WO2023124471A1 - 一种多源废渣基混凝土3d打印材料及制备方法 - Google Patents

一种多源废渣基混凝土3d打印材料及制备方法 Download PDF

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WO2023124471A1
WO2023124471A1 PCT/CN2022/127571 CN2022127571W WO2023124471A1 WO 2023124471 A1 WO2023124471 A1 WO 2023124471A1 CN 2022127571 W CN2022127571 W CN 2022127571W WO 2023124471 A1 WO2023124471 A1 WO 2023124471A1
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parts
printing material
agent
sand
source waste
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PCT/CN2022/127571
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English (en)
French (fr)
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钱元弟
金仁才
唐刚
方圆
何兆芳
王新成
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中国十七冶集团有限公司
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
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    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • C04B14/068—Specific natural sands, e.g. sea -, beach -, dune - or desert sand
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    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
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    • C04B16/04—Macromolecular compounds
    • C04B16/06—Macromolecular compounds fibrous
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    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/06—Macromolecular compounds fibrous
    • C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B16/0625—Polyalkenes, e.g. polyethylene
    • C04B16/0633—Polypropylene
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    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/06—Macromolecular compounds fibrous
    • C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B16/0641—Polyvinylalcohols; Polyvinylacetates
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    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/06—Macromolecular compounds fibrous
    • C04B16/0675—Macromolecular compounds fibrous from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B16/0691—Polyamides; Polyaramides
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    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
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    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • C—CHEMISTRY; METALLURGY
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    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • C04B18/142—Steelmaking slags, converter slags
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/003—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • C04B24/122—Hydroxy amines
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • C04B24/123—Amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
    • 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 concrete building materials, and in particular relates to a multi-source waste slag-based concrete 3D printing material and a preparation method thereof.
  • 3D printing technology is booming in medical, aerospace, construction, electronics, clothing, intelligent manufacturing and other fields.
  • 3D printing technology has the advantages of no mold, refinement, and editability, and has broad application prospects, promoting the development of the construction industry to a higher dimension.
  • construction in the construction industry requires a large amount of cement and other cementitious materials, and cement production is a high energy-consuming industry, which seriously deviates from my country's "double carbon" strategy.
  • the metallurgical and coal power industries produce a large amount of bulk solid waste such as steel slag, slag, and fly ash in the production process.
  • the above-mentioned solid waste is relatively difficult to dispose of at present, and it is mainly disposed of by open-air stacking.
  • this disposal method consumes a large amount of arable land resources, on the other hand, the accumulation of waste residues can easily cause air, water and soil pollution, and have a negative impact on the environment.
  • Steel slag, slag, and fly ash are rich in potential gelling components such as calcium oxide, silicon oxide, and aluminum oxide, which have the potential to become building materials.
  • 3D printing concrete materials usually need to introduce a large amount of fine aggregate components, but the particle size of rigid fine aggregate is relatively large, and the compatibility with other components in concrete materials is insufficient. At the same time, the fine aggregate has strong rigidity, and the lack of effective buffer connection between the fine aggregate particles makes the prepared 3D printed concrete material insufficient in toughness. The above-mentioned deficiency makes the prepared 3D printed concrete material often suffer from brittle fracture.
  • the purpose of the present invention is to provide a multi-source waste slag-based concrete 3D printing material and its preparation method. Introducing a variety of metallurgical, coal and electricity waste slag into this multi-source waste slag-based concrete 3D printing material can effectively reduce the amount of cement used, which is in line with the national "double carbon" strategy.
  • the synergistic reaction of additives and complexing agents can effectively improve the excellent early strength and cohesion of the multi-source waste slag-based concrete 3D printing material;
  • the complexing agent can be released synchronously, and cycle through the complexing agent ⁇ metal ion complexing agent (metal ion complexation) ⁇ complexing agent (metal ion release, gelling material formation, complexing agent reuse) Repair the internal pore structure and flow channel of concrete, endow the multi-source waste slag-based concrete 3D printing material with continuous excellent late strength and weather resistance; introduce tough organic components such as polydopamine, polyurethane, and melamine-formaldehyde resin on the surface of fine aggregate , prepare functional fine aggregate, and introduce the functional fine aggregate and fiber into the concrete 3D printing material, and endow the multi-source waste slag-based concrete 3D printing material with excellent toughness and deformation ability through the synergistic effect of the two.
  • the multi-source waste slag-based concrete 3D printing material meets the high-performance concrete standard and can meet the requirements of 3D printing for rapid solidification; by introducing a surface film-forming agent with a specific hydrophilic-lipophilic ratio, the surface film-forming agent is an emulsion copolymer system.
  • the surface film-forming agent can be evenly dispersed in the concrete during the mixing process. After printing, it can migrate to the surface of the printed concrete component through the low surface energy of the lipophilic section to form a film on its own, thus endowing the multi-source waste residue-based concrete with 3D printing.
  • the smoothness of the material increases the toughness of the surface of the material and prevents the surface of the component from cracking and falling off; the preparation method of the multi-source waste slag-based concrete 3D printing material is simple and easy to operate and implement.
  • each raw material is composed of the following components in parts by weight:
  • the Portland cement is one or more of P.O32.5 cement and P.O42.5 cement mixed in any proportion.
  • the solid waste gel material is one or more of fly ash, steel slag and slag mixed in any proportion, the specific surface area is 400-1000m2/kg, and the sieve residue of 45 ⁇ m square holes is less than 1.5%.
  • the functionalized fine aggregate is polydopamine modified natural river sand, polyurethane modified natural river sand, melamine-formaldehyde resin modified natural river sand, polydopamine modified recycled machine-made sand, polyurethane modified recycled machine-made sand 1.
  • One or more of melamine-formaldehyde resin modified regenerated machine-made sand is mixed in any proportion;
  • the water reducer is one or more of naphthalene-based water reducers, sodium lignosulfonate water reducers, and polycarboxylate water reducers mixed in any proportion.
  • the interface stimulating agent is one or more of sodium silicate (Na 2 SiO 3 ), potassium silicate (K 2 SiO 3 ), sodium hydroxide (NaOH), and potassium hydroxide mixed in any proportion.
  • sodium silicate Na 2 SiO 3
  • potassium silicate K 2 SiO 3
  • sodium hydroxide NaOH
  • potassium hydroxide mixed in any proportion.
  • the complexing agent is one or more of sodium ethylenediaminetetraacetate, triethanolamine, sodium ethylenediaminetetramethylene phosphate, and polyhydroxyacrylic acid mixed in any proportion.
  • the water retaining agent is one or more of hydroxymethyl propyl cellulose ether, hydroxyethyl propyl cellulose ether, hydroxymethyl propyl starch ether, hydroxyethyl propyl starch ether Mix in any proportion.
  • the surface film-forming agent is an emulsion copolymer system with certain hydrophilic-lipophilic properties
  • the solid content of the emulsion copolymer system is 5-50%
  • the mass ratio of the hydrophilic segment in the emulsion copolymer is 0.5-13.5%
  • the mass ratio of the lipophilic segment is 86.5-99.5%
  • the hydrophilic segment is one or more combinations of acrylic acid, acrylamide, methacrylic acid, and methacrylamide
  • the lipophilic segment is methyl acrylate, acrylic acid Ethyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, trifluoroethyl acrylate, pentafluoropropyl acrylate, octafluoropentyl acrylate, heptadecafluorononyl acrylate, decafluoroacrylate
  • the fibers are one or more of polyethylene fibers, polyvinyl alcohol fibers, polypropylene fibers, carbon fibers, and Kevlar fibers mixed in any proportion.
  • the fiber length is 2-15mm.
  • the latex powder is one or more of styrene-butadiene copolymer, tertiary ethylene carbonate copolymer, and ethylene-vinyl acetate copolymer mixed in any proportion.
  • a method for preparing a multi-source waste slag-based concrete 3D printing material comprising the following steps:
  • step S1 the stirring speed is 200-300rpm/min, and the stirring time is 5-10 minutes;
  • step S2 the stirring speed is 100-300rpm/min, and the stirring time is 5-8 minutes;
  • step S3 the stirring speed is 300-500 rpm/min, and the stirring time is 5-15 minutes.
  • the metal ions precipitated in cement and waste slag cementitious materials are complexed and enriched by a complexing agent to form a metal ion complex, and the metal ion complex
  • the combination reaction between the compound and the hydration product calcium hydroxide and the interface stimulating agent forms a gelling component mainly composed of calcium silicate hydrate, calcium aluminate hydrate, and calcium aluminosilicate hydrate, thereby improving the microscopic pores of the prepared concrete and The pores formed by printing are repaired, which endows the multi-source waste slag-based concrete 3D printing material with excellent early strength and cohesion.
  • the metal ion complex can simultaneously release the complexing agent while reacting with the calcium hydroxide in the cement and the interface activator to form a gelling component, It can be used sustainably, and through the cycle of complexing agent ⁇ metal ion complexing agent (metal ion complexation) ⁇ complexing agent (metal ion release, cementitious material formation, complexing agent reuse) to continuously affect the internal pore structure and flow of concrete
  • the multi-source waste slag-based concrete 3D printing material is endowed with continuous excellent late strength and weather resistance.
  • a kind of multi-source waste slag-based concrete 3D printing material provided by the present invention by functionalizing the surface of rigid fine aggregate particles, introducing polydopamine, polyurethane, melamine-formaldehyde resin, preparing functional fine aggregate, and passing
  • the synergistic effect between functionalized fine aggregate and fiber can effectively improve the toughness and deformation ability of this multi-source waste slag-based concrete 3D printing material.
  • the surface film-forming agent is an emulsion copolymer system, and the surface film-forming agent can be uniformly dispersed in the concrete during the mixing process. After printing, It can migrate to the surface of the printed concrete component to form a film by itself through the low surface energy of the lipophilic section, thereby endowing the multi-source waste residue-based concrete 3D printing material with smooth characteristics, and increasing the toughness of the material surface to avoid cracking and falling off the surface of the component.
  • a multi-source waste slag-based concrete 3D printing material calculated in parts by weight Portland cement (P.O 42.5 cement) 50 parts, aluminate cement 50 parts, solid waste cementitious material 300 parts (steel slag 100 parts, fly ash 100 parts 100 parts of slag), 250 parts of functionalized fine aggregate (polydopamine modified natural river sand), 0.3 parts of water reducer (naphthalene-based water reducer), 0.3 parts of water retaining agent (hydroxyethyl propyl cellulose ether 0.3 parts), 0.3 parts of interface stimulating agent (0.2 parts of sodium silicate, 0.1 parts of sodium hydroxide), 0.5 parts of complexing agent (0.3 parts of triethanolamine, 0.2 parts of sodium edetate), 10 parts of surface film-forming agent (solid content 15%, acrylic acid-trifluoroethyl acrylate copolymer, acrylic acid content 8.5%, trifluoroethyl acrylate content 91.5%), fiber 0.5 part (polypropylene fiber 0.5
  • S1 50 parts of Portland cement (P.O 42.5 cement), 50 parts of aluminate cement, 300 parts of solid waste cementitious materials (100 parts of steel slag, 100 parts of fly ash, 100 parts of slag), 250 parts of fine aggregate (polydopamine modified natural river sand), 0.3 parts of water reducing agent (naphthalene-based water reducing agent), 0.3 parts of water retaining agent (hydroxyethyl propyl cellulose ether), 0.5 parts of complexing agent (0.3 parts of triethanolamine, ethyl 0.2 parts of sodium diamine tetraacetate), 4 parts of latex powder (2 parts of styrene-butadiene copolymer, 2 parts of tertiary carbonic acid ethylene copolymer), 10 parts of surface film-forming agent (solid content 15%, acrylic acid-acrylic acid three Fluoroethyl ester copolymer, acrylic acid content 8.5%, trifluoroethyl acrylate content 91.5%),
  • a multi-source waste slag-based concrete 3D printing material calculated in parts by weight, Portland cement 60 parts (30 parts of P.O32.5 cement, 30 parts of P.O 42.5 cement), 40 parts of aluminate cement, solid waste cementitious material 400 parts (150 parts of steel slag, 150 parts of fly ash, 100 parts of slag), 300 parts of functionalized fine aggregate (100 parts of polydopamine modified recycled machine-made sand, 200 parts of polyurethane modified natural river sand), 0.4 parts of water reducer Parts (0.2 parts of naphthalene-based superplasticizer, 0.2 parts of polycarboxylate superplasticizer), 0.4 parts of water-retaining agent (0.2 parts of hydroxymethyl propyl cellulose ether, 0.2 parts of hydroxymethyl propyl starch ether), interface stimulating agent 0.3 parts (0.15 parts of potassium silicate, 0.15 parts of sodium hydroxide), 0.6 parts of complexing agent (sodium edetate), 14 parts of surface film-forming agent (solid content 25%,
  • the interface trigger agent (0.15 parts of potassium silicate, 0.15 parts of sodium hydroxide) was dissolved in 480 parts of water, and stirred at 150 rpm/min for 7 minutes to obtain the interface trigger agent solution;
  • a multi-source waste slag-based concrete 3D printing material is 30 parts of Portland cement (P.O32.5 cement), 70 parts of aluminate cement, and 300 parts of solid waste cementitious material (150 parts of steel slag, powder 120 parts of coal ash, 30 parts of slag), 300 parts of functionalized fine aggregate (melamine-formaldehyde resin modified regeneration mechanism river sand), 0.4 parts of water reducing agent (0.2 parts of naphthalene-based water reducing agent, sodium lignosulfonate 0.2 parts of water reducing agent), 0.3 parts of water retaining agent (0.15 parts of hydroxyethyl propyl cellulose ether, 0.15 parts of hydroxymethyl propyl starch ether), 0.3 parts of interface stimulating agent (0.15 parts of potassium silicate, 0.15 parts of sodium hydroxide part), 0.5 part of complexing agent (sodium ethylenediamine tetramethylene phosphate), 25 parts of surface film-forming agent (solid content 20%,
  • S1 30 parts of Portland cement (P.O 32.5 cement), 70 parts of aluminate cement, 300 parts of solid waste cementitious materials (150 parts of steel slag, 120 parts of fly ash, 30 parts of slag), 300 parts of functional fine Aggregate (melamine-formaldehyde resin modified natural river sand), 0.4 parts of water reducer (0.2 parts of naphthalene-based water reducer, 0.2 parts of lignosulfonate sodium salt water reducer), 0.3 parts of water retaining 0.15 parts of base cellulose ether, 0.15 parts of hydroxymethyl propyl starch ether), 0.5 parts of complexing agent (sodium ethylenediamine tetramethylene phosphate), 6 parts of latex powder (3 parts of styrene-butadiene copolymer, 3 parts of ethylene-vinyl acetate copolymer), 25 parts of surface film-forming agent (solid content 20%, acrylamide-heptadecafluorodecyl acryl
  • the interface trigger agent (0.15 parts of potassium silicate, 0.15 parts of sodium hydroxide) was dissolved in 450 parts of water, and stirred at 100 rpm/min for 6 minutes to obtain the interface trigger agent solution;
  • a multi-source waste slag-based concrete 3D printing material calculated in parts by weight, Portland cement 35 parts (P.O42.5 cement), aluminate cement 65 parts, solid waste cementitious material 400 parts (steel slag 150 parts, powder 150 parts of coal ash, 100 parts of slag), 300 parts of functionalized fine aggregate (150 parts of polyurethane modified natural river sand, 150 parts of polydopamine modified recycled machine-made sand), 0.4 parts of water reducing agent (0.2 parts of naphthalene series water reducing agent 0.1 part, lignosulfonate sodium salt superplasticizer 0.1 part, polycarboxylate superplasticizer 0.1 part), water retaining agent 0.4 part (hydroxymethyl propyl cellulose ether 0.2 part, hydroxymethyl propyl starch ether 0.2 part) , 0.4 parts of interface stimulating agent (0.2 parts of sodium silicate, 0.2 parts of sodium hydroxide), 0.4 parts of complexing agent (triethanolamine), 15 parts of surface film-forming agent (solid content 30%
  • a multi-source waste slag-based concrete 3D printing material is 30 parts of Portland cement (P.O42.5 cement), 70 parts of aluminate cement, and 400 parts of solid waste cementitious material (250 parts of steel slag, powder 150 parts of coal ash), 300 parts of functionalized fine aggregate (polyurethane modified recycled machine-made sand), 0.4 parts of water reducer (0.2 part of naphthalene-based water reducer, 0.2 part of polycarboxylate water reducer), 0.4 part of water retaining agent (0.2 part of hydroxymethyl propyl cellulose ether, 0.1 part of hydroxymethyl propyl starch ether, 0.1 part of hydroxyethyl propyl starch ether), 0.4 part of interface stimulating agent (0.3 part of sodium silicate, 0.1 part of sodium hydroxide ), 0.7 parts of complexing agent (0.5 parts of sodium ethylenediamine tetramethylene phosphate, 0.2 parts of polyhydroxyacrylic acid), 28 parts of surface film-
  • test piece The size of the test piece is 40*40*160mm.
  • the test piece is at a temperature of 20 ⁇ 2°C and a relative humidity of 95%. Conditions to maintain to the test age.
  • Condensation test piece refer to the provisions in GB/T50080-2016 "Standards for Test Methods of Performance of Ordinary Concrete Mixtures”.
  • Fluidity refer to the provisions in GB/T50448-2015 "Technical Specifications for the Application of Cement-based Grouting Materials”.
  • Flexural strength and compressive strength refer to the provisions in GB/TGB/T17671-2000 "Cement Mortar Strength Test Method (ISO Method)”.
  • Test results The results of setting time, fluidity, flexural strength, compressive strength, toughness measurement, and interlayer bonding strength are shown in Table 1.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Initial setting/min 25 twenty two 18 29 15
  • Final setting/min 51 48
  • 42 61
  • Fluidity/mm 181 187
  • 166 193
  • 1 day compressive strength/MPa 52.35 49.45 55.76 58.72
  • 60.56 1 day flexural strength/MPa 12.34 13.65 13.74 14.66 15.62

Abstract

本发明公开一种多源废渣基混凝土3D打印材料及制备方法，属于混凝土建筑材料领域，各原料以重量份计：硅酸盐水泥10-80份，铝酸盐水泥20-70份、固废胶凝材料300-500份、功能化细骨料200-500份、减水剂0.2-0.5份、保水剂0.1-0.5份，界面激发剂0.1-0.4份、络合剂0.4-0.8份、表面成膜剂0.2-3.0份、纤维0.2-0.6份，乳胶粉2-8份，水200份-880份。采用金属离子络合物在与水泥中氢氧化钙以及界面激发剂反应形成胶凝成分同时，同步释放出络合剂，可持续使用，并通过络合剂→金属离子络合剂(金属离子络合)→络合剂(金属离子释放胶凝材料形成，络合剂重复使用)循环持续对混凝土内部孔隙结构及流道进行修复，赋予该打印材料持续优异的晚期强度和耐候性，其制备方法过程简单，易于操作实施。

Description

一种多源废渣基混凝土3D打印材料及制备方法 技术领域
本发明属于混凝土建筑材料技术领域，具体涉及一种多源废渣基混凝土3D打印材料及制备方法。
背景技术
随着计算机技术的兴起，3D打印技术在医疗、航空航天、建筑、电子、服装、智能制造等领域蓬勃发展。在建筑行业，3D打印技术具有无模、精细化、可编辑等优点，具有广阔的应用前景，推动建筑业向更高的维度发展。与此同时，建筑行业施工需要大量的水泥等胶凝材料，而水泥生产属于高耗能行业，严重背离我国的“双碳”战略。冶金、煤电行业在生产过程中产生大量的钢渣、矿渣、粉煤灰等大宗固体废渣。上述固体废渣目前处置相对困难，主要通过露天堆放的方式进行处理。该处置方式一方面消耗大量的耕地资源，另一方面废渣堆积也极易造成空气、水体以及土壤污染，对环境造成负面影响。钢渣、矿渣、粉煤灰中富含氧化钙、氧化硅、氧化铝等潜在胶凝成分，具有成为建筑材料的潜质。
通常情况下，3D打印混凝土材料通常需要引入大量的细骨料成分，但是刚性细骨料颗粒粒径较大，与混凝土材料中其他组分相容性不足。与此同时，细骨料刚性较强，细骨料颗粒之间缺乏有效的缓冲连接，使得制备的3D打印混凝土材料韧性不足，上述不足使得制备的3D打印混凝土材料经常发生脆性断裂。
为了满足3D打印要求，混凝土材料应均有较高的早期强度，较短的凝结时间，合适的骨料粒径。同时，3D打印混凝土通常不允许添加钢筋，故需要混凝土材料具有较强的韧性与变形能力。此外，在打印过程中，常规3D打印混凝土粘聚性较差，使得制品的力学性能和耐候性受到影响。
发明内容
1.本发明要解决的技术问题：
针对现有混凝土3D打印材料存在的水泥使用量大、强度低、韧性差、粘聚性不足的问题，本发明的目的在于提供一种多源废渣基混凝土3D打印材料及制备方法。将多种冶金、煤电废渣引入该多源废渣基混凝土3D打印材料有效降低水泥使用量，契合国家“双碳”战略，通过对刚性细骨料进行功能化，通过废渣胶凝材料、表面激发剂、络合剂的协效反应有效提高该多源废渣基混凝土3D打印材料优异的早期强度和粘聚性；形成的金属离子络合物在与水泥中氢氧化钙以及界面激发剂形成胶凝成分的同时，可以同步释放出络合剂，并通过络合剂→金属离子络合剂(金属离子络合)→络合剂(金属离子释放，胶凝材料形成，络合剂重复使用)循环对混凝土内部孔隙结构以及流道进行修复，赋予该多源废渣基混凝土3D打印材料持续优异的晚期强度和耐候性；通过在细骨料表面引入聚多巴胺、聚氨酯、三聚氰胺-甲醛树脂等韧性有机成分，制备功能化细骨料，并将该功能性细骨料与纤维引入该混凝土3D打印材料，通过两者的协效作用赋予该多源废渣基混凝土3D打印材料优异的韧性和变形能力，该多源废渣基混凝土3D打印材料符合高性能混凝土标准，能够满足3D打印对于快速凝固的要求；通过引入特定亲水-亲油比例的表面成膜剂，该表面成膜剂为乳液共聚体系，该表面成膜剂在拌和过程中可均匀分散在混凝土中，其在完成打印之后，可以通过亲油段低表面能作用迁移到打印混凝土构件表面自行成膜，从而赋予该多源废渣基混凝土3D打印材料光滑的特性，并增加材料表面的韧性，避免构件表面开裂脱落；该多源废渣基混凝土3D打印材料制备方法简单，易于操作实施。
2.技术方案
为了实现上述目的，本发明采用的技术方案是：
本发明所述的一种多源废渣基混凝土3D打印材料及制备方法，各原料以重量份计，由以下组分组成：
Figure PCTCN2022127571-appb-000001
优选地，所述硅酸盐水泥为P.O32.5水泥和P.O42.5水泥中的一种或多种按任意比例混合。
优选地，所述固废凝胶材料为粉煤灰、钢渣和矿渣中的一种或多种按任意比例混合，比表面积400-1000m2/kg,45μm方孔孔筛余1.5％以下，
优选地，所述功能化细骨料为聚多巴胺改性天然河砂、聚氨酯改性天然河砂、三聚氰胺-甲醛树脂改性天然河砂、聚多巴胺改性再生机制砂、聚氨酯改性再生机制砂、三聚氰胺-甲醛树脂改性再生机制砂中的一种或多种按任意比例混合；
聚多巴胺改性天然河砂或聚多巴胺改性再生机制砂的制备方法：
天然河砂或再生机制砂烘干，配置0.01-10g/L多巴胺溶液，调节pH值至7-11，将天然河砂或再生机制砂粉末分散于多巴胺溶液中搅拌0.2-20h,将样品过滤干燥，即可得到聚多巴胺改性天然河砂或聚多巴胺改性再生机制砂；
聚氨酯改性天然河砂或聚氨酯改性再生机制砂的制备方法：
2-10份季戊四醇溶于3--150份二甲亚砜，再加入5-25份2,4-甲苯-二异 氰酸酯和75-375份1,4二氧六环，搅拌均匀后加入60-300份天然河砂或再生机制砂的细骨料，150-7501,4二氧六环，0.6-3份司盘-80和0.25-1.25份三乙烯二胺，加热反应一定时间后(80℃2-15小时)后过滤，得到聚氨酯改性天然河砂或聚氨酯改性再生机制砂；
三聚氰胺-甲醛树脂改性天然河砂或三聚氰胺-甲醛树脂改性再生机制砂的制备方法：
10-50份三聚氰胺，3-50份甲醛和50-250份水，调节pH至碱性，35-90℃搅拌3-250min后即可得到三聚氰胺-甲醛树脂预聚体；
将30-300份天然河砂或再生机制砂分散在75-750份醇溶液中，加入三聚氰胺-甲醛预聚体，条件pH至酸性(1-6.9)，35-95℃下加热搅拌15-300min，降低至室温，烘干即可获得三聚氰胺-甲醛树脂改性天然河砂或三聚氰胺-甲醛树脂改性再生机制砂。
优选地，所述减水剂为萘系减水剂、木质素磺酸钠盐减水剂、聚羧酸减水剂中的一种或多种按任意比例混合。
优选地，所述界面激发剂为硅酸钠(Na 2SiO 3)、硅酸钾(K 2SiO 3)、氢氧化钠(NaOH)、氢氧化钾的一种或多种按任意比例混合。
优选地，所述络合剂为乙二胺四乙酸钠、三乙醇胺、乙二胺四甲叉磷酸钠、聚羟基丙烯酸中的一种或多种按任意比例混合。
优选地，所述保水剂为为羟甲基丙基纤维素醚、羟乙基丙基纤维素醚、羟甲基丙基淀粉醚、羟乙基丙基淀粉醚中的一种或多种按任意比例混合。
优选地，所述表面成膜剂为具有一定亲水-亲油特性的乳液共聚体系，该乳液共聚体系固含量为5-50％，乳液共聚物中亲水链段质量比为0.5-13.5％，亲油链段质量比为86.5-99.5％，亲水链段为丙烯酸、丙烯酰胺、甲基丙烯酸、甲基丙烯酰胺中的一种或多种组合；亲油链段为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸辛酯、丙烯酸三氟乙酯、丙烯酸五氟丙酯、丙烯酸八氟戊酯、丙烯酸十七氟壬酯、丙烯酸十七氟癸酯、 甲基丙烯酸三氟乙酯、甲基丙烯酸五氟丙酯、甲基丙烯酸八氟戊酯、甲基丙烯酸十七氟壬酯、甲基丙烯酸十七氟癸酯中的一种或多种组合。
优选地，所述纤维为聚乙烯纤维、聚乙烯醇纤维、聚丙烯纤维、碳纤维、凯夫拉纤维中的一种或多种按任意比例混合。
优选地，所述纤维长度2-15mm。
优选地，所述乳胶粉为苯乙烯-丁二烯共聚物、叔碳酸乙烯共聚物、乙烯-醋酸乙烯共聚物中的一种或多种按任意比例混合。
一种多源废渣基混凝土3D打印材料的制备方法，其包括以下步骤：
S1：将硅酸盐水泥、铝酸盐水泥、固废胶凝材料、功能化细骨料、减水剂、保水剂、乳胶粉、纤维在搅拌机中搅拌获得固体粉状混合物；
S2:将界面激发剂溶于水中，搅拌得到界面激发剂溶液；
S3：将界面激发剂溶液加入固体粉状混合物中，搅拌得到多源废渣基混凝土3D打印材料。
优选地：步骤S1中，搅拌速度为200-300rpm/分钟，搅拌时间为5-10分钟；
优选地：步骤S2中，搅拌速度为100-300rpm/分钟，搅拌时间为5-8分钟；
优选地：步骤S3中，搅拌速度为300-500rpm/分钟，搅拌时间为5-15分钟。
3.有益效果
与现有技术相比，本发明的有益效果为：
(1)将冶金、煤电等行业大宗固体废渣(钢渣、粉煤灰、矿渣)作为胶凝材料替代水泥，用于制备一种多源废渣基混凝土3D打印材料，实现上述废渣的高价值化利用。
(2)本发明提供的一种多源废渣基混凝土3D打印材料，通过络合剂将水泥、废渣胶凝材料中析出的金属离子进行络合富集形成金属离子络合物，金属离子络合物与水化产物氢氧化钙、界面激发剂进行结合反应形成以水化硅酸钙、水化铝酸钙、水化硅铝酸钙为主体的胶凝成分，从而对制备的混凝土微观孔隙以 及打印形成的孔道进行修复，赋予该多源废渣基混凝土3D打印材料优异的早期强度和粘聚性。
(3)本发明提供的一种多源废渣基混凝土3D打印材料，金属离子络合物在与水泥中氢氧化钙以及界面激发剂反应形成胶凝成分的同时，可以同步释放出络合剂，可持续使用，并通过络合剂→金属离子络合剂(金属离子络合)→络合剂(金属离子释放，胶凝材料形成，络合剂重复使用)循环持续对混凝土内部孔隙结构以及流道进行修复，赋予该多源废渣基混凝土3D打印材料持续优异的晚期强度和耐候性。
(4)本发明提供的一种多源废渣基混凝土3D打印材料，通过对刚性细骨料颗粒表面进行功能化，引入聚多巴胺、聚氨酯、三聚氰胺-甲醛树脂，制备功能化细骨料，并通过功能化细骨料与纤维之间的协效作用，有效提高该多源废渣基混凝土3D打印材料的韧性和变形能力。
(5)通过引入特定亲水-亲油比例的表面成膜剂，该表面成膜剂为乳液共聚体系，该表面成膜剂在拌和过程中可均匀分散在混凝土中，其在完成打印之后，可以通过亲油段低表面能作用迁移到打印混凝土构件表面自行成膜，从而赋予该多源废渣基混凝土3D打印材料光滑的特性，并增加材料表面的韧性，避免构件表面开裂脱落。
(6)该多源废渣基混凝土3D打印材料制备方法简单，易于操作实施。
具体实施方式
下面结合实施例对本发明做进一步详细的描述，但本发明的实施方式不限于此。
实施例1
一种多源废渣基混凝土3D打印材料，以重量份计算硅酸盐水泥(P.O 42.5水泥)50份，铝酸盐水泥50份、固废胶凝材料300份(钢渣100份、粉煤灰100份、矿渣100份)、功能化细骨料250份(聚多巴胺改性天然河砂)、减水剂0.3份(萘系减水剂)、保水剂0.3份(羟乙基丙基纤维素醚0.3份)，界面激发剂 0.3份(硅酸钠0.2份，氢氧化钠0.1份)、络合剂0.5份(三乙醇胺0.3份、乙二胺四乙酸钠0.2份)、表面成膜剂10份(固含量15％，丙烯酸-丙烯酸三氟乙酯共聚物，丙烯酸含量8.5％，丙烯酸三氟乙酯含量91.5％)、纤维0.5份(聚丙烯纤维0.5份，纤维长度6mm)，乳胶粉4份(苯乙烯-丁二烯共聚物2份、叔碳酸乙烯共聚物2份)，水390份。
聚多巴胺改性天然河砂的制备方法：
天然河砂烘干，配置0.01-10g/L多巴胺溶液，调节pH值至7-11，将天然河砂或再生机制砂粉末分散于多巴胺溶液中搅拌5h,将样品过滤干燥，即可得到聚多巴胺改性天然河砂。
上述多源废渣基混凝土3D打印材料，其制备步骤如下：
S1：将50份硅酸盐水泥(P.O 42.5水泥)、50份铝酸盐水泥、300份固废胶凝材料(钢渣100份、粉煤灰100份、矿渣100份)、250份细骨料(聚多巴胺改性天然河砂)、0.3份减水剂(萘系减水剂)、0.3份保水剂(羟乙基丙基纤维素醚)、络合剂0.5份(三乙醇胺0.3份、乙二胺四乙酸钠0.2份)、乳胶粉4份(苯乙烯-丁二烯共聚物2份、叔碳酸乙烯共聚物2份)、表面成膜剂10份(固含量15％，丙烯酸-丙烯酸三氟乙酯共聚物，丙烯酸含量8.5％，丙烯酸三氟乙酯含量91.5％)、纤维0.5份(聚丙烯纤维，纤维长度6mm)在搅拌机中以250rpm/分钟搅拌8分钟获得固体粉状混合物；
S2:将界面激发剂(硅酸钠0.2份，氢氧化钠0.1份)溶于390份水中，以100rpm/分钟搅拌5分钟得到界面激发剂溶液；
S3：将界面激发剂溶液加入固体粉状混合物中，以400rpm/分钟搅拌10分钟得到多源废渣基混凝土3D打印材料。
实施例2
一种多源废渣基混凝土3D打印材料，以重量份计算硅酸盐水泥60份(P.O32.5水泥30份、P.O 42.5水泥30份)，铝酸盐水泥40份、固废胶凝材料400份(钢渣150份、粉煤灰150份、矿渣100份)、功能化细骨料300份(聚多巴 胺改性再生机制砂100份、聚氨酯改性天然河砂200份)、减水剂0.4份(萘系减水剂0.2份、聚羧酸减水剂0.2份)、保水剂0.4份(羟甲基丙基纤维素醚0.2份、羟甲基丙基淀粉醚0.2份)、界面激发剂0.3份(硅酸钾0.15份，氢氧化钠0.15份)、络合剂0.6份(乙二胺四乙酸钠)、表面成膜剂14份(固含量25％，甲基丙烯酸-丙烯酸辛酯共聚物，甲基丙烯酸含量5.0％，丙烯酸辛酯含量95.0％)、纤维0.4份(聚乙烯醇纤维0.2份，纤维长度10mm；聚丙烯纤维0.2份，纤维长度6mm)，乳胶粉5份(苯乙烯-丁二烯共聚物3份、乙烯-醋酸乙烯共聚物2份)，水480份。
聚多巴胺改性再生机制砂的制备方法：
再生机制砂烘干，配置0.01-10g/L多巴胺溶液，调节pH值至7-11，将天然河砂或再生机制砂粉末分散于多巴胺溶液中搅拌4h,将样品过滤干燥，即可得到聚多巴胺改性再生机制砂；
聚氨酯改性天然河砂的制备方法：
2-10份季戊四醇溶于3--150份二甲亚砜，再加入5-25份2,4-甲苯-二异氰酸酯和75-375份1,4二氧六环，搅拌均匀后加入60-300份天然河砂的细骨料，150-7501,4二氧六环，0.6-3份司盘-80和0.25-1.25份三乙烯二胺，加热反应一定时间后(80℃2-15小时)后过滤，得到聚氨酯改性天然河砂。
上述多源废渣基混凝土3D打印材料，其制备步骤如下：
S1：将60份硅酸盐水泥(P.O 32.5水泥30份、P.O 42.5水泥30份)、40份铝酸盐水泥、400份固废胶凝材料(钢渣150份、粉煤灰150份、矿渣100份)、300份功能化细骨料(聚多巴胺改性再生机制砂100份、聚氨酯改性天然河砂200份)、0.4份减水剂(萘系减水剂0.2份、聚羧酸减水剂0.2份)、0.4份保水剂(羟甲基丙基纤维素醚0.2份、羟甲基丙基淀粉醚0.2份)、络合剂0.6份(乙二胺四乙酸钠)、乳胶粉5份(苯乙烯-丁二烯共聚物3份、乙烯-醋酸乙烯共聚物2份)、表面成膜剂14份(固含量25％，甲基丙烯酸-丙烯酸辛酯共聚物，甲基丙烯酸含量5.0％，丙烯酸辛酯含量95.0％)、纤维0.4份(聚乙烯醇纤维0.2 份，纤维长度10mm；聚丙烯纤维0.2份，纤维长度6mm)在搅拌机中以200rpm/分钟搅拌6分钟获得固体粉状混合物；
S2:将界面激发剂(硅酸钾0.15份，氢氧化钠0.15份)溶于480份水中，以150rpm/分钟搅拌7分钟得到界面激发剂溶液；
S3：将界面激发剂溶液加入固体粉状混合物中，以400rpm/分钟搅拌10分钟得到多源废渣基混凝土3D打印材料。
实施例3
一种多源废渣基混凝土3D打印材料，以重量份计算硅酸盐水泥30份(P.O32.5水泥)，铝酸盐水泥70份、固废胶凝材料300份(钢渣150份、粉煤灰120份、矿渣30份)、功能化细骨料300份(三聚氰胺-甲醛树脂改性再生机制河砂)、减水剂0.4份(萘系减水剂0.2份、木质素磺酸钠盐减水剂0.2份)、保水剂0.3份(羟乙基丙基纤维素醚0.15份、羟甲基丙基淀粉醚0.15份)、界面激发剂0.3份(硅酸钾0.15份，氢氧化钠0.15份)、络合剂0.5份(乙二胺四甲叉磷酸钠)、表面成膜剂25份(固含量20％，丙烯酰胺-丙烯酸十七氟癸酯共聚物，丙烯酰胺含量13.5％，丙烯酸十七氟癸酯含量86.5％)、纤维0.4份(聚乙烯醇纤维0.4份，纤维长度10mm)，乳胶粉6份(苯乙烯-丁二烯共聚物3份、乙烯-醋酸乙烯共聚物3份)，水450份。
三聚氰胺-甲醛树脂改性再生机制砂的制备方法：
10-50份三聚氰胺，3-50份甲醛和50-250份水，调节pH至碱性，35-90℃搅拌3-250min后即可得到三聚氰胺-甲醛树脂预聚体；
将30-300份再生机制砂分散在75-750份醇溶液中，加入三聚氰胺-甲醛预聚体，条件pH至酸性(1-6.9)，35-95℃下加热搅拌15-300min，降低至室温，烘干即可获得三聚氰胺-甲醛树脂改性天然河砂或三聚氰胺-甲醛树脂改性再生机制砂。
上述多源废渣基混凝土3D打印材料，其制备步骤如下：
S1：将30份硅酸盐水泥(P.O 32.5水泥)、70份铝酸盐水泥、300份固废 胶凝材料(钢渣150份、粉煤灰120份、矿渣30份)、300份功能化细骨料(三聚氰胺-甲醛树脂改性天然河砂)、0.4份减水剂(萘系减水剂0.2份、木质素磺酸钠盐减水剂0.2份)、0.3份保水剂(羟乙基丙基纤维素醚0.15份、羟甲基丙基淀粉醚0.15份)、络合剂0.5份(乙二胺四甲叉磷酸钠)、乳胶粉6份(苯乙烯-丁二烯共聚物3份、乙烯-醋酸乙烯共聚物3份)、表面成膜剂25份(固含量20％，丙烯酰胺-丙烯酸十七氟癸酯共聚物，丙烯酰胺含量13.5％，丙烯酸十七氟癸酯含量86.5％)、纤维0.4份(聚乙烯醇纤维0.4份，纤维长度10mm)在搅拌机中以200rpm/分钟搅拌5分钟获得固体粉状混合物；
S2:将界面激发剂(硅酸钾0.15份，氢氧化钠0.15份)溶于450份水中，以100rpm/分钟搅拌6分钟得到界面激发剂溶液；
S3：将界面激发剂溶液加入固体粉状混合物中，以350rpm/分钟搅拌8分钟得到多源废渣基混凝土3D打印材料。
实施例4
一种多源废渣基混凝土3D打印材料，以重量份计算硅酸盐水泥35份(P.O42.5水泥)，铝酸盐水泥65份、固废胶凝材料400份(钢渣150份、粉煤灰150份、矿渣100份)、功能化细骨料300份(聚氨酯改性天然河砂150份、聚多巴胺改性再生机制砂150份)、减水剂0.4份(萘系减水剂0.2份、木质素磺酸钠盐减水剂0.1份、聚羧酸减水剂0.1份)、保水剂0.4份(羟甲基丙基纤维素醚0.2份、羟甲基丙基淀粉醚0.2份)，界面激发剂0.4份(硅酸钠0.2份，氢氧化钠0.2份)、络合剂0.4份(三乙醇胺)、表面成膜剂15份(固含量30％，甲基丙烯酰胺-甲基丙烯酸五氟丙酯共聚物，甲基丙烯酰胺含量10.0％，甲基丙烯酸五氟丙酯含量90.0％)、纤维0.4份(聚乙烯醇纤维0.2份，纤维长度10mm；凯夫拉纤维0.2份，6mm)，乳胶粉4份(苯乙烯-丁二烯共聚物2份、叔碳酸乙烯共聚物2份)，水540份。
聚多巴胺改性再生机制砂的制备方法：
再生机制砂烘干，配置0.01-10g/L多巴胺溶液，调节pH值至7-11，将再 生机制砂粉末分散于多巴胺溶液中搅拌0.2-20h,将样品过滤干燥，即可得到聚多巴胺改性天然河砂或聚多巴胺改性再生机制砂；
聚氨酯改性天然河砂的制备方法：
2-10份季戊四醇溶于3--150份二甲亚砜，再加入5-25份2,4-甲苯-二异氰酸酯和75-375份1,4二氧六环，搅拌均匀后加入60-300份天然河砂的细骨料，150-7501,4二氧六环，0.6-3份司盘-80和0.25-1.25份三乙烯二胺，加热反应一定时间后(80℃2-15小时)后过滤，得到聚氨酯改性天然河砂。
上述多源废渣基混凝土3D打印材料，其制备步骤如下：
S1：将35份硅酸盐水泥(P.O 42.5水泥)、65份铝酸盐水泥、400份固废胶凝材料(钢渣150份、粉煤灰150份、矿渣100份)、300份功能化细骨料(聚氨酯改性天然河砂150份、聚多巴胺改性再生机制砂150份)、0.4份减水剂(萘系减水剂0.2份、木质素磺酸钠盐减水剂0.1份、聚羧酸减水剂0.1份)、0.4份保水剂(羟甲基丙基纤维素醚0.2份、羟甲基丙基淀粉醚0.2份)、络合剂0.4份(三乙醇胺)、乳胶粉4份(苯乙烯-丁二烯共聚物2份、叔碳酸乙烯共聚物2份)、表面成膜剂15份(固含量30％，甲基丙烯酰胺-甲基丙烯酸五氟丙酯共聚物，甲基丙烯酰胺含量10.0％，甲基丙烯酸五氟丙酯含量90.0％)、纤维0.4份(聚乙烯醇纤维0.2份，纤维长度10mm；凯夫拉纤维0.2份，6mm)在搅拌机中以150rpm/分钟搅拌6分钟获得固体粉状混合物；
S2:将界面激发剂(硅酸钠0.2份，氢氧化钠0.2份)溶于540份水中，以150rpm/分钟搅拌6分钟得到界面激发剂溶液；
S3：将界面激发剂溶液加入固体粉状混合物中，以450rpm/分钟搅拌9分钟得到多源废渣基混凝土3D打印材料。
实施例5
一种多源废渣基混凝土3D打印材料，以重量份计算硅酸盐水泥30份(P.O42.5水泥)，铝酸盐水泥70份、固废胶凝材料400份(钢渣250份、粉煤灰150份)、功能化细骨料300份(聚氨酯改性再生机制砂)、减水剂0.4份(萘系减 水剂0.2份、聚羧酸减水剂0.2份)、保水剂0.4份(羟甲基丙基纤维素醚0.2份、羟甲基丙基淀粉醚0.1份、羟乙基丙基淀粉醚0.1份)，界面激发剂0.4份(硅酸钠0.3份，氢氧化钠0.1份)、络合剂0.7份(乙二胺四甲叉磷酸钠0.5份、聚羟基丙烯酸0.2份)、表面成膜剂28份(固含量40％，甲基丙烯酸-甲基甲基丙烯酸八氟戊酯共聚物，甲基丙烯酸含量8.0％，甲基丙烯酸八氟戊酯含量92.0％)、纤维0.4份(聚乙烯纤维0.2份，纤维长度6mm；碳纤维0.2份，6mm)，乳胶粉5份(苯乙烯-丁二烯共聚物2份、叔碳酸乙烯共聚物2份、乙烯-醋酸乙烯共聚物1份)，水580份。
聚多巴胺改性天然河砂或聚多巴胺改性再生机制砂的制备方法：
天然河砂或再生机制砂烘干，配置0.01-10g/L多巴胺溶液，调节pH值至7-11，将天然河砂或再生机制砂粉末分散于多巴胺溶液中搅拌0.2-20h,将样品过滤干燥，即可得到聚多巴胺改性天然河砂或聚多巴胺改性再生机制砂；
聚氨酯改性再生机制砂的制备方法：
2-10份季戊四醇溶于3--150份二甲亚砜，再加入5-25份2,4-甲苯-二异氰酸酯和75-375份1,4二氧六环，搅拌均匀后加入60-300份再生机制河砂的细骨料，150-7501,4二氧六环，0.6-3份司盘-80和0.25-1.25份三乙烯二胺，加热反应一定时间后(80℃2-15小时)后过滤，得到聚氨酯改性再生机制砂。
上述多源废渣基混凝土3D打印材料，其制备步骤如下：
S1：将30份硅酸盐水泥(P.O 42.5水泥)、75份铝酸盐水泥、400份固废胶凝材料(钢渣250份、粉煤灰150份)、300份功能化细骨料(聚氨酯改性再生机制砂)、0.4份减水剂(萘系减水剂0.2份、聚羧酸减水剂0.2份)、0.4份保水剂(羟甲基丙基纤维素醚0.2份、羟甲基丙基淀粉醚0.1份、羟乙基丙基淀粉醚0.1份)、络合剂0.7份(乙二胺四甲叉磷酸钠0.5份、聚羟基丙烯酸0.2份)、乳胶粉5份(苯乙烯-丁二烯共聚物2份、叔碳酸乙烯共聚物2份、乙烯-醋酸乙烯共聚物1份)、表面成膜剂28份(固含量40％，甲基丙烯酸-甲基甲基丙烯酸八氟戊酯共聚物，甲基丙烯酸含量8.0％，甲基丙烯酸八氟戊酯含量 92.0％)、纤维0.4份(聚乙烯纤维0.2份，纤维长度6mm；碳纤维0.2份，6mm)在搅拌机中以160rpm/分钟搅拌7分钟获得固体粉状混合物；
S2:将界面激发剂(硅酸钠0.3份，氢氧化钠0.1份)溶于580份水中，以180rpm/分钟搅拌7分钟得到界面激发剂溶液；
S3：将界面激发剂溶液加入固体粉状混合物中，以400rpm/分钟搅拌12分钟得到多源废渣基混凝土3D打印材料。
试验
对实施例1-5所得的3D打印用多源废渣基混凝土的凝结时间、流动度、抗折强度、抗压强度等参数分别进行测试，具体如下：
试件制备：试件尺寸为40*40*160mm,具体制作方法参考GB/T17671-2020《水泥胶砂强度检验方法(ISO法)》，试件在温度为20±2℃，相对湿度95％条件下养护到试验龄期。
凝结试件：参照GB/T50080-2016《普通混凝土拌合物性能试验方法标准》中的规定。
流动度：参照GB/T50448-2015《水泥基灌浆材料应用技术规范》中的规定。
抗折强度和抗压强度：参照GB/TGB/T17671-2000《水泥胶砂强度检验方法(ISO法)》中的规定。
试验结果：凝结时间、流动度、抗折强度、抗压强度、韧性测量、层间黏结强度的结果，如表1所示。
表1：性能测试结果
试验 实施例1 实施例2 实施例3 实施例4 实施例5
初凝/min 25 22 18 29 15
终凝/min 51 48 42 61 34
流动度/mm 181 187 166 193 153
1天抗压强度/MPa 52.35 49.45 55.76 58.72 60.56
1天抗折强度/MPa 12.34 13.65 13.74 14.66 15.62
3天抗压强度/MPa 68.87 70.45 59.25 65.74 70.63
3天抗折强度/MPa 16.98 17.77 15.35 16.54 18.51
28天抗压强度/MPa 148.67 142.84 130.65 150.63 149.96
28天抗折强度/MPa 30.65 31.59 27.85 32.66 30.50
层间黏结强度/MPa 5.16 5.74 5.85 6.13 6.62
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明精神实质与原理下所做的改变、修饰、替代、组合、简化均应为等效的置换方式，都包含在本发明的保护范围内。

Claims (10)

  1. 一种多源废渣基混凝土3D打印材料，其特征在于，所述多源废渣基混凝土3D打印材料中各原料以重量份计：硅酸盐水泥10-80份，铝酸盐水泥20-70份、固废胶凝材料300-500份、功能化细骨料200-500份、减水剂0.2-0.5份、保水剂0.1-0.5份，界面激发剂0.1-0.4份、络合剂0.4-0.8份、表面成膜剂0.2-3.0份、纤维0.2-0.6份，乳胶粉2-8份，水200份-880份。
  2. 如权利要求1所述的多源废渣基混凝土3D打印材料，其特征在于，所述硅酸盐水泥为P.O32.5水泥和P.O42.5水泥中的一种或多种按任意比例混合。
  3. 如权利要求1所述的多源废渣基混凝土3D打印材料，其特征在于，所述固废凝胶材料为粉煤灰、钢渣和矿渣中的一种或多种按任意比例混合，比表面积400-1000 m2/kg,45μm方孔孔筛余1.5％以下。
  4. 如权利要求1所述的多源废渣基混凝土3D打印材料，其特征在于，所述功能化细骨料为聚多巴胺改性天然河砂、聚氨酯改性天然河砂、三聚氰胺-甲醛树脂改性天然河砂、聚多巴胺改性再生机制砂、聚氨酯改性再生机制砂、三聚氰胺-甲醛树脂改性再生机制砂中的一种或多种按任意比例混合；
    聚多巴胺改性天然河砂或聚多巴胺改性再生机制砂的制备方法：
    天然河砂或再生机制砂烘干，配置0.01-10g/L多巴胺溶液，调节pH值至7-11，将天然河砂或再生机制砂粉末分散于多巴胺溶液中搅拌0.2-20h,将样品过滤干燥，即可得到聚多巴胺改性天然河砂或聚多巴胺改性再生机制砂；
    聚氨酯改性天然河砂或聚氨酯改性再生机制砂的制备方法：
    2-10份季戊四醇溶于3--150份二甲亚砜，再加入5-25份2,4-甲苯-二异氰酸酯和75-375份1,4二氧六环，搅拌均匀后加入60-300份天然河砂或再生机制砂的细骨料，150-7501,4二氧六环，0.6-3份司盘-80和0.25-1.25份三乙烯二胺，加热反应一定时间后(80℃2-15小时)后过滤，得到聚氨酯改性天然河砂或聚氨酯改性再生机制砂；
    三聚氰胺-甲醛树脂改性天然河砂或三聚氰胺-甲醛树脂改性再生机制砂的制备方法：
    10-50份三聚氰胺，3-50份甲醛和50-250份水，调节pH至碱性，35-90℃搅拌3-250min后即可得到三聚氰胺-甲醛树脂预聚体；
    将30-300份天然河砂或再生机制砂分散在75-750份醇溶液中，加入三聚氰胺-甲醛预聚体，条件pH至酸性(1-6.9)，35-95℃下加热搅拌15-300min，降低至室温，烘干即可获得三聚氰胺-甲醛树脂改性天然河砂或三聚氰胺-甲醛树脂改性再生机制砂。
  5. 如权利要求1所述的多源废渣基混凝土3D打印材料，其特征在于，所述减水剂为萘系减水剂、木质素磺酸钠盐减水剂、聚羧酸减水剂中的一种或多种按任意比例混合，所述络合剂为乙二胺四乙酸钠、三乙醇胺、乙二胺四甲叉磷酸钠、聚羟基丙烯酸中的一种或多种按任意比例混合。
  6. 如权利要求1所述的多源废渣基混凝土3D打印材料，其特征在于，所述界面激发剂为硅酸钠、硅酸钾、氢氧化钠、氢氧化钾中的一种或多种按任意比例混合，所述保水剂为为羟甲基丙基纤维素醚、羟乙基丙基纤维素醚、羟甲基丙基淀粉醚、羟乙基丙基淀粉醚中的一种或多种按任意比例混合。
  7. 如权利要求1所述的多源废渣基混凝土3D打印材料，其特征在于，所述表面成膜剂为具有一定亲水-亲油特性的乳液共聚体系，该乳液共聚体系固含量为5-50％，乳液共聚物中亲水链段质量比为0.5-13.5％，亲油链段质量比为86.5-99.5％，其亲水链段为丙烯酸、丙烯酰胺、甲基丙烯酸、甲基丙烯酰胺中的一种或多种组合；亲油链段为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸辛酯、丙烯酸三氟乙酯、丙烯酸五氟丙酯、丙烯酸八氟戊酯、丙烯酸十七氟壬酯、丙烯酸十七氟癸酯、甲基丙烯酸三氟乙酯、甲基丙烯酸五氟丙酯、甲基丙烯酸八氟戊酯、甲基丙烯酸十七氟壬酯、甲基丙烯酸十七氟癸酯中的一种或多种组合。
  8. 如权利要求1所述的多源废渣基混凝土3D打印材料，其特征在于，所述纤维为聚乙烯纤维、聚乙烯醇纤维、聚丙烯纤维、碳纤维、凯夫拉纤维中的一种或多种按任意比例混合，所述纤维长度2-15mm。
  9. 如权利要求1所述的多源废渣基混凝土3D打印材料，其特征在于，所述乳胶粉为苯乙烯-丁二烯共聚物、叔碳酸乙烯共聚物、乙烯-醋酸乙烯共聚物中的一种或多种按任意比例混合。
  10. 一种如权利要求1-9所述的多源废渣基混凝土3D打印材料的制备方法，其特征在于，包括以下步骤：
    S1：将硅酸盐水泥、铝酸盐水泥、固废胶凝材料、功能化细骨料、减水剂、保水剂、乳胶粉、络合剂、纤维在搅拌机中以200-300rpm/分钟搅拌5-10分钟获得固体粉状混合物；
    S2:将界面激发剂溶于水中，以100-300rpm/分钟搅拌5-8分钟得到界面激发剂溶液；
    S3：将界面激发剂溶液加入固体粉状混合物中，以300-500rpm/分钟搅拌5-15分钟得到多源废渣基混凝土3D打印材料。
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