WO2009068899A2 - Gypsum formulations - Google Patents

Gypsum formulations Download PDF

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Publication number
WO2009068899A2
WO2009068899A2 PCT/GB2008/051047 GB2008051047W WO2009068899A2 WO 2009068899 A2 WO2009068899 A2 WO 2009068899A2 GB 2008051047 W GB2008051047 W GB 2008051047W WO 2009068899 A2 WO2009068899 A2 WO 2009068899A2
Authority
WO
WIPO (PCT)
Prior art keywords
water
slurry
gypsum
clay
comb
Prior art date
Application number
PCT/GB2008/051047
Other languages
French (fr)
Other versions
WO2009068899A3 (en
Inventor
Robin Fisher
Original Assignee
Bpb Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bpb Ltd filed Critical Bpb Ltd
Priority to EP08855381.3A priority Critical patent/EP2222613B1/en
Priority to CA2707151A priority patent/CA2707151C/en
Priority to PL08855381T priority patent/PL2222613T3/en
Publication of WO2009068899A2 publication Critical patent/WO2009068899A2/en
Publication of WO2009068899A3 publication Critical patent/WO2009068899A3/en
Priority to US12/783,164 priority patent/US8617451B2/en

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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
    • 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
    • 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
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2623—Polyvinylalcohols; Polyvinylacetates
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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 present invention concerns the production of gypsum formulations - especially using gypsum formulations which are suitable for the manufacture of gypsum building boards.
  • Such gypsum building boards can be surface reinforced, for example, as plasterboard (which is generally reinforced with paper liners) or gypsum board (which may be reinforced at or near the surface by a woven or non-woven reinforcement, or solely reinforced in its core).
  • Gypsum stucco slurry (and optionally fibre reinforcement) is typically shaped through an extruder or between rollers or belts.
  • the gypsum slurry is sandwiched between surface reinforcements before shaping. In this arrangement, the edges of the surface reinforcement or liner sheets are typically sealed together.
  • the wet slurry is allowed to set and the set board is cut into desired lengths and dried to form the final board.
  • suitable such basic water-soluble polymers include polyvinyl pyrrolidone, polyvinyl alcohol (either fully or partially hydrolysed), and certain cold water soluble starch derivatives (such as oxidised, dextrinised or ethylated starch).
  • Such polymers having preferential affinity for the clay (relative to the comb-branched copolymer) and are capable of forming surface hydrogen bonds with the clay, thereby helping to disperse the clay and inhibiting deleterious interaction with the comb-branched copolymer fluidiser. This effect helps to improve the dose efficiency of the fluidiser.
  • a preferred such water-soluble polymer is one which is soluble in cold water, such that it can be supplied as an aqueous solution thereby avoiding the need for an extra step to dissolve the polymer in hot water before addition to a slurry mixer.
  • a preferred amount of such a basic water-soluble polymer is from 0.01 to 2 grams per gram of clay present in the slurry.
  • polyvinyl alcohol such as about 88% hydrolysed.
  • Such a polymer can perform four functions simultaneously, namely
  • the polyvinyl alcohol may be silanised - for example, by reaction of the hydroxyl groups in PVA with silanol functional groups.
  • silanised polyvinyl alcohols are hydrolysed vinyl ester polymers having a degree of hydrolysis of from 75 to 100% of the vinyl ester groups, and a content of silane-containing comonomer units of from 0.01 to 10 mol%.
  • Such silanised polyvinyl alcohols are disclosed in detail in US Patent 7052773.
  • the comb-based copolymer flluidiser is preferably present in an amount of 0.005 to 1 % based on the total weight of the slurry.
  • the comb-based copolymer may be produced by a method as described in, for example, US Patent 6527850, 6869988 and 7070648.
  • the basic water-soluble polymer and/or the comb-based copolymer may be added to a whipped aqueous foam to be mixed with a gypsum slurry, such an aqueous foam being produced by foaming water containing at least one foaming agent.
  • the resulting board is lighter because it contains air bubbles, as is well known.
  • the water present in such a foam is typically ground water or tap water, which may have been filtered.
  • Other non-deleterious materials, adjuvants and ingredients may, when appropriate, be present in the water from which the foam is made.
  • the gypsum slurry which is mixed with the whipped aqueous foam comprises hydratable gypsum (calcium sulfate), which has generally been obtained by gypsum calcination.
  • the slurry may contain other non-deleterious mineral materials and/or ions such as phosphate and/or magnesium ions.
  • the hydratable calcium sulfate may be, for example, anhydrous calcium sulfate (anhydrite Il or III) or a calcium sulfate hemihydrate (CaSO 4 .0.5 H 2 O) in its alpha- or beta- crystalline form.
  • the gypsum is typically mixed with water to form a slurry before mixing with the aqueous foam described above; the water from which the slurry is made is typically ground water or tap water, which may have been filtered. Other non-deleterious materials, adjuvants and ingredients may, when appropriate, be present in the water from which the slurry is made.
  • the pH of the slurry is typically in the range 6.5 to 9.5, and the slurry may contain optional further ingredients, such as starch, water reducing agents, moisture repellents (such as silicone oils or waxes), reinforcing fibres, set accelerators and retarders, deformation inhibitors (such as anti-sagging agents), anti-shrink additives, recalcination inhibitors, foam stabilisers, levelling aids, bactericides, fungicides, pH adjusters, colouring agents, fire retardants and fillers (such as particulate mineral material or plastics, which may in some embodiments be in expanded form).
  • moisture repellents such as silicone oils or waxes
  • reinforcing fibres set accelerators and retarders
  • deformation inhibitors such as anti-sagging agents
  • anti-shrink additives such as anti-shrink additives
  • recalcination inhibitors foam stabilisers, levelling aids, bactericides, fungicides, pH adjusters, colouring agents, fire retardants and fill
  • the slurry may contain fibre reinforcement, such as glass fibres (typically cut fibres), and may be used to form gypsum board.
  • Gypsum board produced according to the invention may be with or without surface reinforcement or liner sheets; when surface reinforcement is used, it may, for example, be of fibre scrim or fibre mesh.
  • gypsum building board When gypsum building board is produced according to the invention, it is preferably formed to a desired thickness by extrusion or pressing between rollers or belts.
  • the present invention extends to gypsum building board comprising a set aqueous gypsum slurry containing a water swellable clay, a comb-based copolymer fluidiser and a basic water-soluble polymer having preferential affinity for clay.
  • DSG desulphogypsum
  • Wyoming bentonite a naturally swelling clay
  • Ethacryl a commercially available comb-based copolymer which is an ethoxylated acrylic acid polymer
  • other liquid additives as appropriate were added at this stage. Then, the stucco was sprinkled onto the solution over 30 seconds and left to stand for 30 seconds. Mixing time was 10 seconds on low speed. The slump diameter of the slurry was measured on the falling plate consistometer as described in Section C.3.1.1 of BS 1191 : Part i : 1973.

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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)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

A gypsum formulation, typically for producing a gypsum building board, is produced by adding to an aqueous gypsum slurry containing a water swellable clay, acomb- based copolymer fluidiser and a basic water-soluble polymer having preferential affinity for clay, and allowing a layer of theaqueous gypsum slurry to set.

Description

Gypsum formulations
The present invention concerns the production of gypsum formulations - especially using gypsum formulations which are suitable for the manufacture of gypsum building boards.
Such gypsum building boards can be surface reinforced, for example, as plasterboard (which is generally reinforced with paper liners) or gypsum board (which may be reinforced at or near the surface by a woven or non-woven reinforcement, or solely reinforced in its core).
Gypsum stucco slurry (and optionally fibre reinforcement) is typically shaped through an extruder or between rollers or belts. For surface reinforced gypsum board, the gypsum slurry is sandwiched between surface reinforcements before shaping. In this arrangement, the edges of the surface reinforcement or liner sheets are typically sealed together. After shaping of the gypsum board, the wet slurry is allowed to set and the set board is cut into desired lengths and dried to form the final board.
It has been found that water-swellable clays present in some natural sources of gypsum tend to increase the water demand of the slurry which ultimately forms the plaster, typically by forming a flocculated structure in the presence of calcium ions.
It has been proposed in US patent 7261772 to add a comb-branched copolymer that are formed from a polyether having terminal unsaturated groups, for example by polymerising a polyether macromonomer having a polyalkylene oxide chain, reacted with an unsaturated monomer such as acrylic acid or methacrylic acid. The polyalkylene oxide is typically derived from ethylene oxide, propylene oxide, butylenes oxide or the like; for example a polyethylene glycol or polypropylene glycol, or random or block copolymers thereof. The above US patent suggests that certain amine compounds are necessary in the gypsum composition.
We have found that improvements can be achieved if a basic water-soluble polymer having preferential affinity for clay is used instead of the amine compounds specified in the above US patent. According to the invention, therefore, there is provided a method of producing a gypsum slurry containing a water-swellable clay, in which there is added to the gypsum slurry a comb-branched copolymer as described in the abovementioned US patent as fluidiser, and a basic (non-acidic) water-soluble polymer having preferential affinity for clay.
We have found that clays present in gypsum interfere with the action of comb- branched polymer fluidisers, lowering the dose efficiency of such fluidisers. The latter fluidisers become preferentially adsorbed onto clays because the latter are more highly charged.
We have found that if certain basic water-soluble polymers are present in the gypsum slurry, they preferentially adsorb onto clay present in the slurry, thereby performing two functions, as follows:
1 ) to disperse the clay particles, which lowers the water gauge slightly; and 2) to block the sites which would otherwise be occupied by added fluidiser, such blocking allowing the fluidiser to perform its desired function of fluidising the plaster particles, which in turn results in further lowering of the water gauge.
Preferred examples of suitable such basic water-soluble polymers include polyvinyl pyrrolidone, polyvinyl alcohol (either fully or partially hydrolysed), and certain cold water soluble starch derivatives (such as oxidised, dextrinised or ethylated starch).
Such polymers having preferential affinity for the clay (relative to the comb-branched copolymer) and are capable of forming surface hydrogen bonds with the clay, thereby helping to disperse the clay and inhibiting deleterious interaction with the comb-branched copolymer fluidiser. This effect helps to improve the dose efficiency of the fluidiser.
A preferred such water-soluble polymer is one which is soluble in cold water, such that it can be supplied as an aqueous solution thereby avoiding the need for an extra step to dissolve the polymer in hot water before addition to a slurry mixer. A preferred amount of such a basic water-soluble polymer is from 0.01 to 2 grams per gram of clay present in the slurry.
An example of such a water-soluble polymer is polyvinyl alcohol (such as about 88% hydrolysed). Such a polymer can perform four functions simultaneously, namely
1 ) to act as a foaming agent,
2) to disperse the clay allow a reduction in water demand,
3) to increase the efficiency of comb-based copolymer based fluidisers allowing a reduction in water demand, and, in some instances, 4) to increase the paper-gypsum adhesion after drying.
In some embodiments, the polyvinyl alcohol may be silanised - for example, by reaction of the hydroxyl groups in PVA with silanol functional groups. Suitable examples of such silanised polyvinyl alcohols are hydrolysed vinyl ester polymers having a degree of hydrolysis of from 75 to 100% of the vinyl ester groups, and a content of silane-containing comonomer units of from 0.01 to 10 mol%. Such silanised polyvinyl alcohols are disclosed in detail in US Patent 7052773.
The comb-based copolymer flluidiser is preferably present in an amount of 0.005 to 1 % based on the total weight of the slurry. The comb-based copolymer may be produced by a method as described in, for example, US Patent 6527850, 6869988 and 7070648.
The basic water-soluble polymer and/or the comb-based copolymer may be added to a whipped aqueous foam to be mixed with a gypsum slurry, such an aqueous foam being produced by foaming water containing at least one foaming agent.
When an aqueous foam is used in the method according to the invention to produce a building board, the resulting board is lighter because it contains air bubbles, as is well known.
The water present in such a foam is typically ground water or tap water, which may have been filtered. Other non-deleterious materials, adjuvants and ingredients may, when appropriate, be present in the water from which the foam is made. The gypsum slurry which is mixed with the whipped aqueous foam comprises hydratable gypsum (calcium sulfate), which has generally been obtained by gypsum calcination. The slurry may contain other non-deleterious mineral materials and/or ions such as phosphate and/or magnesium ions. The hydratable calcium sulfate may be, for example, anhydrous calcium sulfate (anhydrite Il or III) or a calcium sulfate hemihydrate (CaSO4.0.5 H2O) in its alpha- or beta- crystalline form.
The gypsum is typically mixed with water to form a slurry before mixing with the aqueous foam described above; the water from which the slurry is made is typically ground water or tap water, which may have been filtered. Other non-deleterious materials, adjuvants and ingredients may, when appropriate, be present in the water from which the slurry is made.
The pH of the slurry is typically in the range 6.5 to 9.5, and the slurry may contain optional further ingredients, such as starch, water reducing agents, moisture repellents (such as silicone oils or waxes), reinforcing fibres, set accelerators and retarders, deformation inhibitors (such as anti-sagging agents), anti-shrink additives, recalcination inhibitors, foam stabilisers, levelling aids, bactericides, fungicides, pH adjusters, colouring agents, fire retardants and fillers (such as particulate mineral material or plastics, which may in some embodiments be in expanded form).
The slurry may contain fibre reinforcement, such as glass fibres (typically cut fibres), and may be used to form gypsum board. Gypsum board produced according to the invention may be with or without surface reinforcement or liner sheets; when surface reinforcement is used, it may, for example, be of fibre scrim or fibre mesh.
When gypsum building board is produced according to the invention, it is preferably formed to a desired thickness by extrusion or pressing between rollers or belts.
The present invention extends to gypsum building board comprising a set aqueous gypsum slurry containing a water swellable clay, a comb-based copolymer fluidiser and a basic water-soluble polymer having preferential affinity for clay. Certain aspects and features of the present invention will now be illustrated by the following worked examples.
EXAMPLES
150 g of DSG (desulphogypsum) stucco to which had been added 1.5% by weight Wyoming bentonite (a naturally swelling clay) was used in each test except the control - in the latter no clay was added.
Water at 4O0C was added in the weighed amount into a small Waring blender and 0.1 % trisodium citrate (w/w stucco) as retarder was added to the blend along with solid additives, and the blender was operated for 10 seconds to dissolve the retarder.
Ethacryl (a commercially available comb-based copolymer which is an ethoxylated acrylic acid polymer) and other liquid additives as appropriate were added at this stage. Then, the stucco was sprinkled onto the solution over 30 seconds and left to stand for 30 seconds. Mixing time was 10 seconds on low speed. The slump diameter of the slurry was measured on the falling plate consistometer as described in Section C.3.1.1 of BS 1191 : Part i : 1973.
The results summarised in the following Table 1 show the advantageous increased fluidity achieved by adding a comb-based polymer to an exemplary stucco containing clay. In this case the clay was deliberately added in order to provide experimental control, but similar effects are achieved with stucco which naturally contains water- swellable clay. The proportions of Ethacryl specified are the active contents.
Table 1
Figure imgf000007_0001

Claims

Claims
1 A method of producing a gypsum formulation, which method comprises providing an aqueous gypsum slurry containing a water swellable clay, adding to the gypsum slurry a comb-based copolymer fluidiser and a basic water-soluble polymer having preferential affinity for clay, and allowing a layer of the aqueous gypsum slurry to set.
2 A method according to claim 1 , wherein the water-soluble polymer comprises polyvinyl pyrrolidone, polyvinyl alcohol or a starch derivative.
3. A method according to claim 2, wherein the polyvinyl alcohol is partially silanised.
4 A method according to any of claims 1 to 3, wherein the water-soluble polymer is soluble in cold water.
5 A method according to any of claims 1 to 4, wherein the comb-based copolymer fluidiser comprises a polymer of a polyalkoxylated acrylic or methacrylic acid.
6. A method according to any of claims 1 to 5, wherein the layer of the aqueous slurry is allowed to set to form a building board.
7. A method according to claim 6, wherein the slurry is fed between spaced surface reinforcements so as to form a sandwich structure and the slurry is allowed to set between the surface reinforcements.
8. A method according to claim 7, wherein the slurry contains fibre reinforcement.
PCT/GB2008/051047 2007-11-30 2008-11-11 Gypsum formulations WO2009068899A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP08855381.3A EP2222613B1 (en) 2007-11-30 2008-11-11 Method for producing GYPSUM FORMULATIONS
CA2707151A CA2707151C (en) 2007-11-30 2008-11-11 Gypsum formulations
PL08855381T PL2222613T3 (en) 2007-11-30 2008-11-11 Method for producing GYPSUM FORMULATIONS
US12/783,164 US8617451B2 (en) 2007-11-30 2010-05-19 Method of producing gypsum building boards

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0723442.0 2007-11-30
GB0723442.0A GB2455288B (en) 2007-11-30 2007-11-30 Gypsum formulations

Publications (2)

Publication Number Publication Date
WO2009068899A2 true WO2009068899A2 (en) 2009-06-04
WO2009068899A3 WO2009068899A3 (en) 2009-07-16

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Country Status (6)

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EP (1) EP2222613B1 (en)
CA (1) CA2707151C (en)
GB (1) GB2455288B (en)
PL (1) PL2222613T3 (en)
TR (1) TR201909785T4 (en)
WO (1) WO2009068899A2 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010133886A1 (en) * 2009-05-20 2010-11-25 Bpb Limited Gypsum building boards
WO2011076612A1 (en) 2009-12-24 2011-06-30 Sika Technology Ag Argillaceous gypsum
EP2848597A1 (en) 2013-09-17 2015-03-18 Basf Se Light-weight gypsum board with improved strength and method for making same
US10442732B2 (en) 2016-05-20 2019-10-15 United States Gypsum Company Gypsum slurries with linear polycarboxylate dispersants

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU5584480A (en) * 1979-03-06 1980-09-11 Australian Gypsum Limited Fire rated gypsum board
WO2004094336A2 (en) * 2003-04-16 2004-11-04 Lyondell Chemical Technology, L.P. Solid supported comb-branched copolymers as an additive for gypsum compositions
US7052773B2 (en) * 2002-07-18 2006-05-30 Wacker Polymer Systems Gmbh & Co. Kg Silane-modified polyvinyl alcohol mixtures
US7261772B1 (en) * 2006-10-17 2007-08-28 Lyondell Chemical Technology, L.P. Gypsum composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6527850B2 (en) * 2001-04-11 2003-03-04 Arco Chemical Technology L.P. Use of comb-branched copolymers in gypsum compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU5584480A (en) * 1979-03-06 1980-09-11 Australian Gypsum Limited Fire rated gypsum board
US7052773B2 (en) * 2002-07-18 2006-05-30 Wacker Polymer Systems Gmbh & Co. Kg Silane-modified polyvinyl alcohol mixtures
WO2004094336A2 (en) * 2003-04-16 2004-11-04 Lyondell Chemical Technology, L.P. Solid supported comb-branched copolymers as an additive for gypsum compositions
US7261772B1 (en) * 2006-10-17 2007-08-28 Lyondell Chemical Technology, L.P. Gypsum composition

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010133886A1 (en) * 2009-05-20 2010-11-25 Bpb Limited Gypsum building boards
WO2011076612A1 (en) 2009-12-24 2011-06-30 Sika Technology Ag Argillaceous gypsum
EP2341039A1 (en) 2009-12-24 2011-07-06 Sika Technology AG Concrete containing clay
US9266779B2 (en) 2009-12-24 2016-02-23 Sika Technologies Ag Argillaceous gypsum
EP2848597A1 (en) 2013-09-17 2015-03-18 Basf Se Light-weight gypsum board with improved strength and method for making same
WO2015039890A1 (en) 2013-09-17 2015-03-26 Basf Se Light-weight gypsum board with improved strength and method for making same
US10442732B2 (en) 2016-05-20 2019-10-15 United States Gypsum Company Gypsum slurries with linear polycarboxylate dispersants
US10968138B2 (en) 2016-05-20 2021-04-06 United States Gypsum Company Gypsum slurries with linear polycarboxylate dispersants

Also Published As

Publication number Publication date
PL2222613T3 (en) 2019-09-30
GB2455288B (en) 2012-12-05
GB2455288A (en) 2009-06-10
CA2707151C (en) 2016-08-16
GB0723442D0 (en) 2008-01-09
EP2222613A2 (en) 2010-09-01
TR201909785T4 (en) 2019-07-22
EP2222613B1 (en) 2019-04-10
CA2707151A1 (en) 2009-06-04
WO2009068899A3 (en) 2009-07-16

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