WO2023164988A1 - 一种原位协同改性增强水泥基复合材料及其应用 - Google Patents

一种原位协同改性增强水泥基复合材料及其应用 Download PDF

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WO2023164988A1
WO2023164988A1 PCT/CN2022/084964 CN2022084964W WO2023164988A1 WO 2023164988 A1 WO2023164988 A1 WO 2023164988A1 CN 2022084964 W CN2022084964 W CN 2022084964W WO 2023164988 A1 WO2023164988 A1 WO 2023164988A1
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whiskers
situ
based composite
composite material
cement
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PCT/CN2022/084964
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English (en)
French (fr)
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尹兵
华先乐
侯东帅
亓东美
华旭江
王攀
李绍纯
金祖权
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青岛理工大学
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Publication of WO2023164988A1 publication Critical patent/WO2023164988A1/zh

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    • 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
    • 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
    • C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention belongs to the technical field of building materials, and in particular relates to an in-situ synergistically modified reinforced cement-based composite material and its application.
  • cement-based materials are the most widely used building materials, but cement-based materials are porous heterogeneous materials with low flexural strength.
  • Polymer modification is a method that can increase the flexural strength of cement-based materials.
  • Polymers can form interlinked and penetrating networks with cement hydration products in concrete, which can disperse and transfer stress, and prevent or weaken the expansion of cracks.
  • the polymer can also improve the interface structure and properties of the cementitious material-aggregate, enhance the cohesion between the components, improve the strength of the transition zone, and greatly improve the performance of the material.
  • some polymers Because of its special functional group, it can chemically interact with cement hydration products or metal ions to form a special bridge bond, enhance the bonding force between materials, and improve the performance of concrete.
  • the in-situ polymerization of polymer monomers helps the polymer to distribute evenly in cement-based materials, improves compatibility and bonding, and can fill the microscopic pores of cement-based materials through in-situ polymerization of polymers in cement-based materials, Theoretically dense materials are prepared, the toughness is enhanced, and the flexural strength is greatly improved.
  • the in-situ polymerization of polymer monomers will inhibit and delay the hydration of cement, so that the compressive strength, especially the early compressive strength, will be significantly reduced (E.Knapen, D.Van Gemert, Cement hydration and microstructure formation in the presence of water -soluble polymers, Cement and Concrete Research. 39(2009) 6–13.
  • the object of the present invention is to provide an in-situ synergistically modified reinforced cement-based composite material, which has excellent flexural strength and good compressive strength.
  • the invention provides an in-situ synergistically modified reinforced cement-based composite material, which includes a cementitious material, a polymer monomer, an initiator, a crosslinking agent and whiskers;
  • the functional groups of the polymer monomers include carbon-carbon double bonds and carboxyl groups
  • the whiskers include organic whiskers and/or inorganic non-metallic whiskers.
  • the carboxyl group is replaced by a group that can be hydrolyzed into a carboxyl group.
  • the polymer monomers include acrylamide monomers, acrylic polymer monomers, butyl methacrylate monomers, ethylene glycol dimethacrylate monomers and hydroxyethyl methacrylate monomers one or more of.
  • the mass ratio of the cementitious material to the polymer monomer is 100:(0.1-10); the content of whiskers in the in-situ synergistically modified reinforced cement-based composite material is 0.5-10 vol.%.
  • the organic whiskers include one or more of cellulose whiskers, chitin whiskers, polybutylacrylate-styrene whiskers and poly-4-hydroxybenzoate whiskers;
  • Non-metallic whiskers include one or more of carbide whiskers, oxide whiskers, nitride whiskers, halide whiskers, graphite whiskers and inorganic salt whiskers; the inorganic salt whiskers Including one or more of carbonate whiskers, sulfate whiskers, borate whiskers and titanate whiskers.
  • the initiator includes one or more of persulfate, sulfite, organic peroxide-ferrous salt system, multi-electron transfer high-valence compound-sulfite system and non-peroxide initiator various;
  • the mass ratio of the polymer monomer to the initiator is 100:(0.5-5).
  • the molecules of the crosslinking agent contain amino groups;
  • the crosslinking agent is a polyamino crosslinking agent;
  • the mass ratio of the polymer monomer to the crosslinking agent is 100:(0.3-5).
  • the crosslinking agent includes N,N'-methylenebisacrylamide, hexamethylenetetramine/hydroquinone, polyethyleneimine, p-phenylenediamine and dimethylaminoethyl methacrylate one or more of esters.
  • the present invention also provides the application of the in-situ synergistically modified reinforced cement-based composite material described in the above technical solution in building materials.
  • the application includes the following steps:
  • the invention provides an in-situ synergistically modified reinforced cement-based composite material, including cementitious materials, polymer monomers, initiators, crosslinking agents and whiskers; the functional groups of the polymer monomers include carbon-carbon double bonds and carboxyl groups; the whiskers include organic whiskers and/or inorganic non-metallic whiskers.
  • the in-situ polymerization of polymer monomers can overcome some defects of conventional polymer modification and form a uniformly distributed polymer network, and because of the presence of chemical bonds, a tightly combined
  • the organic-inorganic network can significantly improve the flexural strength of cement-based materials; whiskers can fill in the pores between cement particles, and its filling effect makes the concrete structure more uniform and dense, and can inhibit the generation and expansion of micro-cracks. This micro-aggregate benefit can improve the compressive strength of concrete.
  • whiskers can not only improve cement-based materials, but also strengthen the polymer network generated by in-situ polymerization of monomers, improve the stability and toughness of the polymer network, and further improve the compressive and flexural properties of cement-based composites.
  • whiskers have strong surface energy and are easy to adsorb polar groups.
  • the carboxyl groups present in the polymer monomers are ionically bonded to the surface of the whiskers, so there is a chemical bond between the polymer monomers and the whiskers.
  • the physical adsorption combined with adsorption, intermolecular force and electrostatic force makes the weak whisker-gelling material interface or the whisker-whisker easy agglomeration interface become the whisker-polymer-gelling material tightly bonded interface, Make the whiskers tightly combined with the gelling material and improve whisker agglomeration.
  • the in-situ polymerization of polymer monomers can modify the surface of the whiskers and adsorb them, which can improve the dispersion and bonding of the whiskers in the cement matrix, so that the densification and strengthening effects of the whiskers on the cement matrix can be fully exerted; at the same time , the polymer network formed by the in-situ polymerization of whiskers and polymer monomers is interspersed and combined, combining the rigidity and dimensional stability of whiskers with the toughness of polymer monomers and polymer materials, further improving the impact of in-situ polymerization on cement-based materials.
  • the enhancement of material flexural strength reduces the adverse effect of in-situ polymerization on the compressive strength of cement-based composites.
  • the in-situ synergistic modification of polymer monomers and whiskers greatly enhanced the comprehensive performance of cement-based materials.
  • the test results show that the 7d flexural strength of the in-situ synergistically modified reinforced cement-based composite material provided by the present invention is 6.8-11.3MPa, the 28d flexural strength is 7.9-13.2MPa; the 7d compressive strength is 38.9-50.5MPa , the 28d compressive strength is 51.2-60.7MPa, which greatly improves the flexural strength while maintaining high compressive strength, and the flexural strength is higher than that of cement-based materials that do not add modified substances (polymer monomers, whiskers). 40-120%, and the compressive strength reaches 85-98% of the cement-based material without adding modified substances (polymer monomers, whiskers).
  • Fig. 1 is the SEM figure of comparative example 2 gained test piece
  • Fig. 2 is the SEM figure of comparative example 2 gained test block
  • Fig. 3 is the SEM figure of embodiment 2 gained test piece
  • Fig. 4 is the SEM figure of embodiment 2 gained test block
  • Fig. 5 is the SEM image of the test piece obtained in Example 5 after soaking in 1wt.% hydrochloric acid for 60s.
  • the invention provides an in-situ synergistically modified reinforced cement-based composite material, which includes a cementitious material, a polymer monomer, an initiator, a crosslinking agent and whiskers;
  • the functional groups of the polymer monomers include carbon-carbon double bonds and carboxyl groups
  • the whiskers include organic whiskers and/or inorganic non-metallic whiskers.
  • each component is a commercially available product well known to those skilled in the art.
  • the in-situ synergistically modified reinforced cement-based composite material provided by the invention includes a cementitious material.
  • the cementitious material preferably includes cement.
  • the cement is preferably ordinary Portland cement.
  • the grade of the ordinary Portland cement is preferably grade 32.5, grade 42.5 or grade 52.5.
  • the in-situ synergistically modified reinforced cement-based composite material preferably further includes aggregates and/or admixtures.
  • the aggregate preferably includes sand and/or stones.
  • the present invention has no special limitation on the sand, and the sand well known to those skilled in the art can be used; the present invention has no special limitation on the stone, and the stone well known to those skilled in the art can be used.
  • the mass ratio of the cement to the aggregate is preferably 1:(1-3), more preferably 1:(1.5-2.5).
  • the admixture preferably includes silica fume and/or fly ash.
  • the mass ratio of the admixture to cement is preferably ⁇ 1.
  • the in-situ synergistically modified reinforced cement-based composite material provided by the invention includes polymer monomers.
  • the functional groups of the polymer monomers include carbon-carbon double bonds and carboxyl groups.
  • the functional group of the polymer monomer includes a carbon-carbon double bond and a group that can be hydrolyzed into a carboxyl group.
  • the polymer monomers preferably include acrylamide monomers, acrylic polymer monomers, butyl methacrylate monomers, ethylene glycol dimethacrylate monomers and hydroxyethyl methacrylate monomers.
  • the acrylamide monomer preferably includes one or more of acrylamide, methylolacrylamide and N-isopropylacrylamide.
  • the mass ratio of the gelling material to the polymer monomer is preferably 100:(0.1-10), more preferably 100:(1-7), and still more preferably 100:(3-5).
  • the in-situ synergistically modified reinforced cement-based composite material provided by the invention includes an initiator.
  • the initiator preferably includes persulfate, sulfite, organic peroxide-ferrous salt system, multi-electron transfer high-valence compound-sulfite system and non-peroxide initiators one or more.
  • the persulfate preferably includes one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
  • the sulfite preferably includes sodium sulfite and/or sodium bisulfite.
  • the organic peroxide-ferrous salt system preferably includes tert-butyl hydroperoxide-ferrous sulfate.
  • the multi-electron transfer high-valence compound-sulfite system preferably includes sodium chlorate-sodium sulfite.
  • the non-peroxide initiator preferably includes ceric ammonium nitrate-thiourea.
  • the mass ratio of the polymer monomer to the initiator is preferably 100:(0.5-5), more preferably 100:(0.8-3), and still more preferably 100:(1-2).
  • the in-situ synergistically modified reinforced cement-based composite material provided by the invention includes a crosslinking agent.
  • the crosslinking agent is preferably a polyamino crosslinking agent.
  • the crosslinking agent preferably includes N,N'-methylenebisacrylamide, hexamethylenetetramine/hydroquinone, polyethyleneimine, p-phenylenediamine and methacrylic acid dimethicone One or more of methylaminoethyl esters.
  • the mass ratio of the polymer monomer to the crosslinking agent is preferably 100:(0.3-5), more preferably 100:(0.4-3), and still more preferably 100:(0.5-2).
  • the in-situ synergistically modified reinforced cement-based composite material provided by the invention includes whiskers.
  • the whiskers include organic whiskers and/or inorganic non-metallic whiskers.
  • the organic whiskers preferably include one or more of cellulose whiskers, chitin whiskers, polybutylacrylate-styrene whiskers and poly-4-hydroxybenzoate whiskers.
  • the inorganic non-metallic whiskers preferably include one or more of carbide whiskers, oxide whiskers, nitride whiskers, halide whiskers, graphite whiskers and inorganic salt whiskers kind.
  • the inorganic salt whiskers preferably include one or more of carbonate whiskers, sulfate whiskers, borate whiskers and titanate whiskers.
  • the content of whiskers in the in-situ synergistically modified reinforced cement-based composite material is preferably 0.5-10 vol.%, more preferably 0.8-6 vol.%, and even more preferably 1-4 vol.%.
  • the present invention also provides the application of the in-situ synergistically modified reinforced cement-based composite material described in the above technical solution in building materials.
  • the application preferably includes the following steps:
  • the invention mixes polymer monomers, initiators, crosslinking agents and water to obtain an in-situ polymerization solution.
  • the preparation temperature of the in-situ synergistically modified reinforced cement-based composite material slurry in the application is preferably 0-50°C, more preferably 0-40°C.
  • the invention controls the preparation temperature of in-situ synergistically modified cement-based composite material slurry to prevent premature polymerization of polymer monomers.
  • the mixing of the polymer monomer, initiator, cross-linking agent and water is preferably after the polymer monomer and water are mixed, and then the resulting polymer monomer solution, initiator and cross-linking agent mix.
  • the stirring is preferably magnetic stirring; the stirring time is preferably 5-10 min.
  • the invention mixes the gelling material and whiskers to obtain the gelling material-whisker dry material.
  • the mixing of the gelling material and whiskers is preferably stirring; the speed of rotation during the stirring is preferably 135-145 rpm, and the speed of revolution is preferably 57-67 rpm; the time is preferably 1-5 minutes, more preferably 2 to 3 minutes.
  • the in-situ synergistically modified reinforced cement-based composite material also includes aggregates and/or admixtures
  • the aggregates and/or admixtures are preferably used at the same timing as the cementitious material.
  • the present invention mixes the cementitious material-whisker dry material with the in-situ polymerization solution to obtain an in-situ synergistically modified reinforced cement-based composite material slurry.
  • the mass ratio of the gelling material to water is preferably 1:(0.35-0.4), more preferably 1:(0.37-0.4), most preferably 1:0.4.
  • the mixing method of the gelling material-whisker dry material and the in-situ polymerization solution is preferably stirring; the stirring preferably includes first stirring and second stirring.
  • the rotation rate in the first stirring is preferably 135-145 rpm, and the revolution rate is preferably 57-67 rpm; the stirring time is preferably 1-3 minutes, more preferably 1.5-2.5 minutes.
  • the rotation rate in the second stirring is preferably 275-295 rpm, and the revolution rate is preferably 115-135 rpm; the stirring time is preferably 60-120 s, more preferably 90-100 s.
  • the equipment to be stirred is preferably a JJ-5 cement mortar mixer.
  • the present invention pours and maintains the in-situ synergistically modified reinforced cement-based composite material slurry.
  • the present invention has no special limitation on the pouring, and the pouring well-known to those skilled in the art can be adopted.
  • the in-situ synergistically modified reinforced cement-based composite material slurry is sequentially molded, vibrated, smoothed, covered Membrane and formwork removal.
  • the oscillation time is preferably 60s.
  • the film material for coating is preferably a plastic wrap.
  • the film covering time is preferably 24 hours.
  • the curing is preferably standard curing; the temperature of the standard curing is preferably 18-22°C; and the humidity is preferably ⁇ 95%.
  • the cementitious material-whisker dry material and the in-situ polymerization solution were stirred and mixed for 2 minutes at a rotation of 140 rpm and a revolution of 62 rpm, and then stirred and mixed for 90 seconds at a rotation of 285 rpm and a revolution of 125 rpm to obtain an in-situ synergistically modified reinforced cement-based composite material slurry ;
  • the in-situ synergistically modified reinforced cement-based composite material slurry is molded, shaken for 60s, smoothed and covered with a film for 24 hours, the mold is removed, and standard curing is carried out under the conditions of 18-22°C and humidity ⁇ 95%.
  • the in-situ synergistic modification strengthens the content of whiskers in the cement-based composite material to 1 vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • the mass ratio of polymer monomer (acrylamide monomer) to initiator is 100:1.33
  • polymer monomer (acrylamide monomer) and crosslinking agent N,N'- methylenebisacrylamide
  • the in-situ synergistic modification strengthens the content of whiskers in the cement-based composite material to 2vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • the mass ratio of polymer monomer (acrylamide monomer) to initiator (ammonium persulfate) is 100:1.33
  • polymer monomer (acrylamide monomer) and crosslinking agent N,N'- methylenebisacrylamide
  • the in-situ synergistic modification strengthens the content of whiskers in the cement-based composite material to 3vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • the mass ratio of polymer monomer (acrylamide monomer) to initiator (ammonium persulfate) is 100:1.33
  • polymer monomer (acrylamide monomer) and crosslinking agent N,N'- methylenebisacrylamide
  • the in-situ synergistic modification strengthens the content of whiskers in the cement-based composite material to 4 vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • the mass ratio of polymer monomer (acrylamide monomer) to initiator (ammonium persulfate) is 100:1.33
  • polymer monomer (acrylamide monomer) and crosslinking agent N,N'- methylenebisacrylamide
  • the consumption of acrylamide monomer is 60g, the consumption of ammonium persulfate is 1g, the consumption of N,N'-methylenebisacrylamide is 0.5g, the consumption of calcium carbonate whisker is 77.5g, the remaining technical means and embodiment 1 consistent, obtain embodiment 5;
  • the in-situ synergistic modification strengthens the content of whiskers in the cement-based composite material to 2.5vol.%, and the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:4, the mass ratio of polymer monomer (acrylamide monomer) to initiator (ammonium persulfate) is 100:1.33, and the mass ratio of polymer monomer (acrylamide monomer) to crosslinking agent (N,N' -methylenebisacrylamide) in a mass ratio of 100:0.67.
  • ammonium persulfate 0.225g, and all the other technical means are consistent with embodiment 2, obtain embodiment 6;
  • the in-situ synergistic modification strengthens the content of whiskers in the cement-based composite material to 1 vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • the mass ratio of polymer monomer (acrylamide monomer) to initiator is 100:0.5
  • polymer monomer (acrylamide monomer) and crosslinking agent N,N'- methylenebisacrylamide
  • ammonium persulfate 0.45g, and all the other technical means are consistent with embodiment 2, obtain embodiment 7;
  • the in-situ synergistic modification strengthens the content of whiskers in the cement-based composite material to 1 vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • the mass ratio of polymer monomer (acrylamide monomer) to initiator is 100:1
  • polymer monomer (acrylamide monomer) and crosslinking agent N,N'- methylenebisacrylamide
  • the in-situ synergistic modification strengthens the content of whiskers in the cement-based composite material to 1 vol.%, and the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3, the mass ratio of polymer monomer (acrylamide monomer) to initiator (ammonium persulfate) is 100:1.5, polymer monomer (acrylamide monomer) and crosslinking agent (N,N'- methylenebisacrylamide) in a mass ratio of 100:0.67.
  • the in-situ synergistic modification strengthens the content of whiskers in the cement-based composite material to 1 vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • the mass ratio of polymer monomer (acrylamide monomer) to initiator (ammonium persulfate) is 100:2
  • polymer monomer (acrylamide monomer) and crosslinking agent (N,N'- methylenebisacrylamide) in a mass ratio of 100:0.67.
  • Example 1 The acrylamide monomer in Example 1 was replaced by a methylolacrylamide monomer, and the rest of the technical means were consistent with Example 1, and Example 10 was obtained.
  • the cementitious material-whisker dry material and the in-situ polymerization solution were stirred and mixed for 2 minutes at a rotation of 140 rpm and a revolution of 62 rpm, and then stirred and mixed for 90 seconds at a rotation of 285 rpm and a revolution of 125 rpm to obtain an in-situ synergistically modified reinforced cement-based composite material slurry ;
  • the in-situ synergistically modified reinforced cement-based composite slurry was molded, shaken for 60s, smoothed and covered with a film for 24 hours, the mold was removed, and standard curing was carried out under the conditions of 18-22°C and humidity ⁇ 95%.
  • the in-situ synergistic modification strengthens the content of whiskers in the cement-based composite material to 1 vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • the mass ratio of polymer monomer (acrylamide monomer) to initiator is 100:1.33
  • polymer monomer (acrylamide monomer) and crosslinking agent N,N'- methylenebisacrylamide
  • the mass ratio of cementitious material (ordinary Portland cement) to polymer monomer (acrylamide monomer) is 100:3, polymer monomer (acrylamide monomer) and initiator
  • the mass ratio of the agent (ammonium persulfate) is 100:1.33
  • the mass ratio of the polymer monomer (acrylamide monomer) to the crosslinking agent (N,N'-methylenebisacrylamide) is 100:0.67.
  • the obtained dry material and 600g of water were stirred and mixed for 2 minutes at a rotation of 140rpm and a revolution of 62rpm, and then stirred and mixed for 90s at a rotation of 285rpm and a revolution of 125rpm.
  • the obtained slurry was molded and shaken for 60s. , Carry out standard curing under the conditions of 18-22°C and humidity ⁇ 95%.
  • the content of whiskers in the cement-based composite material is 2vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer (polyacrylamide) is 100:3
  • the polymer is polypropylene Amides rather than monomers are polymerized in situ.
  • the whisker content in the cement-based composite material is 2vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • no trigger agent, crosslinking agent is no trigger agent, crosslinking agent.
  • the content of whiskers in the cement-based composite material is 2vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • the polymer The mass ratio of monomer (acrylamide monomer) to initiator (ammonium persulfate) is 100:1.33
  • the mass ratio of polymer monomer (acrylamide monomer) to crosslinking agent (tetramethylethylenediamine) is 100: 0.248.
  • the content of whiskers in the cement-based composite material is 2vol.%
  • the mass ratio of the cementitious material (ordinary Portland cement) to the polymer monomer (acrylamide monomer) is 100:3
  • the polymer The mass ratio of monomer (acrylamide monomer) to initiator (ammonium persulfate) is 100:2.5
  • the mass ratio of polymer monomer (acrylamide monomer) to initiator (sodium sulfite) is 100:2.5.
  • the mass ratio of monomer (acrylamide monomer) to crosslinker (N,N'-methylenebisacrylamide) is 100:0.1.
  • the 7d flexural strength of the in-situ synergistically modified reinforced cement-based composite material provided by the present invention is 6.8-11.3MPa
  • the 28d flexural strength is 7.9-13.2MPa
  • the 7d compressive strength is 38.9-50.5MPa
  • the 28d compressive strength is 51.2-60.7MPa
  • the flexural strength is 40-120% higher than that of cement-based materials without modified substances (Comparative Example 1, Comparative Example 5)
  • the compressive strength has reached that without modified substances 85% to 98% of the cement-based materials (comparative example 1, comparative example 5).

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Abstract

建材材料技术领域，特别涉及一种原位协同改性增强水泥基复合材料及其应用。原位协同改性增强水泥基复合材料，包括胶凝材料、聚合物单体、引发剂、交联剂和晶须；所述聚合物单体的官能团包括碳碳双键和羧基；所述晶须包括有机晶须和/或无机非金属晶须。聚合物单体原位聚合对晶须的表面改性及吸附结合，改善晶须在基体中的分散性及结合性，充分发挥晶须对水泥基体的致密、增强作用；晶须与聚合物单体原位聚合形成的聚合物网络穿插结合，将晶须的刚性、尺寸稳定性与聚合物高分子材料的柔性和韧性相结合，进一步提升了原位聚合对水泥基材料抗折强度的增强作用，降低了原位聚合对水泥基复合材料抗压强度的不利影响。

Description

一种原位协同改性增强水泥基复合材料及其应用
本申请要求于2022年03月02日提交中国专利局、申请号为CN202210197316.9、发明名称为“一种原位协同改性增强水泥基复合材料及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于建材材料技术领域，特别涉及一种原位协同改性增强水泥基复合材料及其应用。
背景技术
水泥基材料是应用最广泛的建筑材料，但水泥基材料属于多孔非均质材料，抗折强度低。聚合物改性是一种可以提高水泥基材料抗折强度的方法。
聚合物在混凝土中可以与水泥水化产物形成相互交联、贯穿的网络，能分散和转移应力，阻止或减弱裂缝的扩展。同时，聚合物还能改善胶凝材料-集料的界面结构和性质，增强了各组分之间的黏结性，提高了过渡区的强度，大大改善材料的性能，除此之外，一些聚合物因其特殊的官能团能与水泥水化产物或金属离子发生化学作用，形成特殊的桥键作用，增强材料间的结合力，使混凝土的性能提高。但是常规的聚合物改性混凝土存在聚合物分布不均匀，聚合物与水化产物相容性、结合性不佳等问题，导致聚合物对水泥基材料韧性(抗折强度)的改性效果仍不理想(Z.Sun,Q.Xu,Micromechanical analysis of polyacrylamide-modified concrete for improving strengths,Materials Science and Engineering:A.490(2008)181–192.以及R.Wang,J.Li,T.Zhang,L.Czarnecki,Chemical interaction between polymer and cement in polymer-cement concrete,Bulletin of the Polish Academy of Sciences Technical Sciences.64(2016)785–792.)。
聚合物单体原位聚合有助于聚合物在水泥基材料中均匀分布，改善相容性和结合性，而且可以通过聚合物在水泥基材料中的原位聚合填充水泥基材料的微观孔隙，制备出理论上的致密材料，增强韧性，使抗折强度极大提升。但是，聚合物单体原位聚合会抑制、延缓水泥的水化，使抗压强度，尤其是早期抗压强度降低明显(E.Knapen,D.Van Gemert,Cement hydration and microstructure formation in the presence ofwater-soluble polymers,Cement and Concrete Research. 39(2009)6–13.以及X.Kong,S.Emmerling,J.Pakusch,M.Rueckel,J.Nieberle,Retardation effect of styrene-acrylate copolymer latexes on cement hydration,Cement and Concrete Research.75(2015)23–41.)。所以单独的聚合物单体原位聚合无法兼顾提高水泥基复合材料的韧性(抗折强度)和抗压强度，其综合性能限制了材料的广泛应用。
发明内容
有鉴于此，本发明的目的在于提供一种原位协同改性增强水泥基复合材料，具有优异的抗折强度和良好的抗压强度。
为了实现上述发明的目的，本发明提供以下技术方案：
本发明提供了一种原位协同改性增强水泥基复合材料，包括胶凝材料、聚合物单体、引发剂、交联剂和晶须；
所述聚合物单体的官能团包括碳碳双键和羧基；
所述晶须包括有机晶须和/或无机非金属晶须。
优选的，所述羧基替换为可水解为羧基的基团。
优选的，所述聚合物单体包括丙烯酰胺类单体、丙烯酸类聚合物单体、甲基丙烯酸丁酯单体、乙二醇二甲基丙烯酸酯单体和甲基丙烯酸羟乙酯单体中的一种或多种。
优选的，所述胶凝材料与聚合物单体的质量比为100：(0.1～10)；所述原位协同改性增强水泥基复合材料中晶须的含量为0.5～10vol.％。
优选的，所述有机晶须包括纤维素晶须、甲壳素晶须、聚丙烯酸丁酯-苯乙烯晶须和聚4-羟基苯甲酸酯晶须中的一种或多种；所述无机非金属晶须包括碳化物晶须、氧化物晶须、氮化物晶须、卤化物晶须、石墨类晶须和无机盐类晶须中的一种或多种；所述无机盐类晶须包括碳酸盐晶须、硫酸盐晶须、硼酸盐晶须和钛酸盐晶须中的一种或多种。
优选的，所述引发剂包括过硫酸盐、亚硫酸盐、有机过氧化物-亚铁盐体系、多电子转移高价态化合物-亚硫酸盐体系和非过氧化物类引发剂中的一种或多种；
所述聚合物单体与引发剂的质量比为100：(0.5～5)。
优选的，所述交联剂的分子含有氨基；所述交联剂为多氨基交联剂；
所述聚合物单体与交联剂的质量比为100：(0.3～5)。
优选的，所述交联剂包括N,N'-亚甲基双丙烯酰胺、六亚甲基四胺/对苯二酚、聚乙烯亚胺、对苯二胺和甲基丙烯酸二甲氨基乙酯中的一种或多种。
本发明还提供了上述技术方案所述原位协同改性增强水泥基复合材料在建筑材料中的应用。
优选的，所述应用包括以下步骤：
将聚合物单体、引发剂、交联剂和水混合，得到原位聚合溶液；
将胶凝材料和晶须混合，得到胶凝材料-晶须干料；
将所述胶凝材料-晶须干料和原位聚合溶液混合，得到原位协同改性增强水泥基复合材料浆体，将所得原位协同改性增强水泥基复合材料浆体进行浇注和养护。
本发明提供了一种原位协同改性增强水泥基复合材料，包括胶凝材料、聚合物单体、引发剂、交联剂和晶须；所述聚合物单体的官能团包括碳碳双键和羧基；所述晶须包括有机晶须和/或无机非金属晶须。
在本发明中，聚合物单体在晶须存在条件下，发生的原位聚合可以克服常规聚合物改性的一些缺陷，形成均匀分布的聚合物网络，又因存在化学键，形成了紧密结合的有机-无机网络，能够显著提高水泥基材料的抗折强度；晶须能够填充在水泥颗粒之间的孔隙中，其填充效应使混凝土结构更加均匀、密实，同时可以抑制微裂纹的产生和扩展，这种微集料效益能够改善混凝土的抗压强度。除了上述的聚合物和晶须对于水泥基材料的增强作用外，聚合物单体原位聚合与晶须之间还存在复杂的协同增强作用。首先，晶须不仅可以改善水泥基材料，还可以增强单体原位聚合生成的聚合物网络，提升了聚合物网络的稳定性和韧性，进一步提升水泥基复合材料的抗压抗折性能。其次，晶须具有较强的表面能，易吸附极性基团，同时聚合物单体存在的羧基和晶须表面离子键合，因此聚合物单体与晶须之间存在以化学键结合的化学吸附和分子间作用力、静电力结合的物理吸附，使得晶须-胶凝材料的弱界面或者晶须-晶须的易团聚界面变成晶须-聚合物-胶凝材料的紧密结合界面，使晶须与胶凝材料结合紧密且改善晶须团聚。总之，聚合物单体原位聚合对晶须的表面改性及吸附结合，改善了晶须在水泥基体中的分散性及结合性，使晶须对水泥基体的致密、增强作用充分发挥；同时，晶须与聚合物单体原位聚合形成的聚合物网络穿插结合，将晶须的刚性、尺寸稳定性与聚合物单体高分子材料的韧性相结合，进一步提 升了原位聚合对水泥基材料抗折强度的增强作用，降低了原位聚合对水泥基复合材料抗压强度的不利影响。聚合物单体与晶须的原位协同改性作用极大增强了水泥基材料的综合性能。
实施例测试结果表明，本发明提供的原位协同改性增强水泥基复合材料的7d抗折强度为6.8～11.3MPa，28d抗折强度为7.9～13.2MPa；7d抗压强度为38.9～50.5MPa，28d抗压强度为51.2～60.7MPa，在大幅提高抗折强度的同时保持高的抗压强度，抗折强度较不掺加改性物质(聚合物单体、晶须)的水泥基材料提升40～120％，抗压强度达到了不掺加改性物质(聚合物单体、晶须)的水泥基材料的85～98％。
附图说明
图1为对比例2所得试块的SEM图；
图2为对比例2所得试块的SEM图；
图3为实施例2所得试块的SEM图；
图4为实施例2所得试块的SEM图；
图5为实施例5所得试块在1wt.％盐酸中浸泡60s后的SEM图。
具体实施方式
本发明提供了一种原位协同改性增强水泥基复合材料，包括胶凝材料、聚合物单体、引发剂、交联剂和晶须；
所述聚合物单体的官能团包括碳碳双键和羧基；
所述晶须包括有机晶须和/或无机非金属晶须。
在本发明中，若无特殊说明，所述各组分均为本领域技术人员熟知的市售商品。
本发明提供的原位协同改性增强水泥基复合材料包括胶凝材料。在本发明中，所述胶凝材料优选包括水泥。在本发明中，所述水泥优选为普通硅酸盐水泥。在本发明中，所述普通硅酸盐水泥的级别优选为32.5级、42.5级或52.5级。
在本发明中，所述原位协同改性增强水泥基复合材料优选还包括骨料和/或掺合料。
在本发明中，所述骨料优选包括砂和/或石子。本发明对所述砂没有特殊限定，采用本领域技术人员熟知的砂即可；本发明对所述石子没有特殊限定，采 用本领域技术人员熟知的石子即可。在本发明中，所述水泥与骨料的质量比优选为1：(1～3)，更优选为1：(1.5～2.5)。
在本发明中，所述掺合料优选包括硅灰和/或粉煤灰。在本发明中，所述掺合料与水泥的质量比优选≤1。
本发明提供的原位协同改性增强水泥基复合材料包括聚合物单体。在本发明中，所述聚合物单体的官能团包括碳碳双键和羧基。作为本发明的并列技术方案，所述聚合物单体的官能团包括碳碳双键和可水解为羧基的基团。在本发明中，所述聚合物单体优选包括丙烯酰胺类单体、丙烯酸类聚合物单体、甲基丙烯酸丁酯单体、乙二醇二甲基丙烯酸酯单体和甲基丙烯酸羟乙酯单体中的一种或多种。在本发明中，所述丙烯酰胺类单体优选包括丙烯酰胺、羟甲基丙烯酰胺和N-异丙基丙烯酰胺中的一种或多种。
在本发明中，所述胶凝材料与聚合物单体的质量比优选为100：(0.1～10)，更优选为100：(1～7)，再优选为100：(3～5)。
本发明提供的原位协同改性增强水泥基复合材料包括引发剂。在本发明中，所述引发剂优选包括过硫酸盐、亚硫酸盐、有机过氧化物-亚铁盐体系、多电子转移高价态化合物-亚硫酸盐体系和非过氧化物类引发剂中的一种或多种。在本发明中，所述过硫酸盐优选包括过硫酸铵、过硫酸钾和过硫酸钠中的一种或多种。在本发明中，所述亚硫酸盐优选包括亚硫酸钠和/或亚硫酸氢钠。在本发明中，所述有机过氧化物-亚铁盐体系优选包括过氧化氢叔丁基-硫酸亚铁。在本发明中，所述多电子转移高价态化合物-亚硫酸盐体系优选包括氯酸钠-亚硫酸钠。在本发明中，所述非过氧化物类引发剂优选包括硝酸铈铵-硫脲。
在本发明中，所述聚合物单体与引发剂的质量比优选为100：(0.5～5)，更优选为100：(0.8～3)，再优选为100：(1～2)。
本发明提供的原位协同改性增强水泥基复合材料包括交联剂。在本发明中，所述交联剂优选为多氨基交联剂。在本发明中，所述交联剂优选包括N,N'-亚甲基双丙烯酰胺、六亚甲基四胺/对苯二酚、聚乙烯亚胺、对苯二胺和甲基丙烯酸二甲氨基乙酯中的一种或多种。
在本发明中，所述聚合物单体与交联剂的质量比优选为100：(0.3～5)，更优选为100：(0.4～3)，再优选为100：(0.5～2)。
本发明提供的原位协同改性增强水泥基复合材料包括晶须。在本发明中，所 述晶须包括有机晶须和/或无机非金属晶须。在本发明中，所述有机晶须优选包括纤维素晶须、甲壳素晶须、聚丙烯酸丁酯-苯乙烯晶须和聚4-羟基苯甲酸酯晶须中的一种或多种。在本发明中，所述无机非金属晶须优选包括碳化物晶须、氧化物晶须、氮化物晶须、卤化物晶须、石墨类晶须和无机盐类晶须中的一种或多种。在本发明中，所述无机盐类晶须优选包括碳酸盐晶须、硫酸盐晶须、硼酸盐晶须和钛酸盐晶须中的一种或多种。
在本发明中，所述原位协同改性增强水泥基复合材料中晶须的含量优选为0.5～10vol.％，更优选为0.8～6vol.％，再优选为1～4vol.％。
本发明还提供了上述技术方案所述原位协同改性增强水泥基复合材料在建筑材料中的应用。
在本发明中，所述应用优选包括以下步骤：
将聚合物单体、引发剂、交联剂和水混合，得到原位聚合溶液；
将胶凝材料和晶须混合，得到胶凝材料-晶须干料；
将所述胶凝材料-晶须干料和原位聚合溶液混合，得到原位协同改性增强水泥基复合材料浆体，将所得原位协同改性增强水泥基复合材料浆体进行浇注和养护。
本发明将聚合物单体、引发剂、交联剂和水混合，得到原位聚合溶液。
在本发明中，所述应用中原位协同改性增强水泥基复合材料浆料的制备温度优选为0～50℃，更优选为0～40℃。本发明控制原位协同改性增强水泥基复合材料浆料的制备温度，以防止聚合物单体过早聚合。
在本发明中，所述聚合物单体、引发剂、交联剂和水的混合优选为将聚合物单体和水混合后，再将所得的聚合物单体溶液、引发剂和交联剂混合。
本发明对所述聚合物单体、引发剂、交联剂和水的混合方式没有特殊限定，采用本领域技术人员熟知的混合即可，具体的，如搅拌。在本发明中，所述搅拌优选为磁力搅拌；所述搅拌的时间优选为5～10min。
本发明将胶凝材料和晶须混合，得到胶凝材料-晶须干料。
在本发明中，所述胶凝材料和晶须的混合优选为搅拌；所述搅拌中自转的速率优选为135～145rpm，公转的速率优选为57～67rpm；时间优选为1～5min，更优选为2～3min。
在本发明中，当所述原位协同改性增强水泥基复合材料还包括骨料和/或掺 合料时，所述骨料和/或掺合料优选与胶凝材料的使用时机相同。
得到原位聚合溶液和胶凝材料-晶须干料后，本发明将所述胶凝材料-晶须干料和原位聚合溶液混合，得到原位协同改性增强水泥基复合材料浆体。
在本发明中，所述胶凝材料和水的质量比优选为1：(0.35～0.4)，更优选为1：(0.37～0.4)，最优选为1：0.4。
在本发明中，所述胶凝材料-晶须干料和原位聚合溶液的混合的方法优选为搅拌；所述搅拌优选包括第一搅拌和第二搅拌。在本发明中，所述第一搅拌中自转的速率优选为135～145rpm，公转的速率优选为57～67rpm；搅拌时间优选为1～3min，更优选为1.5～2.5min。在本发明中，所述第二搅拌中自转的速率优选为275～295rpm，公转的速率优选为115～135rpm；搅拌时间优选为60～120s，更优选为90～100s。在本发明的实施例中，所搅拌的设备优选为JJ-5型水泥胶砂搅拌机。
得到原位协同改性增强水泥基复合材料浆体后，本发明将所述原位协同改性增强水泥基复合材料浆体进行浇注和养护。
本发明对所述浇注没有特殊限定，采用本领域技术人员熟知的浇注即可，具体的，如将所述原位协同改性增强水泥基复合材料浆体依次装模、震荡、抹平、覆膜和拆模。在本发明中，所述震荡的时间优选为60s。在本发明中，所述覆膜用膜材料优选为保鲜膜。在本发明中，所述覆膜的时间优选为24h。
在本发明中，所述养护优选为标准养护；所述标准养护的温度优选为18～22℃；湿度优选≥95％。
为了进一步说明本发明，下面结合实施例对本发明提供的一种原位协同改性增强水泥基复合材料及其应用进行详细地描述，但不能将它们理解为对本发明保护范围的限定。显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
将45g丙烯酰胺单体和600g水搅拌，得到聚合物单体溶液；将所得聚合物单体溶液、0.6g过硫酸铵和0.3g的N,N'-亚甲基双丙烯酰胺混合，磁力搅拌5min，得到原位聚合溶液；
将1500g普通硅酸盐水泥(P.O 42.5级)和31g碳酸钙晶须在自转140rpm、 公转62rpm下搅拌混合2min，得到胶凝材料-晶须干料；
将胶凝材料-晶须干料和原位聚合溶液在自转140rpm、公转62rpm下搅拌混合2min，然后在自转285rpm、公转125rpm下搅拌混合90s，得到原位协同改性增强水泥基复合材料浆体；
将原位协同改性增强水泥基复合材料浆体装模，震荡60s，抹平后覆膜24h，拆模，在18～22℃、湿度≥95％条件下进行标准养护。
本实施例中，原位协同改性增强水泥基复合材料中晶须的含量为1vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：1.33，聚合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
实施例2
碳酸钙晶须的用量为62g，其余技术手段与实施例1一致，得到实施例2；
本实施例中，原位协同改性增强水泥基复合材料中晶须的含量为2vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：1.33，聚合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
实施例3
碳酸钙晶须的用量为93g，其余技术手段与实施例1一致，得到实施例3；
本实施例中，原位协同改性增强水泥基复合材料中晶须的含量为3vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：1.33，聚合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
实施例4
碳酸钙晶须的用量为124g，其余技术手段与实施例1一致，得到实施例4；
本实施例中，原位协同改性增强水泥基复合材料中晶须的含量为4vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：1.33，聚 合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
实施例5
丙烯酰胺单体的用量为60g，过硫酸铵的用量为1g，N,N'-亚甲基双丙烯酰胺的用量为0.5g，碳酸钙晶须的用量为77.5g，其余技术手段与实施例1一致，得到实施例5；
本实施例中，原位协同改性增强水泥基复合材料中晶须的含量为2.5vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：4，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：1.33，聚合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
实施例6
过硫酸铵的用量是0.225g，其余技术手段与实施例2一致，得到实施例6；
本实施例中，原位协同改性增强水泥基复合材料中晶须的含量为1vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：0.5，聚合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
实施例7
过硫酸铵的用量是0.45g，其余技术手段与实施例2一致，得到实施例7；
本实施例中，原位协同改性增强水泥基复合材料中晶须的含量为1vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：1，聚合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
实施例8
过硫酸铵的用量是0.675g，其余技术手段与实施例2一致，得到实施例6；
本实施例中，原位协同改性增强水泥基复合材料中晶须的含量为1vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：1.5，聚 合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
实施例9
过硫酸铵的用量是0.9g，其余技术手段与实施例2一致，得到实施例6；
本实施例中，原位协同改性增强水泥基复合材料中晶须的含量为1vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：2，聚合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
实施例10
以羟甲基丙烯酰胺单体代替实施例1中的丙烯酰胺单体，其余技术手段与实施例1一致，得到实施例10。
实施例11
将30g丙烯酰胺单体和400g水搅拌，得到聚合物单体溶液；将所得聚合物单体溶液、0.4g过硫酸铵和0.2g的N,N'-亚甲基双丙烯酰胺混合，磁力搅拌5min，得到原位聚合溶液；
将1000g普通硅酸盐水泥(P.O 42.5级)、900g河砂(粒径为0.075～0.6mm)和26.8g碳酸钙晶须在自转140rpm、公转62rpm下搅拌混合2min，得到胶凝材料-晶须干料；
将胶凝材料-晶须干料和原位聚合溶液在自转140rpm、公转62rpm下搅拌混合2min，然后在自转285rpm、公转125rpm下搅拌混合90s，得到原位协同改性增强水泥基复合材料浆体；
将原位协同改性增强水泥基复合材料浆体装模，震荡60s，抹平后覆膜24h，拆模，在18～22℃、湿度≥95％条件下进行标准养护。
本实施例中，原位协同改性增强水泥基复合材料中晶须的含量为1vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：1.33，聚合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
对比例1
将1500g普通硅酸盐水泥(P.O 42.5级)加入搅拌锅中，在砂浆搅拌机中在自转140rpm、公转62rpm下搅拌2min，加入600g水，在自转140rpm、公转62rpm下搅拌混合2min，然后在自转285rpm、公转125rpm下搅拌混合90s，将所得的浆体装模，震荡60s，抹平后覆膜24h，拆模，在18～22℃、湿度≥95％条件下进行标准养护。
本对比例中，无聚合物单体、引发剂、交联剂和晶须。
对比例2
将1500g普通硅酸盐水泥(P.O 42.5级)和62g碳酸钙晶须在自转140rpm、公转62rpm下搅拌混合2min，得到胶凝材料-晶须干料；
将所得胶凝材料-晶须干料和600g水在自转140rpm、公转62rpm下搅拌混合2min，然后在自转285rpm、公转125rpm下搅拌混合90s，将所得的浆体装模，震荡60s，抹平后覆膜24h，拆模，在18～22℃、湿度≥95％条件下进行标准养护。
本对比例中，无聚合物单体、引发剂和交联剂，水泥基复合材料中晶须的含量为2vol.％。
对比例3
将45g丙烯酰胺单体和600g水搅拌，得到聚合物单体溶液；将所得聚合物单体溶液、0.6g过硫酸铵和0.3g的N,N'-亚甲基双丙烯酰胺混合，磁力搅拌5min，得到原位聚合溶液；
将1500g普通硅酸盐水泥(P.O 42.5级)和原位聚合溶液在自转140rpm、公转62rpm下搅拌混合2min，然后在自转285rpm、公转125rpm下搅拌混合90s，将所得的浆料装模，震荡60s，抹平后覆膜24h，拆模，在18～22℃、湿度≥95％条件下进行标准养护。
本对比例中，无晶须，胶凝材料(普通硅酸盐水泥)和聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：1.33，聚合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.67。
对比例4
将1500g普通硅酸盐水泥(P.O 42.5级)和31g碳酸钙晶须在自转140rpm、公转62rpm下搅拌混合2min，得到胶凝材料-晶须干料；
将所得胶凝材料-晶须干料和600g水在自转140rpm、公转62rpm下搅拌混合2min，然后在自转285rpm、公转125rpm下搅拌混合90s，将所得的浆体装模，震荡60s，抹平后覆膜24h，拆模，在18～22℃、湿度≥95％条件下进行标准养护。
本对比例中，无聚合物单体、引发剂和交联剂，水泥基复合材料中晶须的含量为1vol.％。
对比例5
将1000g普通硅酸盐水泥(P.O 42.5级)和900g河砂(粒径为0.075～0.6mm)加入搅拌锅中，在砂浆搅拌机中在自转140rpm、公转62rpm下搅拌2min，加入600g水后，在自转140rpm、公转62rpm下搅拌混合2min，然后在自转285rpm、公转125rpm下搅拌混合90s，将所得的浆体装模，震荡60s，抹平后覆膜24h，拆模，在18～22℃、湿度≥95％条件下进行标准养护。
本对比例中，无聚合物单体、引发剂、交联剂和晶须。
对比例6
将1500g普通硅酸盐水泥(P.O 42.5级)、45g聚丙烯酰胺聚合物和62g碳酸钙晶须在自转140rpm、公转62rpm下搅拌混合2min，得到干料；
将所得干料和600g水在自转140rpm、公转62rpm下搅拌混合2min，然后在自转285rpm、公转125rpm下搅拌混合90s，将所得的浆体装模，震荡60s，抹平后覆膜24h，拆模，在18～22℃、湿度≥95％条件下进行标准养护。
本对比例中，水泥基复合材料中晶须的含量为2vol.％，胶凝材料(普通硅酸盐水泥)与聚合物(聚丙烯酰胺)的质量比为100：3，聚合物为聚丙烯酰胺而非单体原位聚合。
对比例7
无过硫酸铵和N,N'-亚甲基双丙烯酰胺，其余技术手段与实施例2一致，得到对比例7。
本对比例中，水泥基复合材料中晶须的含量为2vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，无引发剂、交联剂。
对比例8
采用144μL四甲基乙二胺作为交联剂代替N,N'-亚甲基双丙烯酰胺，其余技 术手段与实施例2一致，得到对比例8；
本对比例中，水泥基复合材料中晶须的含量为2vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：1.33，聚合物单体(丙烯酰胺单体)与交联剂(四甲基乙二胺)的质量比为100：0.248。
对比例9
采用1.225g过硫酸铵和1.225g亚硫酸钠作为引发剂代替过硫酸铵单引发体系，交联剂N,N'-亚甲基双丙烯酰胺用量为0.045，其余技术手段与实施例2一致，得到对比例9；
本对比例中，水泥基复合材料中晶须的含量为2vol.％，胶凝材料(普通硅酸盐水泥)与聚合物单体(丙烯酰胺单体)的质量比为100：3，聚合物单体(丙烯酰胺单体)与引发剂(过硫酸铵)的质量比为100：2.5，聚合物单体(丙烯酰胺单体)与引发剂(亚硫酸钠)的质量比为100：2.5，聚合物单体(丙烯酰胺单体)与交联剂(N,N'-亚甲基双丙烯酰胺)的质量比为100：0.1。
按照GB/T 17671-1999水泥胶砂强度检验方法(ISO法)，对实施例1～11和对比例1～9的试块的抗压抗折强度进行测试，测试结果见表1。
表1 实施例1～11和对比例1～9试块抗折强度测试结果(MPa)
Figure PCTCN2022084964-appb-000001
Figure PCTCN2022084964-appb-000002
根据表1可见，本发明提供的原位协同改性增强水泥基复合材料的7d抗折强度为6.8～11.3MPa，28d抗折强度为7.9～13.2MPa；7d抗压强度为38.9～50.5MPa，28d抗压强度为51.2～60.7MPa，抗折强度较不掺加改性物质的水泥基材料(对比例1、对比例5)提升40～120％，抗压强度达到了不掺加改性物质的水泥基材料(对比例1、对比例5)的85～98％。
对实施例2、5和对比例2所得试块进行扫描电子显微测试，所得SEM图见图1～5，其中，图1和图2为对比例2的SEM图，图3和图4为实施例2的SEM图；图5为实施例5的SEM图(实施例5所得试块用1wt.％的盐酸浸泡60s，然后进行SEM测试)。
由图1可见，碳酸钙晶须单独改性时，可在断面观察到裸露的碳酸钙晶须。
由图2可见，碳酸钙晶须单独改性时，碳酸钙晶须发生团聚。
由图3和图4可见，聚合物单体原位聚合与晶须共同作用时，碳酸钙晶须与聚合物网络、水泥基体融为一体，证实了碳酸钙晶须与聚合物原位聚合之间的协同增强作用。
由图5可以观察到清楚的原位聚合生成的聚合物网络结构，碳酸钙晶须的存在可以增强该聚合物网络。
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，人们还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。

Claims (19)

  1. 一种原位协同改性增强水泥基复合材料，包括胶凝材料、聚合物单体、引发剂、交联剂和晶须；
    所述聚合物单体的官能团包括碳碳双键和羧基；
    所述晶须包括有机晶须和/或无机非金属晶须。
  2. 根据权利要求1所述的原位协同改性增强水泥基复合材料，其特征在于，所述羧基替换为可水解为羧基的基团。
  3. 根据权利要求1所述的原位协同改性增强水泥基复合材料，其特征在于，所述聚合物单体包括丙烯酰胺类单体、丙烯酸类聚合物单体、甲基丙烯酸丁酯单体、乙二醇二甲基丙烯酸酯单体和甲基丙烯酸羟乙酯单体中的一种或多种。
  4. 根据权利要求1或2所述的原位协同改性增强水泥基复合材料，其特征在于，所述胶凝材料与聚合物单体的质量比为100：(0.1～10)；所述原位协同改性增强水泥基复合材料中晶须的含量为0.5～10vol.％。
  5. 根据权利要求1所述的原位协同改性增强水泥基复合材料，其特征在于，所述有机晶须包括纤维素晶须、甲壳素晶须、聚丙烯酸丁酯-苯乙烯晶须和聚4-羟基苯甲酸酯晶须中的一种或多种；
    所述无机非金属晶须包括碳化物晶须、氧化物晶须、氮化物晶须、卤化物晶须、石墨类晶须和无机盐类晶须中的一种或多种；所述无机盐类晶须包括碳酸盐晶须、硫酸盐晶须、硼酸盐晶须和钛酸盐晶须中的一种或多种。
  6. 根据权利要求1所述的原位协同改性增强水泥基复合材料，其特征在于，所述引发剂包括过硫酸盐、亚硫酸盐、有机过氧化物-亚铁盐体系、多电子转移高价态化合物-亚硫酸盐体系和非过氧化物类引发剂中的一种或多种；
    所述聚合物单体与引发剂的质量比为100：(0.5～5)。
  7. 根据权利要求1所述的原位协同改性增强水泥基复合材料，其特征在于，所述交联剂为多氨基交联剂；
    所述聚合物单体与交联剂的质量比为100：(0.3～5)。
  8. 根据权利要求7所述的原位协同改性增强水泥基复合材料，其特征在于，所述交联剂包括N,N'-亚甲基双丙烯酰胺、六亚甲基四胺/对苯二酚、聚乙烯亚胺、对苯二胺和甲基丙烯酸二甲氨基乙酯中的一种或多种。
  9. 根据权利要求1所述的原位协同改性增强水泥基复合材料，其特征在于，所述胶凝材料包括水泥。
  10. 根据权利要求9所述的原位协同改性增强水泥基复合材料，其特征在于，所述原位协同改性增强水泥基复合材料还包括骨料和/或掺合料。
  11. 根据权利要求10所述的原位协同改性增强水泥基复合材料，其特征在于，所述骨料包括砂和/或石子；所述水泥和骨料的质量比为1：(1～3)。
  12. 根据权利要求10所述的原位协同改性增强水泥基复合材料，其特征在于，所述掺合料包括硅灰和/或粉煤灰；所述掺合料与水泥的质量比≤1。
  13. 权利要求1～12任一项所述原位协同改性增强水泥基复合材料在建筑材料中的应用。
  14. 根据权利要求13所述的应用，其特征在于，所述应用包括以下步骤：
    将聚合物单体、引发剂、交联剂和水混合，得到原位聚合溶液；
    将胶凝材料和晶须混合，得到胶凝材料-晶须干料；
    将所述胶凝材料-晶须干料和原位聚合溶液混合，得到原位协同改性增强水泥基复合材料浆体，将所得原位协同改性增强水泥基复合材料浆体进行浇注和养护。
  15. 根据权利要求14所述的应用，其特征在于，所述胶凝材料和水的质量比为1：(0.35～0.4)。
  16. 根据权利要求14所述的应用，其特征在于，所述胶凝材料和晶须的混合方式为搅拌；
    所述搅拌中自转的速率为135～145rpm，公转的速率为57～67rpm；时间为1～5min。
  17. 根据权利要求14所述的应用，其特征在于，所述胶凝材料-晶须干料和原位聚合溶液混合的方法为搅拌；
    所述搅拌包括第一搅拌和第二搅拌。
  18. 根据权利要求17所述的应用，其特征在于，所述第一搅拌中自转的速率为135～145rpm，公转的速率为57～67rpm，时间为1～3min；
    所述第二搅拌中自转的速率为275～295rpm，公转的速率为115～135rpm，时间为60～120s。
  19. 根据权利要求14所述的应用，其特征在于，所述养护为标准养护；所 述标准养护的温度为18～22℃；湿度≥95％。
PCT/CN2022/084964 2022-03-02 2022-04-02 一种原位协同改性增强水泥基复合材料及其应用 WO2023164988A1 (zh)

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CN115536299A (zh) * 2022-10-21 2022-12-30 东南大学 一种有机-无机复合增韧材料及其在混凝土中的应用
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