WO2019221914A1 - Support de mousse aqueuse et procédé de production correspondant - Google Patents

Support de mousse aqueuse et procédé de production correspondant Download PDF

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Publication number
WO2019221914A1
WO2019221914A1 PCT/US2019/030308 US2019030308W WO2019221914A1 WO 2019221914 A1 WO2019221914 A1 WO 2019221914A1 US 2019030308 W US2019030308 W US 2019030308W WO 2019221914 A1 WO2019221914 A1 WO 2019221914A1
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WIPO (PCT)
Prior art keywords
foam
gypsum
cement
stable aqueous
fibers
Prior art date
Application number
PCT/US2019/030308
Other languages
English (en)
Inventor
Yen-Yau H. Chao
Original Assignee
Allied Foam Tech Corp.
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
Priority claimed from US15/979,191 external-priority patent/US10730795B2/en
Application filed by Allied Foam Tech Corp. filed Critical Allied Foam Tech Corp.
Publication of WO2019221914A1 publication Critical patent/WO2019221914A1/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
    • C04B28/02—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 hydraulic cements other than calcium sulfates
    • C04B28/04—Portland 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
    • C04B28/02—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 hydraulic cements other than calcium sulfates
    • C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust 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
    • C04B28/02—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 hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous 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
    • C04B28/02—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 hydraulic cements other than calcium sulfates
    • C04B28/08—Slag 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
    • 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
    • C04B2111/00586—Roofing materials
    • 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
    • C04B2111/00586—Roofing materials
    • C04B2111/00594—Concrete roof tiles
    • 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
    • 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
    • C04B2111/72—Repairing or restoring existing buildings or building materials

Definitions

  • hydraulic materials such as calcined gypsum, plaster of Paris, or stucco composites can set and develop strength quickly after adding water.
  • the hardened gypsum products are often without shrinkage and produce good surface finish.
  • Producing calcined gypsum (Calcium sulfate hemihydrate) from the gypsum mineral (Calcium sulfate dihydrate) requires much lower energy than that used in producing cement powder.
  • a great amount of processing water is used (80-90 % by weight of gypsum powder), and most of the water has to be evaporated in the drying process.
  • the higher water solubility of hydrated gypsum products than that of hydrated cement makes most of these gypsum products unsuitable for exterior applications.
  • Such secondary or delayed ettringite crystal formation -3Ca0.Al 2 0 3 .(Ca0.S0 3 ) 3 .32H 2 0 is mostly derived from the interaction of some of the key components of cement (such as the tricalcium aluminate - 3Ca0.Al 2 0 3 ) and the soluble gypsum species. After hardening and upon exposure to the environmental elements, the gypsum component, due to its higher solubility, may continue to react with tricalcium aluminate (3Ca0.Al 2 0 3 ) in the composite to form large crystals of ettringite
  • 3CaOAl203 + 3(CaS04-2H20) + 26H20 3Ca0.Al 2 0 3 .(Ca0.S0 3 ) 3 .32H 2 0
  • Anionic, cationic, zwitterionic or hydrolyzed protein based foam agents commonly used in making lightweight cement or gypsum products are known for their limited foam stability.
  • the foam will start to show volume shrinkage or foam collapse as soon as they were made.
  • the volume shrinkage or foam collapse of a freshly made foam is typically caused by the transformation of the lightweight foam back into its un-foamed liquid state.
  • Foam collapse typically comes from coarsening of the foam bubbles through the coalescing of small bubbles into larger ones.
  • the large bubbles will burst easily and go back to their liquid state because of the fast liquid drainage from the bubble walls.
  • the thinning or the liquid drainage of walls quickly destabilizes the bubbles and causes them to burst.
  • Many attempts have been made to increase the foam stability and reduce liquid drainage.
  • One such attempt is the use of an anionic foam stabilizer to stabilize a cationic foam (US Pat. No.
  • US Pat. No. 5,696,174 employs a two component approach using a foaming agent stabilized with a foam stabilizer. This is similar to the two components epoxy-amine system or the two component isocyanate -polyol system. However, unlike the latter two that use crosslinking chemistry to permanently lock the two components together, these two components turn the foam back to the initial un-foamed liquid state after most of the foam liquid is drained off from the foam surface and causes foam collapse.
  • the present invention provides solutions to many of the problems set forth above.
  • the present invention provides a foam carrier that may carry accelerators, retarders, wax, polymer binder, and fiber or some other very reactive components for a typical slurry.
  • a foam carrier may carry accelerators, retarders, wax, polymer binder, and fiber or some other very reactive components for a typical slurry.
  • a slurry itself may contain only water, water reducer, and hydraulic powder. This approach has the advantage of opening up all kinds of process possibilities and flexibilities, such as avoiding plant mixer downtime for making fast setting composites and making hydraulic articles with targeted performance features, which would be otherwise unattainable if such components are directly mixed into slurries.
  • the additives may be fibers, water reducing plasticizers and superplasticizers, polymer, starch, accelerators, retarders, wax or silicon water resistant additives, colorant, lightweight fillers, or others for hydraulically settable slurries such as cement, concrete and gypsum.
  • Both the fiber containing preformed foam and the hydraulic slurry may, in turn, be prepared separately through a continuous grout mixer or a static mixer.
  • the two streams, one with fiber-containing foam and the other with the hydraulic slurry, can then be mixed or pumped onto a production line or moving belt where panels, backer boards, blocks or cast stones are continuously being produced.
  • a stable aqueous foam carrier comprises: (1) a stable aqueous foam comprising a foam agent and a foam stabilizer; and (2) additives comprising fibers, wherein the fibers are uniformly dispersed in the stable aqueous form carrier, wherein the stable aqueous foam carrier does not contain any of gypsum, cement, concrete, pozzolanic additives, and aggregates.
  • the fibers may be mixed with the stable aqueous foam at a mixing speed from 50 to 500 rpm such that the shear from the mixing do not break foams in the stable aqueous foam.
  • the stable aqueous foam carrier may be used for a hydraulically settable composition, a cementitious article, or a gypsum article.
  • the additives may further comprise lightweight fillers, cement or gypsum accelerators, retarders, water proofing additives, water reducing plasticizers,
  • superplasticizers polymers, colorant, organic and fine inorganic fillers, thickeners or rheology modifiers, or a combination thereof.
  • the stable aqueous foam carrier may be configured to remain without any of foam collapse, foam bubbles coarsening, and liquid drainage for 0.1 - 1 hour so that the stable aqueous foam carrier is mixed thoroughly with a hydraulic slurry.
  • the foam agent may be a long-chain organic cation-forming compound, and the foam stabilizer may be a long-chain anion forming compound.
  • the foam agent and the foaming stabilizer may be present in the stable aqueous foam carrier at a weight ratio of from 0.05: 1 to 15:1.
  • the stable aqueous foam may be configured to maintain the stability thereof without foam collapse in the event that other additives are added thereto.
  • the fibers may be hydrophilic fibers, hydrophobic fibers, or a mixture thereof.
  • the fibers may be hydrophilic organic fibers.
  • the fibers may be from 0.5 to 50 % by weight of the stable aqueous foam.
  • the fibers may have dpf values from 0.5 to 250, preferably from 0.5 to 25, and more preferably from 0.5 to 10.
  • a hydraulically settable composition comprises: (1) a stable aqueous foam carrier and (2) a hydraulic mixture comprising gypsum, cement, concrete, fine pozzolanic additives, aggregates, or a mixture thereof.
  • the hydraulic mixture may comprise gypsum, cement, and fine pozzolanic additives.
  • the cement may be Portland cement Types I - V, aluminum cement, slag cement, or fast setting cement.
  • the hydraulic mixture may comprise calcined gypsum, stucco, alpha- calcium sulfate hemihydrate, beta- calcium sulfate hemihydrate, or a mixture thereof.
  • the hydraulic mixture may comprise fine pozzolanic additives made of metakaolin, silica fume, fly ash, ground furnace slag, or a mixture thereof.
  • the hydraulic mixture may comprise cement, gypsum, and pozzolanic additives with weight percentages of 20-80 % of gypsum, 5- 50% of cement, and 5-40% of pozzolanic additives, based on the hydraulic mixture.
  • the hydraulically settable composition may be configured to set in minutes for quick demolding, to develop high early and final compressive and tensile strengths, and to have water resistance, lightweight, and good surface finish without crack formation upon long term exposure to humid conditions.
  • the hydraulically settable composition may have a density no larger than
  • a cementitious article may be formed from the hydraulically settable composition, wherein the cementitious article is one of a block, a wall and floor panel, a siding, a backer board, a roof deck, a roof tile, a decorative stone, a ceiling tile, a roof shingle and flooring, and a floor underlayment.
  • a cementitious article may be formed from the hydraulically settable composition, wherein the cementitious article is a cement backer board comprising a foamed fiber cementitious core, wherein the foamed fiber cementitious core is sandwiched between (1) a first fiberglass mat or a fiberglass scrim and (2) a second fiberglass mat or a fiberglass scrim.
  • a cementitious article may be formed from the hydraulically settable composition, wherein the cementitious article is a crack resistant and water-resistant building material for roads, foundations, or bridges, wherein the hydraulic mixture comprises cement, fly ash, sand, and aggregate.
  • a gypsum article may be formed from the hydraulically settable composition, wherein the gypsum article is a ceiling tile or a wall board.
  • a gypsum-rich cement composite comprises: (1) a stable aqueous foam carrier and (2) a hydraulic mixture comprising gypsum, cement, and pozzolanic additives, wherein the gypsum-rich cement is suitable for the making of block, wall and floor panel, backer board, siding, roof deck, roof tile, decorative stone, ceiling tile, roof shingle, flooring or floor underlayment, building, patching or repairing material for roads, foundations, or bridges.
  • a process for forming a hydraulically settable composition comprises: (a) preparing an aqueous hydraulic slurry comprising one or more of gypsum, cement, pozzolanic additives, and aggregates; (b) adding a stable aqueous foam comprising a foam agent and a foam stabilizer on a top of the aqueous hydraulic slurry; and (c) adding 0.5- 35% fibers by weight based on the aqueous hydraulic slurry on a top of the stable aqueous foam while the aqueous stable foam is mixed into the aqueous hydraulic slurry.
  • the fibers may be premixed with the stabilized foam and then add the fiber containing stable foam into the aqueous slurry.
  • the fibers may be mixed into the stable aqueous foam at a rotation speed of less than 500 rotations per minute.
  • the combined volume of the stable aqueous foam and the fibers may be 5- 95% of the volume of the aqueous hydraulic slurry.
  • compositions disclosed in the present invention are not necessarily mutually exclusive to each other and may be used together.
  • Figure 2 shows images of: (A) a freshly cast slump cone of foamed cement (Sample 1 in
  • Figure 3 shows images of: (A) 1.8 dpf and 6 mm in length PVA fibers mixed with foam
  • B 1.8 dpf and 6 mm in length PVA fibers mixed with foam AFT-425A/AFT-425B at 180 rpm mixing speed with a flat mixing paddle using a KitchenAid mixer;
  • C 1.0 dpf and 25 mm in length polypropylene fibers mixed with foam AFT-425A/AFT-425B at 60 rpm mixing speed with a flat mixing paddle using a KitchenAid mixer; and
  • D 1.0 dpf and 25 mm in length polypropylene fibers mixed with foam AFT-425A/AFT-425B at 180 rpm mixing speed with a flat mixing paddle using a KitchenAid mixer.
  • Figure 4 shows images of (A) 1.8 dpf PVA fiber mixed with a stable foam at mixing speed 95 rpm with wire whisk for 0.5’; and (B) 1.8 dpf PVA fiber mixed with a stable foam at mixing speed 95 rpm with flat mixing paddle for 0.5’.
  • the stable aqueous foam carrier of the present invention comprises a stable aqueous foam and additives comprising fibers.
  • the additives may further comprise polymers, water reducing plasticizers and superplasticizers, starch, accelerators, retarders, wax or silicon water resistant additives, colorant, or others typically used in hydraulically settable slurries.
  • the fibers are uniformly incorporated into the stable foam, maintaining or enhancing the stability of the foam. Higher mixing efficiency mixing devices such as ribbon mixer, twin paddle mixer, and wire whisk or equivalent are needed to achieve the uniform fiber distribution when lower speed mixing is applied.
  • a suitable stable foam comprises a (1) cationic foam agent and (2) an anionic foam stabilizer.
  • the cationic foam agent (1) is a long-chain organic cation-forming compound having
  • R is an aliphatic hydrocarbon radical having from 8 to 24 carbon atoms
  • Ri is selected form the group consisting of an alkyl group having 1-16 carbon atoms, a hydroxyalkyl group having 1-16 carbon atoms, a benzyl group, a group which, when taken together with the nitrogen, represents a heterocyclic radical, and any of such groups having a hydrogen atom replaced by a fluorine atom
  • R 2 and R 3 are selected form the group consisting of an alkyl group having 1-6 carbon atoms, a hydroxyalkyl group having 1-6 carbon atoms, a benzyl group, a hydrogen atom, a group which, when taken together with the nitrogen, represents a heterocyclic radical, and any of such groups having a hydrogen atom replaced by a fluorine atom
  • X- is an anionic counter ion.
  • the anionic foam stabilizer (2) is a long-chain anionic foam stabilizer having Formula
  • the long-chain organic cation formed from (I) and the long-chain organic anion formed from (II) may be present in a weight ratio of from 0.05:1 to 15:1.
  • the present invention produces large quantities such as several cubic feet or several cubic yards of the stable foam.
  • a 2-4% aqueous dilution of the foam agent, with or without added fillers such as clay or thickeners, is fed into a two pumps foam generator such as Allied Foam Tech’s AFT-G6. Compressed air, for example, at 80 psi is also fed into the generator through an electronically controlled solenoid valve.
  • the preformed foam is then stabilized inside the foam generator using the foam stabilizer that is fed through a second pump. After further homogenization through a plurality of mixing chambers within the foam generator, a stable aqueous foam is produced without any liquid drainage nor foam collapse for minutes to hours.
  • the preformed foam is then pumped into a cement mortar mixer with mixing paddles.
  • Additives may then be mixed into the stable foam with the foam stability unchanged or enhanced and without any foam collapse during the whole mixing process.
  • a foamed cementitious slurry, gypsum slurry or a cement, calcined gypsum, and fine pozzolanic additive mixture of the present invention may be initiated by adding a fiber- containing preformed foam into a mortar mixer containing polymer dispersion, accelerators, retarders, wax, water reducer, and lightweight fillers to produce an extremely stable and non running foamed aqueous foam carrier with very uniform additives distribution.
  • the additive- loaded stable foam carrier may then be mixed with the hydraulic slurry of interest.
  • a foamed fiber and other additives-containing hydraulic slurry may be made by: (1) adding a fiber-containing stable foam carrier into a hydraulic slurry with other non-fiber additives; or (2) adding fibers on top of a stable foam carrier while the foam is being mixed with an aqueous hydraulic slurry.
  • the process (2) which mixes fibers with a stable foam carrier before significant amount of hydraulic slurry is incorporated into the foam, can provide a simple manufacturing process without preparing a separate fiber-containing foamed stream beforehand. Both processes (1) and (2) may provide very good filament dispersion for fine denier hydrophilic fibers such as PVA.
  • the process (1) that premixes the high amount of low dpf PVA fibers with the stable foam before adding it to the hydraulic slurry is preferable.
  • the hydraulic cement used in the current invention may be Type I - V Portland cement, slag cement, calcium sulfoaluminate cement, expansive cement, or rapid set cement.
  • the calcium sulfate hemihydrate or gypsum used in the present invention may be calcined gypsum, stucco, alpha-, beta- calcium sulfate hemihydrate, or a combination thereof.
  • the fine pozzolanic additives used in the present invention to prevent the formation of DEF may be manmade or nature products.
  • Manmade fine pozzolanic additive may be metakaolin, silica fume, ground blast furnace slag, or fly ash, and more preferably metakaolin.
  • the fibers When adding fibers into the stable foam, the fibers may be added in the amount of 0.5 -
  • Hydrophilic and hydrophobic fibers with very different fineness, as expressed by dpf (denier per filament) or decitex (dtex), may be easily and uniformly distributed in the lightweight foam stream.
  • the dpf numbers of the fibers suitable for the present invention may have a range of 0.5 - 100, preferably 0.5 - 25, and more preferably 0.5-10. Fibers such as PVA, nylon, polypropylene, basalt, rayon, and acrylic are suitable for such purposes, and PVA fibers with low dpf are most preferred for such cementitious slurries that require low fiber consumption, high tensile strength, and crack resistance.
  • polymers are used in the foamed composition of the present invention for better water resistance or better adhesion, it may comprise water-soluble or water-dispersable polymers and may be present up to 30% by weight of the foam carrier, or the polymeric additives may be incorporated directly into the hydraulic slurry.
  • the foamed aqueous composition including polymers may be prepared by any known polymerization technique, such as, for example, suspension, emulsion dispersion, or solution polymerization.
  • the polymers present in the foamed aqueous composition may be dispersions of polyurethane, poly-acrylic copolymers,
  • ethylenevinylacetate copolymers synthetic and natural rubber emulsions, polyisocyanate dispersions, and/or aqueous urea formaldehyde solutions.
  • the stable foam carrier of the present invention may optionally contain the various fillers such as clay, limestone powder, lightweight fillers, or aggregates.
  • Lightweight fillers may be perlite, expanded polystyrene beads, and other fillers known to the industry.
  • the use of low dpf hydrophilic fibers-containing foam carrier may function as a lightweight thickener, rheology modifier, or thixotropic additive that may render the hydraulic slurries with desirable slump loss and rheological characteristics for the various manufacturing processes such as quick demolding, and wet cast on various sheet-like coating substrates with controlled degree of wetting, slurry penetration and thickness build-up without running on a production line.
  • Water reducing additives used in the hydraulic slurries that are fully compatible with the foam carrier of the present invention may be conventional plasticizers or superplasticizers of sulfonates or carboxylates.
  • the sulfonate plasticizers can be a sulfonate-containing plasticizer such as lignosulfonates, or superplasticizer such as polynaphthalene sulfonate condensate (PNS) used in the industry having a typical weight average molecular weight of from about 8,000 to about 14,000.
  • PPS polynaphthalene sulfonate condensate
  • Naphthalenesulfonate superplasticizers include the alkali salt of
  • polynaphthalenesulfonic acid and its alkali salts the condensation products of naphthalenesulfonic acids and formaldehyde.
  • Particularly desirable polynaphthalenesulfonates include sodium and calcium naphthalenesulfonate.
  • Such commercial products include Diloflo, GEO Specialty Chemicals, Cleveland, Ohio; Daxad, Hampshire Chemical Corp., Lexington, Mass.; and Lomar D, GEO Specialty Chemicals, Lafayette, Ind.
  • superplasticizers are also called fluidizers or dispersants. They are preferably used as aqueous solutions.
  • the naphthalenesulfonates may be used in dry solid or powder form, such as Lomar D from GEO Specialty Chemicals.
  • Gypsum accelerators may be used in the foam carrier of the present invention to shorten the setting time when they are added into gypsum or gypsum rich cementitious slurries.
  • Some accelerators include finely ground dry calcium sulfate dihydrate, commonly referred to as
  • gypsum seeds or ground gypsum. They may also be used together with sugar or starch. The gypsum seeds enhance nucleation of the set gypsum crystals, thereby increasing the
  • Potassium or ammonium sulfates may also be used as set
  • Gypsum retarders may be used in the foam carrier of the present invention to extend the setting time when they are added into gypsum or gypsum rich cementitious slurries.
  • Such retarders may be a chelating agent selected from at least one of sodium citrate, citric acid, tartaric acid, sodium tartrate, a sodium salt of polyacrylic acid, an acrylic acid sulfonic acid copolymer, an ammonium salt of an acrylic acid sulfonic acid copolymer, a sodium salt of an acrylic acid sulfonic acid copolymer, or a blend of an acrylic acid polymer with a sulfonic acid copolymer and salts thereof.
  • Wax or silicon oil may also be used in the aqueous foam carrier of the present invention for improving water resistance of the hydraulic slurry.
  • Example 1 describes a process of incorporating typical gypsum additives into an aqueous foam stream.
  • Example 6 describes a process for making foamed gypsum with well controlled setting speed by incorporating gypsum accelerator in the foam stream and the gypsum retarder in the gypsum slurry.
  • a stable aqueous foam is prepared with a two-part foam system with (1) foam agent
  • AFT-425A from Allied Foam Tech. and (2) a foam stabilizer AFT-425B from Allied Foam Tech using a Hobart Kitchen Aid 10 speed blender with wire whisk.
  • a 2 - 5 weight % foam agent aqueous solution is foamed at speed 8 (225 rpm) for a few minutes, then a 1 - 5 weight % foam stabilizer is added into the mixing bowl.
  • a stable aqueous foam at a density of 0.03-0.08 g./cc and without any foam collapse nor liquid drainage for minutes is achieved.
  • Incorporating fine filler additives in the foam agent and polymeric additives in the foam stabilizer may extend the foam stability.
  • PVA fibers of different dpfs (1-200) may be blended into the stabilized foam by either manually using a mixing blade or continuing the use of wire whisk at speed 4 (135 rpm) or a flat beater at speed 6 (180 rpm) to mix the specified amount of fibers into the preformed foam.
  • a stable aqueous foam is prepared with Allied Foam Tech's AFT G-6 foam generator and the two-part foam: (1) a foam agent and (2) a foam stabilizer.
  • foam agent a 2-5 % foam agent AFT-425A mixed with 15% by weight kaolin clay is fed into the generator with a positive displacement pump. An 80-90 psi at > 10 SCFM supply of compressed air is fed into the foam generator at the air-liquid mixing chamber.
  • the foam stabilizer consisting of 1-5 % foam stabilizer AFT-425B is fed into the foam through a second positive displacement pump.
  • Four cubic feet of the stabilized foam thus made is fed into a 6 cubic feet capacity cement mortar mixer with mixing paddles, ribbon or twin ribbon mixing blades.
  • a desired quantity of PVA or other fibers are added into the preformed foam in the mixer.
  • Twin ribbon mixer at > 50 rpm is preferred for low dpf fibers.
  • the resulting foam is thick with complete fiber distribution without any fiber lump or fiber ball formation.
  • EXAMPFE 3 Preparation and Curing of Foamed Cementitious Composite from a Fiber- containing Foam and a Hydraulic Slurry of Portland cement Mix
  • a Kitchen Aid mixing bowl 10 grams of a high range water reducer powder such as Lomar D from Diamond Shamrock is added. It is then mixed with 280 grams of water. 1,000 grams of Portland cement Type I or Type I/II at speed 2 (95 rpm) or 4 (135 rpm). Fixed amount of fiber-containing foam prepared from EXAMPLE 1 may then be mixed with the slurry at speed 4 to reach the desired density. The foamed slurry may then be cast into a mold of interest for room temperature cure or for 30 - 60 deg. C moisture cure in a sealed bag for 1 or more days. Moisture cured article may then be unsealed for further drying at room or elevated temperature before strength measurement.
  • a high range water reducer powder such as Lomar D from Diamond Shamrock is added. It is then mixed with 280 grams of water. 1,000 grams of Portland cement Type I or Type I/II at speed 2 (95 rpm) or 4 (135 rpm). Fixed amount of fiber-containing foam prepared from EXAMPLE 1 may then be mixed with the
  • a 0.25-inch-thick cement backerboard is made by mixing (A) a fiber containing aqueous foam with 37 grams of acrylic polymer, 67 grams of pre-foamed aqueous foam, 7 grams of PVA fibers, and 3 grams of polypropylene fibers and (B) a hydraulic slurry with 50 grams of water, 130 grams of Portland cement Type I, 200 grams of fly ash F and 3 grams of Lomar D superplasticizer.
  • An alkali resistant fiberglass scrim is laminated to the top and bottom of the 0.25-inch low slump foamed slurry without the need of a mold.
  • the room temperature dried piece has a modulus of rupture greater than 1,000 psi and an indented compressive strength of greater than 1,000 psi.
  • An aqueous foam is prepared according to EXAMPLE 1 using a stainless steel bowl and
  • An aqueous foam is prepared according to EXAMPLE 1 using a stainless steel bowl and KitchenAid mixer. 30 grams of the stable preformed foam thus made is transferred to a second bowl under low mixing speed (100 to 200 rpm). Suitable amount of gypsum additives such as polyvinyl alcohol fiber, wax emulsion, and gypsum accelerator are then added into the preformed foam. When a uniform mix is achieved, the foam mixture is then added under low speed mixing (100 rpm) into a stucco slurry that contains the proper amount of gypsum retarder. The foamed stucco slurry shows a wide window of controlled setting time through such separation of accelerator containing stream from retarder containing slurry.
  • foamed cement roof decks and void fills two major classes of foam agents - the protein based and the surfactant based foam agents are commonly used with protein based foam offering slightly better foam stability.
  • foamed gypsum boards sulfonate-based aliphatic surfactants are used and the fast setting gypsum mixes allow such less stable foam agents to be used without serious drawbacks.
  • none of these foam agents has the required foam stability to maintain foam firmness and the needed viscoelastic feature long enough (typically 1-10 minutes) to shear apart or effectively disperse all the additives of interest before foam collapse sets in.
  • Comparative Sample 2 in Table I shows that, when a protein-based foam agent Isocem S/B-P with limited foam stability is used in dispersing the low denier (1.8 dpf) PVA fibers, the poor foam stability immediately after foam preparation and the fast loss of foam rigidity/integrity from the poor stability made them very ineffective in dispersing the low denier PVA fibers, which are tightly held together.
  • Figure 1 shows that, after mixing of the PVA fibers with Isocem S/B-P ( Figures 1C and 1D) within 1-2 minutes after the foam was formed, the fast drop in foam stability and the wateriness of the foam texture associated with such foam collapse made most of the PVA fibers remain in their original undispersed state after mixing.
  • the stable foam of the present invention the AFT-425A foam agent/ AFT-425B foam stabilizer (Sample 1 in Table 1) showed very effective filament dispersion of the PVA fibers during the whole mixing process with no drop in foam firmness, no detectable foam collapse, and no liquid drainage from foam.
  • Figures 1A and 1B show that the whole texture and uniform fiber distribution in the AFT-425A/AFT- 425B foam not only were unchanged during the whole mixing process, but also lasted until the foam became totally dry ( Figure 1B), which took more than 20 hours.
  • the stable foam in Figure 1A and Sample 1 in Table 1 shows the required foam stability, firmness and shear stability during the whole process of mixing with the low denier PVA fibers.
  • the stable fiber-foam composite of the present invention did not show any sign of foam collapse, fiber lump, or fiber ball formation through the whole drying process of the composite ( Figure 1B).
  • Such further enhanced foam stability that is sustained for hours to days during the drying process could possibly be explained by some strong synergy between the stable foam and the fine denier PVA fibers in the foam.
  • Aqueous foams are dispersion of air in water. Foams are metastable and they may require the use of stabilizing agents to slow down the different mechanisms of foam ageing such as water drainage, inter-bubble coalescence, and foam coarsening. Water drainage eventually leads to foam coarsening followed by foam collapse.
  • the present invention discovered that a thick and gel like liquid layer formed from the foam of the present invention, with its thick and viscous texture, greatly reduces water drainage and prevents foam collapse as shown in Sample 1 of TABLE 1.
  • the present invention found that the viscous, lightweight, and stable foam of the present invention thus becomes very effective means to tear or disperse very fine denier fibers into filaments under shear by mixing.
  • a conventional protein-based single component foam such as Isocem S/B-P has very watery liquid layers around the foam bubbles.
  • the foam texture of the protein-based foam is non- viscous with fast liquid drainage. The foam is thus very ineffective in breaking up the fiber bundles into their individual filaments upon mixing (comparative Sample 2 in TABLE 1).
  • Undispersed PVA Fibers & Lumps ⁇ 5 % undispersed > 90 % undispersed a AFT-425A & AFT-425B are from Allied Foam Tech, US.
  • Tsocem S/B-P a hydrolyzed protein foam product from Isotech, Italy.
  • Table 3 shows that unexpectedly stable foam was derived from the AFT-425A/AFT- 425B foam with the PVA fibers, and the PVA fibers made it possible to make a very low density, as low as below 5 pcf (80 kg/m 3 ) foamed cement with maintained fine pore texture through the whole drying process.
  • the inventor found no prior art that was able to make foamed cement at a density of equal to or less than 10 pcf (160 kg/m 3 ) using conventional slurry process with Portland cement.
  • Sample 1 in Table 3 was made with 10.8 % of 1.8 dpf PVA fiber by weight based on the cement in the fiber- containing foam of the present invention.
  • Foam/fiber mix added into cement Slurry 100 grams 100 grams
  • AFT-425A and AFT-425B are from Allied Foam Tech Corp.
  • Foam/fiber mix added into cement Slurry 61 grams 55 grams
  • Figure 3 shows that the fiber uniformity of low dpf fibers in the stable foam of the present invention depends very much on the mixing speed when a KitchenAid mixer with a simple mixing blade attachment is used to disperse low denier hydrophilic PVA and hydrophobic pp fibers.
  • a KitchenAid mixer with a simple mixing blade attachment is used to disperse low denier hydrophilic PVA and hydrophobic pp fibers.
  • Figure 3A both the 1.8 dpf PVA fibers
  • Figure 3C the 1.0 dpf polypropylene fibers
  • Figure 4 shows that, when a more efficient mixing device such as a wire whisk instead of a flat mixing blade is used in a kitchenAid mixer, even at a mixing speed of 95 rpm and a 0.5 minute mixing time, the PVA fiber distribution in the stable foam is very uniform when the wire whisk was used (Figure 4A), while undispersed PVA fiber bundles were still present in the foam when the flat mixing paddle was used at the same mixing speed and duration (Figure 4B).
  • a more efficient mixing device such as a wire whisk instead of a flat mixing blade is used in a kitchenAid mixer
  • foamed gypsum or stucco articles such as wall boards or ceiling tiles
  • anionic surfactant based foaming agents such as Stepan AS-40 or Geo Specialties Hyonic PFM-10 with limited foam stability are commonly used.
  • Comparative Sample 2 in Table 5 shows that, even using such fast setting gypsum mixes, a preformed foam of AS-40 showed significant foam collapse immediately after the foamed fiber mix was made. Most of the PVA fibers used in the foam were in their undispersed state during the whole mixing and setting process. In contrast, the foamed gypsum (Sample 1 in Table 5) using the stable foam carrier of the present invention containing all the uniformly distributed fibers, wax emulsion, gypsum accelerator and gypsum retarder did not show any foam collapse until the foamed gypsum was totally set. The foamed mix, with all the gypsum additives, produced a foamed gypsum slurry with all the desirable flow, hardness and weight reduction efficiency. TABLE 5
  • Density 41 pcf (wet) Density > 80 pcf (wet) aSulfonate foam agent from Stepan.
  • a foamed and fiber scrim laminated backer board made from a fast setting gypsum rich cement, pozzolanic additive and lime mixes of the present invention shows that such crack free and fast setting gypsum rich cement mixes may outperform that of commercial cement backer boards such as Wonderboard from Custom Building Products (Sample 2 in Table 7) in lightness, strength, water resistance, surface and core finish.
  • the 1 ⁇ 2” thick backer board shows a bending strength of 1,200 psi at a density of 45 pcf, while the comparative Sample 2 backer board shows a bending strength of 1,100 psi at twice the density (91 pcf).
  • a Wonderboard is a 1 ⁇ 2” thick and fiberglass scrim covered backer board product from Custom Building Products.
  • metakaolin/cement ratio of a gypsum rich cement composition has to be greater than 0.30 in order to avoid ettringite caused product disintegration and expansion after hardening.
  • Comparative Sample 2 (in Table 8) made with metakaolin/cement ratio 0.15 did show severe cube crack and product disintegration in consistency with the result shown in the reference (Composition 2 of Table I in US Pat. No. 6,197,107).
  • the present invention

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne un support de mousse aqueuse stable. Le support de mousse aqueuse stable comprend (1) une mousse aqueuse stable comprenant un agent moussant et un stabilisant de mousse ; et (2) des additifs comprenant des fibres et d'autres additifs utilisés dans des compositions hydrauliques, les additifs étant uniformément dispersés dans le support de mousse aqueuse stable, le support de mousse aqueuse stable ne contenant pas de gypse, de ciment, de béton, d'additifs pouzzolaniques fins et d'agrégats.
PCT/US2019/030308 2018-05-14 2019-05-02 Support de mousse aqueuse et procédé de production correspondant WO2019221914A1 (fr)

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CN113387640A (zh) * 2021-06-02 2021-09-14 南昌航空大学 一种整体超疏水硅酸盐水泥泡沫混凝土制品及其制备方法
CN115010453A (zh) * 2022-05-13 2022-09-06 江苏新盈装配建筑科技有限公司 一种新型泡沫混凝土墙板及其生产系统和工艺

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US20160376193A1 (en) * 2015-06-29 2016-12-29 Allied Foam Tech Corp. Fiber containing aqueous foam composite, the process and use
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EP1363969B1 (fr) * 2000-12-08 2010-09-22 Scott Allan Kuehl Procédé de minimalisation ou adaption de la détection d'un objet
US20170334782A1 (en) * 2014-11-21 2017-11-23 Saint-Gobain Placo Fire resistant calcium sulphate-based products
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113387640A (zh) * 2021-06-02 2021-09-14 南昌航空大学 一种整体超疏水硅酸盐水泥泡沫混凝土制品及其制备方法
CN115010453A (zh) * 2022-05-13 2022-09-06 江苏新盈装配建筑科技有限公司 一种新型泡沫混凝土墙板及其生产系统和工艺

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