calcined gypsum, e.g., 2 to 10 grams of ammonium-exchanged vermiculite per 100 grams of calcined gypsum.
  • the gypsum panels according to this disclosure can meet or even exceed requirements for heat shrinkage and resistance to fire damage with lesser amounts of ammonium-exchanged vermiculite in comparison to gypsum panels with gypsum cores formulated with conventional vermiculite that has not been ammonium-exchanged.
  • the gypsum panels according to this disclosure formed with ammonium- exchange vermiculite are characterized by a decreased heat shrinkage and increased resistance to fire damage when compared to gypsum panels having the same amount of vermiculite which is not ammonium-exchanged.
  • a “gypsum panel” includes any panel having a gypsum core composed of at least set gypsum and ammonium-exchanged vermiculite.
  • the gypsum core may further contain and preferably does contain one or more additives, including, but not limited to, fibers, a polymeric binder and/or starch, a dispersant, a bulking compound, a set retarding agent, a set accelerating agent, a biocide, a water-repellant, a foaming agent, and/or any combination thereof.
  • Non-limiting examples of gypsum panels include an acoustical tile, a fiberboard, a fiberglass-mat gypsum panel and a wallboard in which a gypsum core is sandwiched between two paper cover sheets, a face cover sheet and a back cover sheet.
  • the gypsum panels of this disclosure are wallboards, including light-weight wallboards and/or light weight glass-mat gypsum panels which are made with foam.
  • This wallboard and gypsum panels may be referred in this disclosure as a gypsum panel having a foamed gypsum core.
  • Gypsum panel 10 may be substantially rectangular in its shape and has a width (x), a length (y) and a thickness (z). In some preferred embodiments, a value of length (y) is greater than a value of width (x) and accordingly, the panel 10 has 4 long edges of the (y) length, three of which are shown in Fig.
  • a direction across the length (y) may be referred to as the longitudinal direction
  • a direction across the width (x) may be referred to as the long transverse direction
  • a direction through the thickness (z) may be referred to as the short transverse direction.
  • Embodiments of gypsum panel 10 include panels of various thickness, width and length, and these dimensions can be adjusted as needed. Gypsum panels typically vary in thickness (z) from about 'A inch to about one inch, depending on their expected use and application. Gypsum panels may include those with a length (y) in the range of 8 to 16 ft., e.g., 8 ft, 10 ft or 16 ft (2438-4877 mm), a width (x) of 4 ft. (1219 mm) or 54 in. (1372 mm). Any of these panels can have a thickness from about l A inch to about one inch, with some preferred embodiments having a thickness (z) of 5/8 inch (15.9 mm). Gypsum panels 10 of other dimensions are also envisioned.
  • “about” means plus-minus 5% of the specified numeric value, e.g. “about 100” means 100+5.
  • the gypsum panel 10 has two long surfaces for the width-length (x-y) area, a first of these long surfaces is shown as 10S in Fig. 1.
  • a second long surface, 10S' is opposite to the first long surface 10S and is not visible in Fig. 1.
  • the first long surface 10S is called a face surface as it is typically visible to a dweller when the gypsum panel 10 is installed as a wall or ceiling.
  • the second long surface 10S' is called a back surface as it typically faces studs.
  • a gypsum core 12 is sandwiched between two cover sheets, a first cover sheet or a facer, 14, applied over the first long surfaceiOS and a second cover sheet or a backer, 16, applied over the second long surface 10S'.
  • the gypsum panel 10 may not have cover sheet 14 and/or cover sheet 16. If at least one of the cover sheets 14 and 16 is present, either cover sheet 14 or 16, or both, may be a paper cover sheet or a fiberglass mat. In some preferred embodiments, cover sheet 14 and cover sheet 16 are paper cover sheets.
  • the first cover sheet, 14, may be referred to as a face cover sheet or a facer and the second cover sheet, 16, may be referred to as a back cover sheet or a backer.
  • the gypsum core 12 is bound to the cover sheets 14 and 16.
  • the gypsum panel 10 is a wallboard comprising the gypsum core 12 disposed (sandwiched) between and attached to the face paper sheet 14 and the back paper sheet 16.
  • the gypsum core 12 may be laminated with a coating and/or an additional gypsum slurry layer on at least a portion of at least one of long surfaces IOS and IOS'. Any of the coatings and/or additional gypsum slurry layers can be helping with attaching (adhering) the gypsum core 12 to the face paper cover sheet 14 and/or the back paper cover sheet 16.
  • the face paper cover sheet or glass mat 14 may be folded around the long edges 10L to reinforce and protect the gypsum core 12, and the ends of the cover sheet 14 may be cut square and even.
  • at least some of the long edges 10L may be tapered, allowing panel joints to be reinforced and concealed during installation.
  • the gypsum panel 10 may further comprise one or more coatings (not shown in Fig. 1) that can be applied over the gypsum core 12 and/or at the edges of the gypsum panel 10 for example in order to improve binding of the gypsum core 12 to the cover sheets 14 and/or 16 and/or to improve the strength of the panel edges.
  • a coating e.g., a paint and/or water-resistant coating, may be also applied over the external surface (not in contact with the surface of the gypsum core) of the cover sheet 14 and/or cover sheet 16.
  • the gypsum core 12 contains set gypsum and ammonium- exchanged vermiculite, and preferably, the gypsum core 12 may contain one or more other additives as discussed in more detail below.
  • the gypsum panels according to the present disclosure can be formed from a gypsum slurry in which calcined gypsum (stucco) hardens (sets) by reacting with water.
  • calcined gypsum stucco
  • Suitable calcined gypsum can be obtained by calcining naturally occurring gypsum and/or synthetic gypsum.
  • Gypsum is a natural mineral containing calcium sulfate dihydrate (CaSO 4 X2H 2 O). Depending on a gypsum source, gypsum may comprise 90 to 95% pure calcium sulfate dihydrate.
  • calcined gypsum (calcium sulfate hemihydrate, CaSO 4 X1/2H 2 O) may contain alpha calcium sulfate hemihydrate, beta calcium sulfate hemihydrate, or any combination thereof.
  • Methods for producing calcined gypsum from gypsum and synthetic gypsum are known in the art, including methods disclosed in U.S. patents 3,410,655, 7,754,006 and 8,343,273, the entire disclosures of which are herein incorporated by reference.
  • Calcined gypsum may contain some minor amounts of other minerals, e.g., clay and/or calcium carbonate.
  • the gypsum core 12 in the gypsum panel 10 may comprise set synthetic gypsum produced as a by-product of fossil-fueled power plants.
  • gypsum core 12 may comprise up to 95 % wt of set gypsum.
  • Ammonium-exchanged vermiculite can be obtained by ion-exchanging vermiculite in an aqueous solution containing a source of ammonium ions such as an ammonium salt, ammonium hydroxide (NH4OH) and/or urea (NH2CONH2).
  • a source of ammonium ions such as an ammonium salt, ammonium hydroxide (NH4OH) and/or urea (NH2CONH2).
  • Suitable salts are organic and inorganic salts, including, but not limited to, ammonium dihydrogen phosphate (NH 4 H 2 PO 4 , “ADP”), ammonium monohydrogen phosphate ((NH 4 ) 2 HPO 4 , “AMP”), ammonium phosphate ((NH 4 ) 3 PO 4 , “AP”), ammonium sulfate (NH4)2SO4), ammonium carbonate ((NH 4 ) 2 CO 3 ), ammonium acetate (NH4CH2CHOO), or any combination thereof.
  • ADP ammonium dihydrogen phosphate
  • AMP ammonium monohydrogen phosphate
  • AP ammonium phosphate
  • AP ammonium sulfate
  • ammonium carbonate (NH 4 ) 2 CO 3 )
  • ammonium acetate (NH4CH2CHOO), or any combination thereof.
  • vermiculite of any grade, and preferably of U.S. Grade 4 and/or 5 can be mixed with an aqueous solution containing an ammonium salt, ammonium hydroxide (NH4OH) and/or urea (NH2CONH2) and incubated in the solution for a period of time ranging from about 2 minutes to about 2 days and more preferably for about 5 minutes to about 10 hours, preferably with shaking and/or stirring.
  • the ammonium salt, ammonium hydroxide and/or urea concentration in the solution may be in the range 1 and 40% .
  • the solution may contain 1 part by weight of the ammonium salt, ammonium hydroxide and/or urea per 5 to 50 parts by weight of vermiculite.
  • a total volume of an ammonium-exchanging solution can be adjusted such that all or substantially all vermiculite particles are immersed into the ammonium-exchanging solution.
  • the ratio of the ammonium-exchange solution by volume to vermiculite may be in the range from 1:0.1 to 1:10, e.g., 1:0.5; 1:1 or 1:5.
  • Preferred concentrations for ammonium-exchanging solutions may be in the range from about 1% to about 40% by weight and more preferably from about 1% to about 10% by weight, e.g., 2.5%, 5% or 7.5% by weight, of an ammonium salt, ammonium hydroxide and/or urea. Most preferred aqueous ammonium-exchanging solutions include those comprising 2.5% to 7.5% by weight of one or more ammonium salts.
  • This ion-exchanging reaction can be conducted in the range from 19°C to 50°C, preferably in the range from 19°C to 30°C.
  • a person of skill will also recognize obvious modifications, including increasing or decreasing the temperature, increasing or decreasing a salt concentration, and/or increasing or decreasing the incubation time.
  • ammonium-changed vermiculite can be filtered from the solution and optionally at least partially dried, preferably at an elevated temperature, e.g., in the range from 90°F to 120°F for a period of time, preferably for 0.5 to 12 hours. Or, in alternative, ammonium-exchanged vermiculite can be added into a gypsum slurry without drying.
  • a gypsum core can be made from a gypsum slurry comprising calcined gypsum, water, vermiculite and an ammonium salt, ammonium hydroxide and/or urea, and optionally any other additives typically used in manufacturing gypsum cores.
  • vermiculite is ion- exchanged into ammonium-exchanged vermiculite directly in the gypsum slurry and while the gypsum slurry is getting mixed, distributed and formed into a gypsum core.
  • a gypsum slurry may contain from 2% to 10% of vermiculite by weight of calcined gypsum.
  • an ammonium salt, ammonium hydroxide and/or urea can be used in the following ratio: one part of dry powder (ammonium salt, ammonium hydroxide and/or urea) per 5 to 50 parts of vermiculite.
  • Suitable organic and inorganic ammonium salts include, but not limited to, ammonium dihydrogen phosphate (NH4H2PO4, “ADP”), ammonium monohydrogen phosphate ((NH 4 ) 2 HPO 4 , “AMP”), ammonium sulfate (( (NH 4 ) 2 SO) 4 ,) ammonium carbonate ((NH 4 ) 2 CO 3 ), ammonium acetate (NH 4 CH 2 CHOO), or any combination thereof.
  • a combination of ammonium dihydrogen phosphate (NH4H2PO4, “ADP”) and ammonium sulfate (( (NH 4 ) 2 SO) 4 can be used.
  • Ammonium sulfate and ADP can be used in any proportion to each other, and preeerably in the ratio range from 10: 1 to 1: 10 by weight, respectively.
  • suitable gypsum slurries include those in which a water-to- calcined gypsum ratio by weight (known as the water- to- stucco ratio, WSR) is in the range from 0.5 to 1.5, preferably from 0.5 to 1.3, more preferably from 0.7 to 1, and most preferably from 0.7 to 1.3, e.g., 0.7, 0.8, 0.9, 1, 1.1, 1.2 or 1.3.
  • WSR water-to- calcined gypsum ratio by weight
  • a gypsum slurry may comprise from 40% to 70% by weight of calcined gypsum.
  • Ammonium-exchanged vermiculite according to this disclosure is expandable when exposed to heat, and more specifically when exposed to 850°C known as a thermal test, ammonium-exchanged vermiculite may produce a volume expansion of 300% or even higher than 300%.
  • grades of vermiculite may be determined based on a percentage of particles by weight retained on a sieve with openings of a predetermined size.
  • a person of skill will recognize the following U.S. sieve numbers and their corresponding opening sizes.
  • Grade 4 vermiculite includes vermiculite with particle sizes wherein from 25% to 60% of particles by weight are retained on a No. 40 sieve (0.420 mm openings) or a No. 50 sieve (0.297 mm openings), with the remaining passed-through 25% of particles by weight being retained on a No. 70 sieve (0.210 mm openings) and then the remaining passed-through 15% of particles by weight being retained on a No. 100 sieve (0.149 mm opening).
  • Grade 4 includes vermiculite with 90% by weight of particles being smaller than 0.841 mm and 25% to 60% by weight of particles being larger than 0.420 mm, as can be determined by sieving particles through a No. 20 (0.841 mm openings) sieve and then sieving passed-through particles through a No. 40 (0.420 mm opening) sieve and weighing particles that were retained on each of the sieves.
  • Grade 5 vermiculite includes vermiculite with particle sizes, wherein 30% to 76% of particles by weight are retained on a No. 100 sieve (0.149 mm openings) and 20% of particles by weight are retained on a No. 50 sieve (0.297 mm openings).
  • Grade 5 vermiculite includes vermiculite with 30% to 76% of particles by weight being larger than 0.149 mm and no more than 20% of particles being larger than 0.297 mm, as determined by sieving the particles through a No. 50 sieve (0.297 mm openings) and then sieving passed-through particles through a No. 100 sieve (0.149 mm openings) and weighing particles that were retained on each of the sieves.
  • Gypsum panels according to this disclosure include those in which a gypsum core contains ammonium-exchanged vermiculite produced from vermiculite with larger particles such as for example, Grade 4 vermiculite.
  • Suitable ammonium-exchanged vermiculite in the gypsum core of this disclosure includes vermiculite in which 40% to 80% by weight, preferably about 55% to about 65% by weight, and most preferably about 60% of vermiculite particles by weight from vermiculite total have a size in the range from 0.297 mm to 0.420 mm, as determined by sieving the particles through a No. 40 sieve (0.420 mm openings), collecting particles that passed through the sieve and then sieving them through a No. 50 sieve (0.297 mm openings).
  • the gypsum panel according to this disclosure may comprise a gypsum core which contains ammonium-exchanged vermiculite of Grade 4, Grade 5, or any combination thereof.
  • a fire-resistant gypsum panel can be obtained with ammonium-exchanged vermiculite of different grades, including larger particles such as for example as ammonium- exchanged vermiculite which contains particles ranging in sizes from about 0.297 mm to about 0.841 mm, and preferably containing particles which are ranging in sizes from about 0.420 mm to about 0.841 mm, as can be determined by sieving particles through sieves listed in Table 1.
  • Gypsum panels according to this disclosure include fire-resistant gypsum wallboard, such as ULX and ULIX (ultralight) gypsum panels, or any fire-resistant gypsum panels comprising ammonium-exchanged vermiculite.
  • fire-resistant gypsum wallboard such as ULX and ULIX (ultralight) gypsum panels, or any fire-resistant gypsum panels comprising ammonium-exchanged vermiculite.
  • These gypsum panels comprise a gypsum core containing a set gypsum intermixed with various additives and ammonium-exchanged vermiculite, preferably an amount of ammonium-exchanged vermiculite being in the range from 2% to 10% by weight of calcined gypsum.
  • the additives may include, but are not limited to, one or more of the following: starch, fibers, a dispersant, a foaming agent, a phosphate compound and/or agents that accelerate or delay a setting reaction in a gypsum slurry.
  • “High Temperature (Thermal) Shrinkage” of a gypsum core can be measured in accordance with ASTM C 1795-15, wherein the gypsum core is heated at about 1560 °F (850 °C) for one hour. Thermal shrinkage can be measured as a percentage from a pre-test gypsum core thickness value (z-shrinkage or z-direction shrinkage) and as a percentage from a pre-test gypsum core value for the x-y (width-length) area (x-y shrinkage or x-y-direction shrinkage).
  • wallboards having a gypsum core that contains ammonium-exchanged vermiculite according to this disclosure have a reduced z-direction shrinkage in comparison to wallboards that comprise vermiculite which was not ammonium-exchanged.
  • the z-direction shrinkage was less than 6% and more preferably less than 5% in some embodiments of a gypsum core containing ammonium-exchanged vermiculite according to this disclosure.
  • a gypsum core with ammonium-exchange vermiculite permits producing fire-resistant wallboard with a thermal insulation index (TI) of at least 20 minutes, 30 minutes or greater, when measured in accordance with ASTM C 1795-15.
  • the wallboard may include gypsum panels with a gypsum core of reduced density, e.g., about 40 pound per cubic foot (pcf) or less and preferably, about 35 pcf or less.
  • Some preferred gypsum panels according to this disclosure may have a gypsum core density in the range from 30 pcf to 40 pcf, and more preferably from 32 pcf to 38 pcf, and most preferably from 35 pcf to 37 pcf.
  • a gypsum core can be formed from a gypsum slurry containing calcined gypsum (stucco, calcium sulfate hemihydrate), water, ammonium-exchanged vermiculite and one or more additives as used in gypsum cores and gypsum slurries.
  • additives include, but are not limited to, binders, fibers, set accelerators, set retarders, dehydration inhibitors, adhesives, bulking agents, dispersants, thickeners, bactericides, fungicides, pH adjusters, leveling or non-leveling agents, water repellants, colorants, aqueous foams or any combination thereof.
  • the gypsum slurry may be formulated with vermiculite and one or more of ammonium salt, ammonium hydroxide and/or urea which can be used in an amount of about one part by weight of one or more of ammonium salt, ammonium hydroxide and/or urea per about 5 to about 50 parts by weight of vermiculite.
  • the gypsum cores and gypsum slurries according to this disclosure may comprise one or more starches, including raw starch, hydroxy ethylated starch, acid- modified starch, pregelatinized starch or any combination thereof.
  • starch may include pregelatinized starch which can be obtained by cooking and gelatinizing raw starch in water, for example at a temperature of about 185 °F, or higher.
  • a pregelatinized starch can be added to the gypsum slurry in a dry form and/or in a predispersed liquid form.
  • Commercially available pregelatinized starches include com flour starch.
  • Suitable starches may also include acid-modified starch, e.g., acid-modified corn starch and/or hydroxyethylated starch.
  • Suitable non-gelatinized starches may include commercially available wheat starch.
  • the gypsum slurries and gypsum cores of this disclosure may comprise from 0.1% to 5% of starch, preferably from about 0.2% to about 2% of starch by weight of calcined gypsum.
  • the gypsum cores and gypsum slurries according to this disclosure may comprise fibers.
  • fibers may include mineral wool fibers, glass fibers, carbon fibers, cellulose fibers or any combination thereof. Some preferred embodiments include those in which glass fibers, preferably E-glass fibers are used.
  • suitable glass fibers may have an average length in the range from 0.5 to 0.76 inches and a diameter of about 11 to about 17 microns.
  • the gypsum slurries and gypsum cores of this disclosure may comprise from about 0.1% to about 2% of fibers by weight of calcined gypsum, preferably from about 0.2% to about 1% of fibers by weight of calcined gypsum.
  • the gypsum cores and gypsum slurries according to this disclosure may comprise one or more of phosphate compounds which are used for increasing gypsum core strength, especially while a gypsum panel is still setting in order to improve wet (green) strength and sag resistance of the gypsum panel.
  • Suitable phosphate compounds include cyclic polyphosphates, condensed phosphoric acids, and monobasic salts or monovalent ions of orthophosphates.
  • Particularly preferred phosphate compounds include, but are not limited to, trimetaphosphate salts and tetrametaphosphate salts.
  • Particularly preferred phosphate compounds include sodium trimetaphosphate (“STMP”), potassium trimetaphosphate, ammonium trimetaphosphate, sodium hexametaphosphate, tetrapotassium tripolyphosphate, ammonium polyphosphate, aluminum trimetaphosphate or any combination thereof.
  • STMP sodium trimetaphosphate
  • potassium trimetaphosphate potassium trimetaphosphate
  • ammonium trimetaphosphate sodium hexametaphosphate
  • tetrapotassium tripolyphosphate ammonium polyphosphate
  • aluminum trimetaphosphate or any combination thereof The gypsum slurries and gypsum cores of this disclosure may comprise from about 0% to about 1% of one or more phosphate compounds by weight of calcined gypsum, preferably from about 0 % to about 1% of one or more phosphate compound by weight of calcined gypsum.
  • the gypsum cores and gypsum slurries according to this disclosure may comprise one or more dispersants.
  • Suitable dispersants include naphthalensulfonates and derivatives, including sodium and/or calcium naphthalenesulfonate.
  • Other suitable dispersants include polycarboxylate dispersants and in particular, polycarboxylic ethers, including those described in U.S. patents 5,798,425, 6,777,517 and 7,767,019.
  • Some gypsum slurries may also comprise one or more lignosulfonates.
  • the gypsum slurries and gypsum cores of this disclosure may comprise from about 0.05% to about 2% of one or more dispersants by weight of calcined gypsum, preferably from about 0.1% to about 1% of one or more phosphate compound by weight of calcined gypsum.
  • the gypsum cores and gypsum slurries according to this disclosure may comprise one or more set retarding and/or accelerating agents. These are compounds that modify a rate at which a gypsum slurry sets.
  • Preferred examples of set accelerating agents include “CSA” which may contain about 95% of calcium sulfate dihydrate co-ground with 5% sugar and then heat processed, as was described in U.S. Patent 3,573,947.
  • Other suitable accelerators include potassium sulfate and “HRA” which comprises calcium sulfate dihydrate freshly ground with sugar at a ratio of about 5 to about 25 pounds of sugar per 100 pounds of calcium sulfate dihydrate, as described in U.S. patent 2,078,199.
  • Other accelerators for controlling a setting reaction in a gypsum slurry include wet gypsum accelerator (WGA) as described in U.S. Patent 6,409,825.
  • a set accelerating agent can be used in any amount suitable for controlling the rate of a calcined gypsum hydration.
  • the gypsum slurry according to this disclosure may comprise from about 0.1% to about 4% of one or more accelerating agents (accelerators), e.g., HRA or CSA, by weight of calcined gypsum, and more preferably from about 0.5% to about 2% of one or more a set accelerating agent by weight of calcined gypsum.
  • accelerating agents e.g., HRA or CSA
  • Suitable set retarding agents delay a hydration reaction of calcined gypsum.
  • Such set retarding agents may include, but are not limited to, commercially available protein retarder SUMA, diethylenetriamine pentaacetic acid (DTPA), tartaric acid, citric acid, maleic acid or salts thereof, including in particular sodium citrate and/or potassium bitartrate (cream of tartar), or any combination thereof.
  • a set retarding agent can be used in a small amount, for example in an amount in the range from about 0.01% to about 1.5% by weight of calcined gypsum, preferably in an amount in the range from about 0.05% to about 0.5% by weight of calcined gypsum.
  • the gypsum panels according to this disclosure include those in which a gypsum core is formed from a gypsum slurry contacted with foam. These are light-weight gypsum cores and gypsum panels which may include those formed from a gypsum slurry mixed with a foaming agent supplied as a foam from a foam generator, as for example was described in U.S. Patents 5,643,510 and 5,683,635, the disclosures of which are incorporated by reference.
  • Gypsum slurries mixed with a foam may produce a gypsum core comprising air voids.
  • Some gypsum cores according to this disclosure may contain air voids.
  • Some gypsum cores according to this disclosure may contain air voids with a diameter in the range from about 75 micrometers to about 300 micrometers.
  • a diameter of voids on average, an average number of voids per a cubic foot of the gypsum core and the distribution of the voids through the thickness of the gypsum core can be adjusted as may be needed for maintaining the targeted gypsum core density and strength by adjusting a blending ratio of a stable foaming agent comprising an alkyl chain containing between 8 and 12 carbons and an ethoxy group having a length of 1 to 4 units (stable soap) to an unstable foaming agent comprising unethoxylated soap with an alkyl chain length of 6 to 16 carbon units (unstable soap).
  • suitable gypsum cores with air voids can be made without co-blending stable and unstable foaming agents and/or only one type of the foaming agent, e.g., stable soap, can be used.
  • Suitable foaming agents may comprise stable soap, unstable soap, or any combination hereof.
  • foaming agents comprising sodium dodecyl sulfate, magnesium dodecyl sulfate, ammonium dodecyl sulfate, potassium dodecyl sulfate, sodium decyl sulfate, alkoxylated alkyl sulfate surfactants, sodium laureth sulfate, potassium laureth sulfate, magnesium laureth sulfate, ammonium laureth sulfate, or any mixtures thereof.
  • foaming agents surfactants, soaps
  • foaming agents comprising sodium dodecyl sulfate, magnesium dodecyl sulfate, ammonium dodecyl sulfate, potassium dodecyl sulfate, sodium decyl sulfate, alkoxylated alkyl sulfate surfactants, sodium laureth sulfate, potassium laureth sulfate, magnesium laureth sul
  • a foaming agent or any blend of foaming agents may be used in any suitable amount to produce a gypsum core with a desired density and strength. In some embodiments, from about 0.01% to about 0.5% of a foaming agent can be used by weight of calcined gypsum.
  • the gypsum core according to this disclosure may comprise one or more water- repellent agent. Such agents may include siloxane.
  • a polymerizable siloxane preferably as an emulsion with may comprise an emulsifying agent, may be added to a gypsum slurry.
  • a catalyst can be also added to the gypsum slurry.
  • Suitable siloxane formulations and catalysts such as magnesium oxide, Class C fly ash, dead-burned magnesium oxide as disclosed in U.S. patents 7,892,472 and 7,803,226, the entire disclosures of which are herein incorporated by reference.
  • Preferred siloxanes include a fluid polymerizable linear siloxane comprising a repeating unit with the general formula R 2 SiO, wherein each of the two Rs independently represents a saturate or unsaturated mono-valent hydrocarbon radical or hydrogen.
  • siloxane is a hydrogen-modified siloxane.
  • a siloxane is an alkyl hydrogen siloxane, and most preferably, methyl hydrogen siloxane.
  • a gypsum core may comprise siloxane in an amount from about 0.3% to about 2% by weight of calcined gypsum.
  • cover sheets which are shown as elements 14 and 16 in Fig. 1.
  • Suitable cover sheets include, but are not limited to a glass mat, e.g., an unwoven fiberglass mat and/or a paper cover sheet.
  • One or both cover sheets may comprise cellulosic fibers, glass fibers, ceramic fibers, mineral wool, or any combination thereof.
  • a cover sheet can be of any suitable thickness with some non-limiting examples being in the range from about 0.014 inches to about 0.022 inches.
  • One or both sheets may be individual sheets or a laminated cover sheet comprising more than one sheet.
  • the cover sheets are paper cover sheets.
  • Examples of a paper cover sheet include, but are not limited to, cover sheets comprising Manila paper, kraft paper and/or newsline paper.
  • a multi-ply paper can be used, e.g., Manila heavy paper and MH Manila HT (high tensile) paper.
  • a face paper cover sheet and a back paper cover sheet may be made from different paper grades and each of the cover sheets may be of different weight. Suitable weight ranges may include in the range from about 33 Ibs/MSF to about 65 Ibs/MSF.
  • a face cover sheet may comprise manila paper of high density, preferably about 55 to about 65 Ib/msf, but a paper cover sheet of different weight can be used as well.
  • Newsline paper of lower density of about 35 to about 45 Ibs/mfs can be used as back cover sheet.
  • one or both cover sheets may have a coating on the cover sheet surface which is not attached to the gypsum core.
  • a coating can comprise a material which makes the surface suitable for various applications such as for example as in floor underlayment, in a roof assembly, as a tile backing, as an exterior sheathing, becoming mold and/or water-resistant, among others.
  • the gypsum panel according to this disclosure may have a gypsum core having a density of from about 30 pcf to 40 pcf.
  • Such gypsum panels can be formulated from a gypsum slurry comprising from about 1100 Ibs/msf to about 1700 Ibs/msf of calcined gypsum for a 5/8 inch thick panel, ammonium-exchange vermiculite in an amount from about 2% to about 10% by weight of calcined gypsum, one or more starches in an amount from about 0.3% to about 3% by weight of calcined gypsum, mineral and/or glass fibers in an amount from about 0.3% to about 0.5% by weight of calcined gypsum, a phosphate compound in an amount from about 0.05% to about 0.4% by weight of calcined gypsum, water with the WSR ratio in the range from about 0.5 to about 1.5
  • this disclosure provides methods for manufacturing a gypsum panel according to this disclosure.
  • Fig. 2 which is a schematic representation of one embodiment for a method according to this disclosure for manufacturing a gypsum panel having a gypsum core comprising set gypsum and ammonium-exchanged vermiculite, generally 100, the method may comprise feeding a first (face) cover sheet 14 from a first roll 102 onto a moving conveyor 104. Feeding calcined gypsum (and optionally other dry additives) 2 and water (and optionally liquid additives) 6 in a mixer 106 which can be a pin-mixer.
  • Suitable mixers are known in the art including those comprising one or more feed inlets opening into a main mixing chamber (body) connected to a discharge conduit, for example as described in U.S. Patents 6,494,609 and 6,874,930, the entire disclosures of which are herein incorporated by reference.
  • Feeding into the mixer 106 via one more feed inlets wet and/or dry ammonium- exchanged vermiculite 4 produced by ammonium-exchanging vermiculite in a solution containing one or more of ammonium salts, ammonium hydroxide and/or urea in a vessel 108.
  • a foam generator 110 may be used to foam one or more foaming agents into foam 7 which may be added to the gypsum slurry 4 either directly to the chamber of the mixer 106 or while the gypsum slurry 4 is in a discharge conduit of the mixer 106.
  • the gypsum slurry 4 is deposited and distributed (spread) on the face cover sheet 14 moving on the conveyor 104.
  • the face cover sheet 14 may be coated with a skim coat slurry comprising a denser gypsum slurry on the inner surface prior to the gypsum slurry 14 being distributed on the cover sheet 14.
  • the edges of the face cover sheet 14 may be folded upward from the surface of the conveyor 104 in order to keep the gypsum slurry 4 in place while the gypsum slurry 4 is hardening.
  • the gypsum slurry 4 is spread on the face cover sheet 14, the gypsum slurry 4 is covered with a back cover sheet 16 fed to the conveyor 104 from a second roll 112.
  • This gypsum panel assembly known as a continuous ribbon of a gypsum panel precursor, is conveyed to a forming station of the conveyor 104 wherein the gypsum panel assembly is sized to a desired thickness by a forming plate of the conveyor 104.
  • the gypsum panel assembly is cut into gypsum panels 10 of desired length (e.g., 4'X8', 4'X10' or 4'X12' or some other width and/or length) at the knife section of the conveyor 104.
  • a gypsum panel 10 exits the conveyor 104 and may be moved into a kiln 114 wherein the gypsum panel 10 continues to harden as the gypsum core 12 continues to set and harden at an elevated temperature, e.g., in the range from about 110 °F to about 550 °F.
  • the present disclosure relates to a building assembly comprising one or more gypsum panels 10 as well as methods for constructing the assembly.
  • a gypsum panel may be attached to a suitable substrate.
  • suitable substrate include, but are not limited to, a load-bearing and non-load bearing wood or steel frame constructed of framing members (studs).
  • substrate include, but are not limited to, a concrete substrate, a metal sheet, one or more of wood plunks, a brick wall, etc.
  • the gypsum panel may be attached to the substrate by any method and with any means typically used in the field for a particular application and a particular frame. Nonlimiting examples include attaching the gypsum panel to the frame members with one or more of a screw, a bolt, a fastener, or any combination thereof.
  • Non-limiting examples of a building assembly according to this disclosure include, but are not limited to, an interior wall, an exterior wall, a ceiling, a roof, a column or a floor, a tile backing.
  • the gypsum panels according to this disclosure may be used in commercial or residential applications, including in new construction or repair and remodeling. In the assembly, a gypsum panel may be used as a substrate surface to which one or more coatings, tiles, shingles or any other surface finishing materials are then applied.
  • Non- limiting examples of wall assemblies include those described in U.S.
  • FIG. 3 depicts one embodiment of a wall assembly according to this disclosure, generally 200, comprising three gypsum panels according to this disclosure 210, 212, and 214 attached (affixed) to framing members (studs) 216 of the frame 217 with fasteners 218.
  • framing members 216 may be coated with adhesive 220 in order to improve attachment of the gypsum panels to the frame.
  • the gypsum panels 210, 212 and 214 abut, creating seams (joints) such 222 along their long edges and also seams (joints) along their short edges, e.g. 224.
  • a gypsum panel assembly according to this disclosure meets the requirements for fire resistant assemblies when tested in a fire resistance test in accordance with ASTM E 119. These gypsum panels may satisfy at least % hour fire rating pursuant to the fire containment and structural integrity procedures and standards U 419.
  • Gypsum panels according to this disclosure include those which are classified as type X board under ASTM 1396/C 1396M-06 because these gypsum panels can be used in an assembly in accordance with ASTM 1396/C 1396M-06 which inhibits transmission of heat through the assembly and meet a one-hour fire-resistance rating.
  • Other fire-rating tests may include one or more of the following tests from Underwriters Laboratories (UL), including UL tests U305, U419, and U423.
  • a beaker containing 100g of vermiculite, 100g of water, and various ammonium salts as listed in Table 2 was placed on the shaker with a speed of 100 rpm. Samples were incubated with shaking for 5, 10 or 480 minutes as noted in Table 2. After incubation was completed, amnionium-exchanged vermiculite was filtered and dried at 110 °F for 12 hours. Then, a thermal expansion test was conducted following the UL follow-up procedure at 850 ! 'C and in accordance with ASTM C 1795-15, wherein the gypsum core is heated at about 1560 °F (850 °C) for one hour. The results of this test are reported in Table 2 below.
  • This process comprises two steps.
  • Step 1 Vermiculite is ion-exchanged in an ammonium salt solution for 10 minutes, then filtered and dried at 110 °F; and [00103] Step 2: Dried NHa- vermiculite is added to a gypsum slurry to make wallboard. The filtered liquid can be recycled and used again for preparing the next batch of ammonium- exchanged vermiculite.
  • Vermiculite can be used either as vermiculite (control board) or as NJT-exchanged vermiculite (invention board).
  • a control board contains 50 Ibs/msf of Grade 4 vermiculite.
  • dry additives containing vermiculite (control) or NtU- exchanged vermiculite (invention) were soaked in a solution containing water and wet additives for 10 seconds and blended for 10 seconds in a Hobart mixer, then foam was injected for 13 seconds and mixing continued for another 2 seconds.
  • a gypsum slurry was poured into a 12"xl2"x 5/8" envelope. After a gypsum slurry was set and hardened, an envelope was sealed by using a paper tape. A sealed board was dried at 450 °F for 15 mins, then it was moved to 360T. After the board was dried at 360 °F for 15 mins, the board was dried at 110 'F overnight.
  • Table 5 reports the X-Y and Z-shrinkage results for boards made with we ammonium-exchanged vermiculite produced by the slurry' process. i
  • the Z-% shrinkage from 43.5 Ibs/MSF of NEU- vermiculite was similar to the Z-% shrinkage from 50 Ibs/MSF of as-is Grade 4 vermiculite.
  • the total usage of vermiculite was reduced by 13%.
  • the Z-% shrinkage from 50 Ibs/MSF of NEU-exchanged 4/5 mixture was similar to that from 50 Ibs/MSF of Grade 4 (Sample 4-0), indicating that the same amount of the NEU-exchanged 4/5 mixture can replace grade 4 vermiculite.
  • Table 6 reports the X-Y and Z-shrinkage results for wallboards prepared with ammonium-exchanged vermiculite prepared by the filtration process.
  • Ammonium salts (powder or liquid form) were mixed with a gypsum slurry containing vermiculite to make a gypsum board. Thus, there was no separate ion-exchanging process. Instead, an ion-exchange process was combined with mixing a gypsum sluny.
  • Table 8 reports another formula for making a 5/8 inch fire-rated wallboard, now without STMP. NH4-exchanged vermiculite is dried NH4-exchanged vermiculite as was used in Table 3.
  • Table 9 reports the X-Y and Z-shrinkage results for boards made with dried ammonium-exchanged vermiculite and according to the formula of Table 8.
  • Table 9 reports results for the samples without STMT. When ammonium- exchanged vermiculite is added to a gypsum slurry, a resulting wallboard still shows a better thermal shrinkage performance than the one without having ammonium-exchanged vermiculite.

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Abstract

La présente invention concerne des produits utiles en tant que matériaux de construction et contenant du gypse durci et de la vermiculite à échange d'ammonium, comprenant un panneau de gypse ayant un noyau de gypse comprenant du gypse durci et de la vermiculite à échange d'ammonium et caractérisé par un retrait thermique réduit et une résistance accrue au feu par rapport au panneau de gypse qui comprend de la vermiculite qui n'a pas été échangée par ammonium. L'invention concerne en outre des procédés de production du panneau de plâtre et de construction d'ensembles de construction avec les panneaux de plâtre, comprenant des parois et des plafonds.
PCT/US2023/061945 2022-02-08 2023-02-03 Panneau de gypse contenant de la vermiculite à échange d'ammonium et procédés associés WO2023154662A1 (fr)

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WO2022233455A1 (fr) * 2021-05-07 2022-11-10 Knauf Gips Kg Panneau de gypse léger résistant à l'affaissement à haute température

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