WO2022007063A1 - Coastal special-shaped structure 3d printing concrete, processing technology and use thereof - Google Patents

Coastal special-shaped structure 3d printing concrete, processing technology and use thereof Download PDF

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WO2022007063A1
WO2022007063A1 PCT/CN2020/105896 CN2020105896W WO2022007063A1 WO 2022007063 A1 WO2022007063 A1 WO 2022007063A1 CN 2020105896 W CN2020105896 W CN 2020105896W WO 2022007063 A1 WO2022007063 A1 WO 2022007063A1
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concrete
printing
sand
pva
water
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PCT/CN2020/105896
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French (fr)
Chinese (zh)
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罗健林
张纪刚
李秋义
高嵩
侯东帅
滕飞
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青岛理工大学
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Priority to JP2021572501A priority Critical patent/JP7362083B2/en
Priority to AU2020457381A priority patent/AU2020457381B2/en
Publication of WO2022007063A1 publication Critical patent/WO2022007063A1/en

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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G21/00—Preparing, conveying, or working-up building materials or building elements in situ; Other devices or measures for constructional work
    • E04G21/02—Conveying or working-up concrete or similar masses able to be heaped or cast
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
    • 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
    • B33Y10/00—Processes of additive manufacturing
    • 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
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • C04B2111/00034—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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/34—Non-shrinking or non-cracking materials
    • C04B2111/343—Crack resistant materials
    • 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 3D printing of coastal structures, and in particular relates to a 3D printing concrete of a special-shaped coastal structure, a processing technology of the 3D printing concrete of the special-shaped coastal structure, and an application in the preparation of a special-shaped coastal structure.
  • reinforced concrete structures are widely used in coastal structural engineering fields such as offshore buildings, bridges and tunnels, wind energy nuclear power plants, oil drilling platforms, and seaports.
  • coastal special-shaped structures such as manhole covers, rainwater grate, underground pipe gallery, egg-shaped water tank, subway segment, honeycomb beam, laminated beam/slab, etc. can be quickly manufactured, which has attracted wide attention.
  • 3D printed concrete generally does not add steel skeleton, but doped with high-strength and high-modulus short-cut steel fibers to achieve the requirements of high early strength and good toughness and deformation of 3D printed concrete.
  • the successful 3D printing of complex concrete components also depends on the characteristics of the corresponding concrete slurry, such as fast setting speed, good water retention and cohesion, good plasticity, interlayer interface bonding and good thixotropy.
  • the concrete for coastal special-shaped structures is a porous, multi-phase heterogeneous material, seawater and oxygen will reach the surface of the steel fiber along the pores in the concrete, generating corrosion free electrons. These electrons are transmitted to the cathode area through the steel fibers, and the negative ions in the solution are transmitted to the anode area through the pore solution, which is easy to form a large number of corrosion micro-batteries, and then fail prematurely.
  • the coastal special-shaped structures have complex surfaces and are mostly thin-walled structures.
  • the 3D printed concrete is a layer-by-layer printing mode, and it is difficult to have a sufficient thickness of the concrete protective layer to protect the randomly dispersed steel fibers from marine corrosion; at the same time, , Common marine anti-corrosion technologies such as surface anti-corrosion coating and cathodic protection are either unusable or ineffective for coastal special-shaped structures with persistent printed interface layers.
  • the purpose of the present invention is to provide an optimized 3D printing concrete for coastal special-shaped structures, and the printed coastal special-shaped structures have better marine anti-corrosion effect, interlayer interface bonding and thixotropic properties.
  • a 3D printing concrete of a coastal special-shaped structure is composed of the following parts by weight of raw materials: 1 part of compound cement, 1-2 parts of recycled sand, fly ash (FA) ) 0.05-0.2 part, polyvinyl alcohol (PVA) 0.005-0.05 part, graphene oxide (GO) 0.0002-0.002 part, steel fiber 0.01-0.05 part, organic fiber 0.005-0.02 part, water reducing agent 0.005-0.01 part, 0.005-0.01 part of setting modifier, 0-0.05 part of mineral admixture and 0.3-0.5 part of water; the PVA also has an oxidant and a catalyst.
  • PVA polyvinyl alcohol
  • GO graphene oxide
  • the coastal special-shaped structure 3D printing concrete prepared by the above-mentioned raw materials and proportions can well meet the printing requirements of the existing robotic arms and structural model parameters, and print coastal special-shaped concrete structures of different specifications.
  • the printed coastal special-shaped structure has good marine durability.
  • the present invention obtains the raw materials and proportions of the above-mentioned 3D printing concrete through continuous attempts, and through the GO with many functional groups such as hydroxyl groups, epoxy groups and carboxyl groups and PVA containing many hydroxyl groups, the 3D printing concrete not only has good cohesion and water retention, but also can Make the adjacent 3D printed concrete thin layers have good interfacial adhesion; GO-PVAH@FA can make the 3D printed concrete slurry have shear thinning effect, and achieve good thixotropy and plasticity of the slurry; The stable combination of water-based GO and PVA electrolyte forms a large number of GO-PVAH microcapacitors.
  • These GO-PVAH microcapacitors uniformly dispersed in the 3D printed concrete thin layer through the FA medium can store a large amount of 3D printed concrete thin layer porous solution electrolyte and electrolyte. Capture the ions migrated from the seawater medium, avoid the formation of corrosion cells in the 3D printed concrete thin-layer steel fiber, effectively prevent the electrochemical corrosion of the steel fiber, and then significantly improve the overall coastal special-shaped structure resistance to chloride ion penetration and seawater corrosion resistance.
  • the second aspect of the present invention provides a processing technology for 3D printing concrete with a coastal special-shaped structure
  • the processing technology includes: drying the concrete with the 3D printing concrete raw material described in the first aspect by 3D printing technology Print out.
  • a third aspect of the present invention provides an application of the coastal special-shaped structure 3D printing concrete described in the first aspect in the preparation of a coastal special-shaped structure.
  • the invention innovatively wraps the dispersed and stable GO-PVAH on the surface of the FA medium to realize its long-term and uniform distribution in the subsequent nano-recycled concrete system, which can effectively offset the problem of greatly reducing the fluidity of recycled concrete when GO is directly mixed with recycled concrete.
  • the surface of GO contains many hydrophilic groups such as hydroxyl groups, epoxy groups and carboxyl groups, which is conducive to the compatibility of GO with cement mortar system, and at the same time GO can give full play to the nanometer
  • the nucleation and template effects can improve the microscopic morphology of the corresponding recycled concrete hardened body
  • GO-PVAH hydrogel and recycled aggregate can well act as internal curing components during the forming process of nano-recycled concrete, and the subsequent moisture is slow
  • the release effectively offsets the thermal shrinkage stress generated by the rapid hydration of cement, and achieves volume stability;
  • the toughening effect of doped chopped steel fibers and the bridging effect of organic fibers will further ensure the mechanical toughness and crack resistance of nano-recycled concrete. Penetration efficiency.
  • the coastal special-shaped structure 3D printing concrete of the present invention firstly, GO containing many functional groups such as hydroxyl groups, epoxy groups and carboxyl groups and PVA containing many hydroxyl groups not only make the 3D printing concrete have good cohesion and water retention, but also Make the adjacent 3D printed concrete thin layer have good interfacial adhesion; secondly, the GO-PVAH@FA containing GO-PVAH@FA can make the 3D printed concrete slurry have shear thinning effect, and achieve good thixotropy and plasticity of the slurry; its Third, the stable combination of GO containing hydrophilic group and PVA electrolyte forms a large number of GO-PVAH microcapacitors.
  • GO-PVAH is synthesized on the surface of FA, and the admixture aqueous solution medium effectively delays the time when GO-PVAH@FA is added to the nano-recycled concrete, and admixtures such as compound cement and FA that reduce alkalinity are used in combination.
  • admixtures such as compound cement and FA that reduce alkalinity are used in combination.
  • the thixotropy, time rheology and plasticity of the nano-recycled concrete slurry are realized by GO-PVAH wrapped with FA medium surface, self-curing of recycled aggregate and ball lubrication effect of FA; GO nano-template, organic fiber bridging and composite
  • the effect of fast setting and early strength of compounded cement comprehensively realizes the functions of continuous early strength, crack resistance and impermeability of nano-recycled concrete; through GO-PVAH and internal curing of recycled aggregate, micro-expansion of compounded cement and FA shrinkage reduction effect, the interface volume stability effect of nano-recycled concrete is realized ;
  • Example 1 is a schematic diagram of the GO-PVA polymer intercalation and GO-PVAH@FA coating process described in Example 3;
  • 1-FA particles 2-GO-PVA hydrogel layer, 21-GO sheet layer, 22-PVA polymer, 23-hydrogel.
  • the GO-PVA intercalation structure is to schematically reflect the intercalation structure formed by the GO sheet and the PVA linear polymer
  • the SEM microscopic morphology of FA is to schematically reflect the spherical hollow structure and size specification of FA, so as to facilitate the present study. better understood by those skilled in the art.
  • FIG. 2 is a flow chart of the 3D printing concrete and the processing technology of the coastal special-shaped structure described in Example 3.
  • FIG. 2 is a flow chart of the 3D printing concrete and the processing technology of the coastal special-shaped structure described in Example 3.
  • the present invention provides a 3D printing concrete, a processing technology and its application in the rapid manufacture of coastal special-shaped structures. Synthesize GO-PVAH on the surface of FA, and effectively delay the time of adding GO-PVAH@FA to the nano-recycled concrete as an admixture in aqueous solution. Combined with low-alkalinity compound cement and FA and other admixtures with reduced alkalinity, the GO is innovatively avoided. The bottleneck problem of deoxidation in strong alkali environment.
  • the thixotropic properties, time-dependent rheology, and water retention of the nano-recycled concrete slurry were realized by GO-PVAH wrapped on the surface of FA medium, the self-curing of recycled aggregates and the ball lubrication effect of FA; the use of GO nano-templates, fiber bridges and composite materials
  • the early-strength and fast-setting effect of the mixed cement comprehensively realizes the continuous early strength and crack resistance and toughening functions of the nano-recycled concrete; the interfacial volume stability of the nano-recycled concrete is realized through the internal curing of GO-PVAH and recycled aggregate, the micro-expansion of the composite cement and the shrinkage reduction effect of FA.
  • a 3D printing concrete of a coastal special-shaped structure is composed of the following parts by weight of raw materials: 1 part of compound cement, 1-2 parts of recycled sand, fly ash (FA) ) 0.05-0.2 part, polyvinyl alcohol (PVA) 0.005-0.05 part, graphene oxide (GO) 0.0002-0.002 part, steel fiber 0.01-0.05 part, organic fiber 0.005-0.02 part, water reducing agent 0.005-0.01 part, 0.005-0.01 part of setting modifier, 0-0.05 part of mineral admixture and 0.3-0.5 part of water; the PVA also has an oxidant and a catalyst.
  • PVA polyvinyl alcohol
  • GO graphene oxide
  • the compound cement is prepared by mixing high Belite sulfoaluminate cement (HBSC), Portland cement and gypsum in a ratio of 1:(0.65-1.25):(0-0.15) by weight.
  • HBSC high Belite sulfoaluminate cement
  • Portland cement Portland cement
  • gypsum gypsum
  • the compound cement obtained by this formula has the characteristics of fast setting and early strength, and the ball lubrication characteristics of FA are helpful for the realization of the printable and buildable functions of the corresponding nano-regenerated concrete.
  • the reclaimed sand includes coarse sand, medium sand, fine sand and ultra-fine sand; wherein, the medium sand ratio is 27%-33%.
  • the coarse sand is coarse sand with a fineness modulus of 3.7-3.1 and an average particle size of 0.5 mm or more.
  • the medium sand is medium sand with a fineness modulus of 3.0-2.3 and an average particle size of 0.5mm-0.35mm.
  • the fine sand is fine sand with a fineness modulus of 2.2-1.6 and an average particle size of 0.35mm-0.25mm.
  • the ultrafine sand is ultrafine sand with a fineness modulus of 1.5-0.7 and an average particle size of 0.25 mm or less.
  • the mass ratio of the coarse sand, medium sand, fine sand and ultra-fine sand is 1:(1.1-2.0):(1-1.5):(1-1.5); the components under this ratio are mixed Afterwards, a good particle gradation curve can be achieved.
  • the specific type of reclaimed sand in the present invention is not particularly limited.
  • the reclaimed sand is reclaimed sand that meets the JC/T2548-2019 specification after crushing and particle shaping of construction waste or industrial waste.
  • the use of recycled sand can effectively improve the self-maintenance effect of nano-recycled concrete slurry, and simultaneously expand the utilization of solid waste resources.
  • the FA is a grade I FA with a loss on ignition ⁇ 5% specified in the GB/T 1596-2017 standard, so as to obtain a better ball lubrication effect.
  • the PVA is a PVA aqueous solution with an average polymerization degree of 500-600 and an alcoholysis degree of 88%; GO is dispersed in the PVA aqueous solution to form a stable GO-PVA prepolymer solution.
  • the PVA oxidant and the PVA catalyst are respectively sodium periodate, potassium permanganate or potassium chlorate mentioned in Chinese patent CN103450489 or CN105885064A, one of concentrated hydrochloric acid, dilute sulfuric acid, dilute nitric acid or boric acid, with The PVA prepolymer was intercalated in the GO sheet structure through an in-situ polymerization intercalation process.
  • the GO is a GO powder with a monolayer rate of ⁇ 90% and an oxygen content of 35-45% or an aqueous dispersion with a concentration of 0.05-10 mg/mL; when using a GO aqueous dispersion, the water is calculated according to the concentration ratio.
  • the mass of GO in the dispersion, the water in the corresponding aqueous dispersion was calculated into the total amount of water used in the 3D printed concrete.
  • the specific type of the water-reducing agent is not particularly limited, and the commercially available products can all meet the use requirements for preparing the coastal special-shaped structure described in the present invention.
  • the water reducing agent is a polycarboxylate superplasticizer, an early-strength polycarboxylate superplasticizer, a sodium naphthalene sulfonate superplasticizer or a melamine resin superplasticizer One or more optimal combinations of the agents.
  • the coagulation adjusting agent is one of anhydrous sodium sulfate, triethanolamine, and nano-C-S-H crystal nucleus.
  • the coastal special-shaped 3D printing concrete provided by the invention is conducive to the rapid setting of concrete through admixtures such as setting modifiers, and will effectively ensure the realization of the rapid setting function of the nano-recycled concrete.
  • the present invention uses steel fibers, the specific source of which is not particularly limited, and the steel fiber materials generally use the production wastes of the steel processing industry.
  • the steel fibers are one or a combination of cutting steel fibers, shearing steel fibers, milling steel fibers, and melting and drawing steel fibers. .
  • the organic fibers in the present invention are one or more of chopped polyvinyl alcohol fibers, polypropylene fibers, and high-density polyethylene fibers. combination of species.
  • the mineral admixture is one or a combination of regenerated fine powder, ground slag, fly ash, pozzolan or silica fume.
  • the source of the raw materials such as the above-mentioned regenerated fine powder is not particularly limited.
  • the water includes, but is not limited to, distilled water, deionized water, tap water or electrolyzed water, which can be selected by technicians according to construction conditions.
  • a second aspect of the present invention provides a processing technology for 3D printing concrete with a coastal special-shaped structure.
  • the processing technology includes: printing the concrete dry mix with the 3D printing concrete raw material described in the first aspect through a 3D printing technology.
  • the specific steps of the concrete dry mix preparation process are as follows: make PVA, GO and oxidant into a GO-PVA prepolymer liquid by in-situ polymerization and intercalation method; mix FA, water reducing agent, catalyst and the GO-PVAH The prepolymer solution is mixed evenly to form FA wrapped with GO-PVAH prepolymer solution to form GO-PVAH@FA; GO-PVAH@FA is dispersed in a solution containing water reducing agent and coagulant to form GO-PVAH@FA suspension;
  • the composite cement, recycled sand, steel fiber, organic fiber and mineral admixture are mechanically mixed in the silo to form a nano-recycled concrete dry mix.
  • the GO-PVAH@FA suspension and the nano-recycled concrete dry mix are rapidly mixed in the 3D printing head, and the printing specifications (speed, flow rate and layer thickness) of the 3D robotic arm are set, and the printing is performed layer by layer. Thin layers of nano-recycled concrete with different layer thicknesses, resulting in a coastal special-shaped structure.
  • S4 Determine the coastal special-shaped structure models of different sizes and material parameters, determine the printing specifications (speed, flow and layer thickness) of the 3D robotic arm, and use methods well-known in the art to combine GO-PVAH@FA suspension with nano-recycled concrete
  • the dry mixture is quickly mixed in the 3D printing head, and the nano-recycled concrete thin layers with different layer thicknesses are printed layer by layer, and finally the coastal special-shaped structure is quickly produced.
  • step S1 the PVA intercalation efficiency and GO dispersion effect in the GO-PVA prepolymer solution can be analyzed by combining automatic titration, rotational viscometer, UV-Vis spectrophotometry, and microtopography.
  • step S2 the GO-PVAH equilibrium swelling rate, light transmittance, structural cross-linking degree, and microscopic distribution can be measured in combination with freeze-drying method, UV-Vis spectrophotometry, TG-DSC comprehensive thermal analysis method, and microscopic topography method. Morphology and density; combined with ethanol drainage method, TG-DSC comprehensive thermal analysis method, peel strength method and film thickness meter method, the overall density, water content and organic content of GO-PVAH@FA, interfacial peel resistance and coating were measured respectively. layer thickness.
  • nano-regenerative concrete can be prepared by the conventional preparation method of nano-regenerative concrete for 3D printing well-known to those skilled in the art. Area), automatic concrete setting time and consistency tester (setting time, consistency, rheology with time), etc. to optimize the type and dosage of the corresponding water reducer and setting modifier.
  • Various properties of the nano-recycled concrete can be carried out in combination with the large-scale printability and marine durability (freeze-thaw resistance, chloride ion resistance, sulfate corrosion resistance) test methods of nano-recycled concrete well-known to those skilled in the art characterization. Electrochemical parameters such as steel fiber corrosion potential, polarization resistance, corrosion current density, electrochemical impedance spectroscopy, etc.
  • the performance parameters such as interlayer bonding and tensile force and interlayer shear force of nano-recycled concrete thin layers with different layer thicknesses are characterized .
  • the construction quality of nano-reclaimed concrete with different layers and the deterioration of interlayer bonding force under the action of freeze-thaw cycles, ion erosion, and sulfate corrosion can be evaluated by methods such as ultrasonic echoes or radar waves that are familiar to those skilled in the art.
  • a third aspect of the present invention provides an application of the coastal special-shaped structure 3D printing concrete described in the first aspect in the preparation of a coastal special-shaped structure.
  • the coastal special-shaped structures include, but are not limited to, manhole covers, rainwater grate, underground pipe gallery, egg-shaped water tank, subway segment, honeycomb beam, laminated beam/slab, and the like.
  • a 3D printing concrete for a special-shaped coastal structure includes the following components: compound cement, recycled sand, fly ash (FA), polyvinyl alcohol (PVA), Graphene oxide (GO), steel fiber, organic fiber, water reducer, coagulant, mineral admixture and water; the mass ratio of the above components is 1:1:0.05:0.005:0.0002:0.01:0.005: (0.005-0.01): 0.005: 0.01: 0.3.
  • the compound cement includes the following components: high belite sulfoaluminate cement (HBSC), Portland cement, gypsum, the mass ratio of each component is 1:0.65:0.1; compound cement has quick setting and early strength
  • HBSC high belite sulfoaluminate cement
  • Portland cement Portland cement
  • gypsum the mass ratio of each component is 1:0.65:0.1
  • compound cement has quick setting and early strength
  • the characteristics and the ball lubrication characteristics of FA contribute to the realization of the printable and buildable functions of the corresponding nano-recycled concrete.
  • the mass ratio of coarse sand, medium sand, fine sand and ultrafine sand in the reclaimed sand is 1:1.1:1:1.
  • the FA is Class I FA with loss on ignition ⁇ 5% specified in the GB/T 1596-2017 standard.
  • the PVA is a PVA aqueous solution with an average polymerization degree of 500-600 and an alcoholysis degree of 88%; the GO is dispersed in the PVA aqueous solution to form a stable GO-PVA prepolymer solution.
  • the PVA oxidant and PVA catalyst are respectively sodium periodate and concentrated hydrochloric acid.
  • the GO powder with a GO monolayer rate of ⁇ 90% and an oxygen content of 40% The GO powder with a GO monolayer rate of ⁇ 90% and an oxygen content of 40%.
  • the water reducing agent is a high-efficiency water reducing agent of polycarboxylic acid type.
  • the coagulation regulator is anhydrous sodium sulfate.
  • the steel fibers are cut steel fibers.
  • the organic fibers are high-density polyethylene fibers.
  • the mineral admixture is regenerated fine powder and ground slag mixed in a mass ratio of 1:1.
  • the water is tap water.
  • a 3D printing concrete for a special-shaped coastal structure includes the following components: compound cement, recycled sand, fly ash (FA), polyvinyl alcohol (PVA), Graphene oxide (GO), steel fiber, organic fiber, water reducing agent, coagulant, mineral admixture and water; the mass ratio of the above components is 1:2:0.2:0.05:0.002:0.05:0.02: 0.01:0.01:0.05:0.5.
  • the compound cement includes the following components: high Belite sulfoaluminate cement (HBSC), Portland cement, and gypsum, and the mass ratio of each component is 1:1.25:0.15.
  • HBSC high Belite sulfoaluminate cement
  • Portland cement Portland cement
  • gypsum gypsum
  • the mass ratio of coarse sand, medium sand, fine sand and ultrafine sand in the reclaimed sand is 1:2.0:1.5:1.5.
  • the FA is Class I FA with loss on ignition ⁇ 5% specified in the GB/T 1596-2017 standard.
  • the PVA is a PVA aqueous solution with an average polymerization degree of 500-600 and an alcoholysis degree of 88%; the GO is dispersed in the PVA aqueous solution to form a stable GO-PVA prepolymer solution.
  • the PVA oxidant and PVA catalyst are potassium permanganate and dilute sulfuric acid respectively.
  • the GO powder with a GO monolayer rate of ⁇ 90% and an oxygen content of 35% The GO powder with a GO monolayer rate of ⁇ 90% and an oxygen content of 35%.
  • the water-reducing agent is an early-strength polycarboxylic acid water-reducing agent.
  • the coagulation regulator is triethanolamine.
  • the steel fibers are sheared steel fibers and milled steel fibers mixed in a mass ratio of 0.5:1.
  • the organic fibers are polypropylene fibers.
  • the mineral admixture is fly ash.
  • the water is deionized water.
  • a processing technology for 3D printing concrete of a coastal special-shaped structure which specifically includes the following steps:
  • composition 40kg Class II granite reclaimed sand (obtained from local C40, 28-year-old concrete structure demolition construction waste in Qingdao, crushed and reshaped, with an average apparent density of 2860kg/m 3 ) (from 8kg coarse sand, 12kg of sand, fine sand and 10kg 10kg ultra fine sand), 0.5kg powder slag (from an apparent density of 2930kg / m 3 BX blast furnace slag weight and obtained by ball milling), and added 1.0kg / m shear steel fiber 3 (length of 3-15mm, the diameter of 0.12-0.25mm, tensile strength ⁇ 2850MPa, Laiwu City Hengtong Engineering materials Co.
  • step S1 the PVA intercalation efficiency and GO dispersion effect in the GO-PVA prepolymer solution are shown in Figure 1.
  • step S2 the swelling rate and coating thickness of GO-PVAH@FA were 30% and 65 ⁇ m, respectively; in step S4, the nano-recycled concrete for 3D printing rain grate substructure was rapidly fabricated, interlayer bonding and marine durability. As shown in Table 1.
  • Figure 1 shows the schematic diagram of the GO-PVA polymer intercalation and GO-PVAH@FA coating structure.
  • the GO-PVA hydrogel layer is coated on the surface of FA particles, and the PVA polymer effectively intercalates the GO sheet structure to form
  • the positive and negative electric double layers of microcapacitors can effectively improve the marine anti-corrosion performance of nano-recycled concrete.
  • step S2 the swelling ratio and coating thickness of GO-PVAH@FA were 40% and 50 ⁇ m, respectively.
  • step S4 the rapid manufacturing, interlayer bonding and marine durability of the nano-recycled concrete for 3D printing of the circular manhole cover structure are also shown in Table 1.
  • step S2 the swelling ratio and coating thickness of GO-PVAH@FA were 40% and 50 ⁇ m, respectively.
  • step S4 the rapid fabrication, interlayer bonding and marine durability of the nano-recycled concrete for 3D printing of the oval water tank structure are also shown in Table 1.
  • step S3 20kg of compound cement is composed of 10kg of 525 type HBSC and 10kg of PO 52.5 Portland cement, does not contain gypsum, and the corresponding minerals are blended
  • the dosage of the material is 0kg.
  • step S2 the swelling ratio and coating thickness of GO-PVAH@FA were 30% and 65 ⁇ m, respectively.
  • step S4 the relevant properties of the nano-recycled concrete for 3D printing are shown in Table 1.

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Abstract

A coastal special-shaped structure 3D printing concrete, a processing technology and the use thereof. The raw materials thereof are compounded cement, regenerated sand, fly ash, polyvinyl alcohol, graphene oxide, steel fibers, organic fibers, a water reducing agent, a thickening time control agent, a mineral admixture and water. The 3D printing concrete has a good cohesive water retention and adjacent thin layer interface cohesiveness. The formation of a micro-capacitor by combining GO with a PVA electrolyte avoids the formation of a corrosion cell in a thin layer of concrete, and the concrete has a good marine durability.

Description

一种滨海异型结构3D打印混凝土、加工工艺及应用A coastal special-shaped structure 3D printing concrete, processing technology and application 技术领域technical field
本发明属于滨海结构3D打印技术领域，具体涉及一种滨海异型结构3D打印混凝土、所述滨海异型结构3D打印混凝土的加工工艺及在制备滨海异型结构中的应用。The invention belongs to the technical field of 3D printing of coastal structures, and in particular relates to a 3D printing concrete of a special-shaped coastal structure, a processing technology of the 3D printing concrete of the special-shaped coastal structure, and an application in the preparation of a special-shaped coastal structure.
背景技术Background technique
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。The information disclosed in this Background section is only for enhancement of understanding of the general background of the invention and should not necessarily be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
目前建筑数字化、工业化、智能化的产业升级状况需要快速制造用于不同规格、结构型式装配建筑用剪力墙、叠合楼板、叠合梁、叠合柱、预制楼梯、整体卫生间、垃圾槽等各类混凝土预制构件。同时，建筑垃圾资源化利用有效纾解城镇生态保护和节能减排压力。近年来快速发展起来，基于机器人3D打印数字化建造方法不仅可以精确控制各类混凝土异型构件的建造精度，制造出优美造型的各类曲面构件，而且不必事先制造模具，不必在制造过程中去处理大量的材料，也不必通过复杂的锻造工艺，最终在生产上实现结构优化、节约材料和节省能源，有效实现装配建筑的工业化、智能化、资源节约化，应用前景十分广阔。The current state of digitalization, industrialization, and intellectualization of buildings requires rapid manufacturing of shear walls, laminated floors, laminated beams, laminated columns, prefabricated stairs, integrated toilets, garbage chutes, etc. for different specifications and structural types. Various types of precast concrete elements. At the same time, the recycling of construction waste can effectively relieve the pressure of urban ecological protection and energy conservation and emission reduction. With the rapid development in recent years, the digital construction method based on robot 3D printing can not only accurately control the construction accuracy of various types of concrete special-shaped components, and produce various types of curved components with beautiful shapes, but also does not need to manufacture molds in advance, and does not need to deal with a large number of concrete components in the manufacturing process. It does not have to go through complex forging processes, and finally realizes structural optimization, material saving and energy saving in production, effectively realizing the industrialization, intelligence and resource saving of assembly buildings, and the application prospect is very broad.
与此同时，钢筋混凝土结构广泛应用在近海建筑、桥梁隧道、风能核电站、钻油井平台、海港码头等滨海结构工程领域。同样基于3D打印技术可以快速制造诸如井盖、雨水篦子、地下管廊、卵型水槽、地铁管片、蜂窝梁、叠合梁/板等滨海异型结构，进而广受关注。At the same time, reinforced concrete structures are widely used in coastal structural engineering fields such as offshore buildings, bridges and tunnels, wind energy nuclear power plants, oil drilling platforms, and seaports. Also based on 3D printing technology, coastal special-shaped structures such as manhole covers, rainwater grate, underground pipe gallery, egg-shaped water tank, subway segment, honeycomb beam, laminated beam/slab, etc. can be quickly manufactured, which has attracted wide attention.
不可忽视的是，3D打印混凝土一般不添加钢筋骨架，而是掺杂高强、高模的短切钢纤维来实现3D打印混凝土的早期强度高、韧性变形佳的要求。然而，混凝土繁杂构件成功3D打印还得仰赖于相应混凝土浆料拥有凝结速度快、保水粘聚性好、可塑性佳、层间界面粘结与触变性佳等特点。与此同时，作为滨海异型结构用混凝土为多孔、多相非均质材料，海水和氧气会沿着混凝土中的孔隙到达钢纤维表面，产生腐蚀自由电子。这些电子通过钢纤维向阴极区传送，溶液中的负离子通过孔隙溶液向阳极区传输，易形成大量腐蚀微电池，进而过早失效。What cannot be ignored is that 3D printed concrete generally does not add steel skeleton, but doped with high-strength and high-modulus short-cut steel fibers to achieve the requirements of high early strength and good toughness and deformation of 3D printed concrete. However, the successful 3D printing of complex concrete components also depends on the characteristics of the corresponding concrete slurry, such as fast setting speed, good water retention and cohesion, good plasticity, interlayer interface bonding and good thixotropy. At the same time, as the concrete for coastal special-shaped structures is a porous, multi-phase heterogeneous material, seawater and oxygen will reach the surface of the steel fiber along the pores in the concrete, generating corrosion free electrons. These electrons are transmitted to the cathode area through the steel fibers, and the negative ions in the solution are transmitted to the anode area through the pore solution, which is easy to form a large number of corrosion micro-batteries, and then fail prematurely.
然而，当发展滨海装配结构用3D打印混凝土材料时，发明人发现存在以下问题：However, when developing 3D printed concrete materials for coastal assembly structures, the inventors found the following problems:
(1)滨海异型结构曲面复杂、多为薄壁结构，3D打印混凝土是逐层打印模式，相应难以拥有足够的混凝土保护层厚度保护随机分散的钢纤维，使其免于海洋腐蚀；与此同时，表面涂防腐层、外加阴极保护等常见海洋防腐技术对持续存在打印界面层的滨海异型结构来说，要么无法使用，要么使用效果差。(1) The coastal special-shaped structures have complex surfaces and are mostly thin-walled structures. The 3D printed concrete is a layer-by-layer printing mode, and it is difficult to have a sufficient thickness of the concrete protective layer to protect the randomly dispersed steel fibers from marine corrosion; at the same time, , Common marine anti-corrosion technologies such as surface anti-corrosion coating and cathodic protection are either unusable or ineffective for coastal special-shaped structures with persistent printed interface layers.
(2)采用常规3D打印混凝土材料打印滨海异型结构时，难以保障在拥有良好流变性、保水粘聚性、力学韧性及体积稳定性能的同时，拥有足够的层间界面粘结与触变性。(2) When using conventional 3D printing concrete materials to print coastal special-shaped structures, it is difficult to ensure sufficient interlayer interface bonding and thixotropy while having good rheology, water retention and cohesion, mechanical toughness and volume stability.
(3)采用常规3D打印混凝土材料打印滨海异型结构时，常难以同步资源化利用建筑或工业固体废弃物，减轻城镇生态保护和节能减排压力，实现绿色环保效益。(3) When using conventional 3D printing concrete materials to print coastal special-shaped structures, it is often difficult to simultaneously recycle construction or industrial solid waste, reduce the pressure of urban ecological protection, energy conservation and emission reduction, and achieve green environmental protection benefits.
发明内容SUMMARY OF THE INVENTION
针对上述背景技术中记载的问题，本发明目的在于提供一种优化的滨海异型结构3D打印混凝土，其打印得到的滨海异型结构具有更好的海洋防腐效果及层间界面粘结与触变性能。In view of the problems described in the above background art, the purpose of the present invention is to provide an optimized 3D printing concrete for coastal special-shaped structures, and the printed coastal special-shaped structures have better marine anti-corrosion effect, interlayer interface bonding and thixotropic properties.
基于上述技术效果，本发明提供以下技术方案：Based on the above technical effects, the present invention provides the following technical solutions:
本发明第一方面，提供一种滨海异型结构3D打印混凝土，所述滨海异型结构3D打印混凝土由以下重量份的原料组成：复配水泥1份、再生砂1-2份、粉煤灰(FA)0.05-0.2份、聚乙烯醇(PVA)0.005-0.05份、氧化石墨烯(GO)0.0002-0.002份、钢纤维0.01-0.05份、有机纤维0.005-0.02份、减水剂0.005-0.01份、调凝剂0.005-0.01份、矿物掺合料0-0.05份和水0.3-0.5份；所述PVA中还具有氧化剂和催化剂。In a first aspect of the present invention, there is provided a 3D printing concrete of a coastal special-shaped structure, the 3D printing concrete of a coastal special-shaped structure is composed of the following parts by weight of raw materials: 1 part of compound cement, 1-2 parts of recycled sand, fly ash (FA) ) 0.05-0.2 part, polyvinyl alcohol (PVA) 0.005-0.05 part, graphene oxide (GO) 0.0002-0.002 part, steel fiber 0.01-0.05 part, organic fiber 0.005-0.02 part, water reducing agent 0.005-0.01 part, 0.005-0.01 part of setting modifier, 0-0.05 part of mineral admixture and 0.3-0.5 part of water; the PVA also has an oxidant and a catalyst.
上述原料及配比制备的滨海异型结构3D打印混凝土，能够很好的配合现有机器臂及结构模型参数打印需求，打印得到不同规格的滨海异型混凝土结构。另外，打印得到的滨海异型结构具有良好的海洋耐久性能。The coastal special-shaped structure 3D printing concrete prepared by the above-mentioned raw materials and proportions can well meet the printing requirements of the existing robotic arms and structural model parameters, and print coastal special-shaped concrete structures of different specifications. In addition, the printed coastal special-shaped structure has good marine durability.
本发明通过不断尝试得到上述3D打印混凝土的原料及配比，通过诸多羟基、环氧基和羧基等官能团的GO与含有诸多羟基的PVA不仅使3D打印混凝土拥有良好的粘聚保水性，还能使相邻3D打印混凝土薄层拥有良好的界面粘结性；含 GO-PVAH@FA可使得3D打印混凝土浆料拥有剪切变稀功效，实现浆料良好的触变性与可塑性；同时，含亲水基团GO与PVA电解液稳定结合形成了大量的GO-PVAH微电容器，这些经FA媒介均匀弥散3D打印混凝土薄层中的GO-PVAH微电容器能大量储存3D打印混凝土薄层孔溶液电解质及捕获海水介质迁移来的离子，避免3D打印混凝土薄层钢纤维中腐蚀电池的形成，有效防止钢纤维电化学腐蚀，进而显著提高整体滨海异型结构抗氯离子渗透、耐海水腐蚀性能。The present invention obtains the raw materials and proportions of the above-mentioned 3D printing concrete through continuous attempts, and through the GO with many functional groups such as hydroxyl groups, epoxy groups and carboxyl groups and PVA containing many hydroxyl groups, the 3D printing concrete not only has good cohesion and water retention, but also can Make the adjacent 3D printed concrete thin layers have good interfacial adhesion; GO-PVAH@FA can make the 3D printed concrete slurry have shear thinning effect, and achieve good thixotropy and plasticity of the slurry; The stable combination of water-based GO and PVA electrolyte forms a large number of GO-PVAH microcapacitors. These GO-PVAH microcapacitors uniformly dispersed in the 3D printed concrete thin layer through the FA medium can store a large amount of 3D printed concrete thin layer porous solution electrolyte and electrolyte. Capture the ions migrated from the seawater medium, avoid the formation of corrosion cells in the 3D printed concrete thin-layer steel fiber, effectively prevent the electrochemical corrosion of the steel fiber, and then significantly improve the overall coastal special-shaped structure resistance to chloride ion penetration and seawater corrosion resistance.
基于上述效果，本发明第二方面，提供一种滨海异型结构3D打印混凝土的加工工艺，所述加工工艺包括：将第一方面所述3D打印混凝土原料通过3D打印技术将所述混凝土干混料打印成型。Based on the above effects, the second aspect of the present invention provides a processing technology for 3D printing concrete with a coastal special-shaped structure, the processing technology includes: drying the concrete with the 3D printing concrete raw material described in the first aspect by 3D printing technology Print out.
本发明第三方面，提供第一方面所述滨海异型结构3D打印混凝土在制备滨海异型结构中的应用。A third aspect of the present invention provides an application of the coastal special-shaped structure 3D printing concrete described in the first aspect in the preparation of a coastal special-shaped structure.
以上一个或多个技术方案的有益效果是：The beneficial effects of the above one or more technical solutions are:
(1)采用本发明的滨海异型结构3D打印混凝土及加工工艺，不仅能快速制造滨海异型结构，而且能有效保障其海洋耐久性能。本发明创新地将分散稳定的GO-PVAH通过外裹FA媒介表面，实现其长效均匀分布于后续纳米再生混凝土体系中，可有效抵消GO直掺再生混凝土时大幅度降低再生混凝土流动性的问题，还给相应纳米再生混凝土浆料带来良好的粘稠度及触变性能；同时，含亲水基团GO组合PVA预聚体均匀分散于再生混凝土中将有效提升纳米再生混凝土的抗离析与经时流变性；其二，再生骨料内养护以及FA的滚珠润滑效应有助于相应再生混凝土保水功能实现；其三，调凝剂等调凝效应以及复配水泥快速凝结特点将进一步保障纳米再生混凝土可打印性及各层可建造性实现。(1) Using the 3D printing concrete and processing technology of the coastal special-shaped structure of the present invention, not only can the coastal special-shaped structure be quickly manufactured, but also its marine durability can be effectively guaranteed. The invention innovatively wraps the dispersed and stable GO-PVAH on the surface of the FA medium to realize its long-term and uniform distribution in the subsequent nano-recycled concrete system, which can effectively offset the problem of greatly reducing the fluidity of recycled concrete when GO is directly mixed with recycled concrete. , and also bring good viscosity and thixotropic properties to the corresponding nano-recycled concrete slurry; at the same time, the hydrophilic group-containing GO combined with PVA prepolymer uniformly dispersed in the recycled concrete will effectively improve the anti-segregation and thixotropic properties of the nano-recycled concrete. Time-dependent rheology; second, the internal curing of recycled aggregate and the ball lubrication effect of FA contribute to the realization of the water retention function of the corresponding recycled concrete; third, the setting adjustment effect of the setting modifier and the rapid setting characteristics of the compound cement will further ensure the nanometer Recycled concrete printability and layer buildability achieved.
3D打印混凝土硬化体力学韧性及耐久性能实现机制：一方面，GO表面含有诸多羟基、环氧基和羧基等亲水基团，有利于GO与水泥胶砂体系相容，同时GO能充分发挥纳米晶核与模板效应，改善相应再生混凝土硬化体微观形貌；另一方面，GO-PVAH水凝胶及再生骨料在纳米再生混凝土成型过程中能很好地充当内养护组分，后续水分缓慢释放有效抵消水泥快速水化时产生的热缩应力，实现体积稳定效能；再一方面，掺杂短切钢纤维增韧及有机纤维桥联效应将进一步保障纳米再生混凝土其力学韧性及抗裂抗渗效能。Mechanism of achieving mechanical toughness and durability of 3D printed concrete hardened body: On the one hand, the surface of GO contains many hydrophilic groups such as hydroxyl groups, epoxy groups and carboxyl groups, which is conducive to the compatibility of GO with cement mortar system, and at the same time GO can give full play to the nanometer The nucleation and template effects can improve the microscopic morphology of the corresponding recycled concrete hardened body; on the other hand, GO-PVAH hydrogel and recycled aggregate can well act as internal curing components during the forming process of nano-recycled concrete, and the subsequent moisture is slow The release effectively offsets the thermal shrinkage stress generated by the rapid hydration of cement, and achieves volume stability; on the other hand, the toughening effect of doped chopped steel fibers and the bridging effect of organic fibers will further ensure the mechanical toughness and crack resistance of nano-recycled concrete. Penetration efficiency.
(2)本发明的滨海异型结构3D打印混凝土，其一，含有诸多羟基、环氧基 和羧基等官能团的GO与含有诸多羟基的PVA不仅使3D打印混凝土拥有良好的粘聚保水性，还能使相邻3D打印混凝土薄层拥有良好的界面粘结性；其二，含GO-PVAH@FA可使得3D打印混凝土浆料拥有剪切变稀功效，实现浆料良好的触变性与可塑性；其三，含亲水基团GO与PVA电解液稳定结合形成了大量的GO-PVAH微电容器，这些经FA媒介均匀弥散3D打印混凝土薄层中的GO-PVAH微电容器能大量储存3D打印混凝土薄层孔溶液电解质及捕获海水介质迁移来的离子，避免3D打印混凝土薄层钢纤维中腐蚀电池的形成，有效防止钢纤维电化学腐蚀，进而显著提高整体滨海异型结构抗氯离子渗透、耐海水腐蚀性能。(2) The coastal special-shaped structure 3D printing concrete of the present invention, firstly, GO containing many functional groups such as hydroxyl groups, epoxy groups and carboxyl groups and PVA containing many hydroxyl groups not only make the 3D printing concrete have good cohesion and water retention, but also Make the adjacent 3D printed concrete thin layer have good interfacial adhesion; secondly, the GO-PVAH@FA containing GO-PVAH@FA can make the 3D printed concrete slurry have shear thinning effect, and achieve good thixotropy and plasticity of the slurry; its Third, the stable combination of GO containing hydrophilic group and PVA electrolyte forms a large number of GO-PVAH microcapacitors. These GO-PVAH microcapacitors in the 3D printed concrete thin layer uniformly dispersed by FA medium can store a large amount of 3D printed concrete thin layer. Porous solution electrolyte and capture ions migrated from seawater medium, avoid the formation of corrosion cells in 3D printed concrete thin-layer steel fibers, effectively prevent electrochemical corrosion of steel fibers, and then significantly improve the overall coastal special-shaped structure resistance to chloride ion penetration and seawater corrosion resistance .
本发明的纳米再生混凝土中，GO-PVAH在FA表面合成，以外加剂水溶液媒介有效延缓GO-PVAH@FA加入纳米再生混凝土时间，组合使用复配水泥以及降低碱度的FA等掺合料，创新性规避GO遇强碱环境脱氧的瓶颈问题。通过GO-PVAH外裹FA媒介表面、再生骨料自养护以及FA的滚珠润滑效应实现纳米再生混凝土浆料触变性、经时流变及可塑性功能实现；利用GO纳米模板、有机纤维桥联及复配水泥快凝早强效应综合实现纳米再生混凝土持续早强及抗裂抗渗功能；通过GO-PVAH及再生骨料内养护、复配水泥微膨胀及FA减缩效应实现纳米再生混凝土界面体积稳定效能；发挥GO-PVAH微电容器储能效应规避3D打印滨海结构中钢纤维腐蚀微电池的形成，实现钢筋腐蚀自免疫效能，创新地同步实现滨海异型结构3D打印混凝土可打印建造性及硬化体早强增韧、抗裂抗渗及腐蚀自免疫效能；同步拓宽固废资源化利用。In the nano-recycled concrete of the invention, GO-PVAH is synthesized on the surface of FA, and the admixture aqueous solution medium effectively delays the time when GO-PVAH@FA is added to the nano-recycled concrete, and admixtures such as compound cement and FA that reduce alkalinity are used in combination. Innovatively avoid the bottleneck problem of GO deoxidation in strong alkaline environment. The thixotropy, time rheology and plasticity of the nano-recycled concrete slurry are realized by GO-PVAH wrapped with FA medium surface, self-curing of recycled aggregate and ball lubrication effect of FA; GO nano-template, organic fiber bridging and composite The effect of fast setting and early strength of compounded cement comprehensively realizes the functions of continuous early strength, crack resistance and impermeability of nano-recycled concrete; through GO-PVAH and internal curing of recycled aggregate, micro-expansion of compounded cement and FA shrinkage reduction effect, the interface volume stability effect of nano-recycled concrete is realized ; Make use of the energy storage effect of GO-PVAH microcapacitors to avoid the formation of steel fiber corrosion microbatteries in 3D printed coastal structures, realize the self-immunity effect of steel corrosion, and innovatively and simultaneously realize the 3D printed concrete of coastal special-shaped structures. Toughening, anti-cracking, impermeability and corrosion self-immunity performance; simultaneously expand the utilization of solid waste resources.
附图说明Description of drawings
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。The accompanying drawings forming a part of the present invention are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention, and do not constitute an improper limitation of the present invention.
图1为实施例3所述GO-PVA聚合插层及GO-PVAH@FA包覆工艺示意图；1 is a schematic diagram of the GO-PVA polymer intercalation and GO-PVAH@FA coating process described in Example 3;
其中：1-FA颗粒、2-GO-PVA水凝胶层，21-GO片层、22-PVA聚合体、23-水凝胶。GO-PVA插层结构是为了示意性反映GO片层与PVA线链型聚合物形成的插层结构，FA的SEM微观形貌是为了示意性反映FA球形中空状结构及尺寸规格，以便于本领域技术人员更好地理解。Among them: 1-FA particles, 2-GO-PVA hydrogel layer, 21-GO sheet layer, 22-PVA polymer, 23-hydrogel. The GO-PVA intercalation structure is to schematically reflect the intercalation structure formed by the GO sheet and the PVA linear polymer, and the SEM microscopic morphology of FA is to schematically reflect the spherical hollow structure and size specification of FA, so as to facilitate the present study. better understood by those skilled in the art.
图2为实施例3所述滨海异型结构3D打印混凝土及加工工艺的流程图。FIG. 2 is a flow chart of the 3D printing concrete and the processing technology of the coastal special-shaped structure described in Example 3. FIG.
具体实施方式detailed description
应该指出，以下详细说明都是例示性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed description is exemplary and intended to provide further explanation of the invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural as well, furthermore, it is to be understood that when the terms "comprising" and/or "including" are used in this specification, it indicates that There are features, steps, operations, devices, components and/or combinations thereof.
针对现有技术的上述不足，本发明提供了一种3D打印混凝土、加工工艺及其在滨海异型结构快速制造中的应用。将GO-PVAH在FA表面合成，以外加剂水溶液媒介有效延缓GO-PVAH@FA加入纳米再生混凝土时间，组合使用低碱度复配水泥以及降低碱度的FA等掺合料，创新性规避GO遇强碱环境脱氧的瓶颈问题。通过GO-PVAH外裹FA媒介表面、再生骨料自养护以及FA的滚珠润滑效应实现纳米再生混凝土浆料触变性能、经时流变、保水功能实现；利用GO纳米模板、纤维桥联及复配水泥早强快凝效应综合实现纳米再生混凝土持续早强与抗裂增韧功能；通过GO-PVAH及再生骨料内养护、复配水泥微膨胀及FA减缩效应实现纳米再生混凝土界面体积稳定效能；发挥GO-PVAH微电容器储能效应规避3D打印滨海结构中钢纤维腐蚀微电池的形成，实现钢筋腐蚀自免疫效能，创新地同步实现滨海异型结构3D打印用纳米再生混凝土可打印建造性及硬化体早强体积稳定、抗裂增韧及腐蚀自免疫效能；同步拓宽固废资源化利用，最终在滨海异型结构快速制造领域蕴含着巨大的经济与环保效益。In view of the above-mentioned deficiencies of the prior art, the present invention provides a 3D printing concrete, a processing technology and its application in the rapid manufacture of coastal special-shaped structures. Synthesize GO-PVAH on the surface of FA, and effectively delay the time of adding GO-PVAH@FA to the nano-recycled concrete as an admixture in aqueous solution. Combined with low-alkalinity compound cement and FA and other admixtures with reduced alkalinity, the GO is innovatively avoided. The bottleneck problem of deoxidation in strong alkali environment. The thixotropic properties, time-dependent rheology, and water retention of the nano-recycled concrete slurry were realized by GO-PVAH wrapped on the surface of FA medium, the self-curing of recycled aggregates and the ball lubrication effect of FA; the use of GO nano-templates, fiber bridges and composite materials The early-strength and fast-setting effect of the mixed cement comprehensively realizes the continuous early strength and crack resistance and toughening functions of the nano-recycled concrete; the interfacial volume stability of the nano-recycled concrete is realized through the internal curing of GO-PVAH and recycled aggregate, the micro-expansion of the composite cement and the shrinkage reduction effect of FA. ; Make use of the energy storage effect of GO-PVAH microcapacitors to avoid the formation of steel fiber corrosion microbatteries in 3D printed coastal structures, realize the self-immunity effect of steel corrosion, and innovatively and simultaneously realize the printability and hardening of nano-regenerated concrete for 3D printing of coastal special-shaped structures. Body early strength and volume stability, crack resistance and toughening and corrosion self-immunity performance; Simultaneously expand the utilization of solid waste resources, and ultimately contain huge economic and environmental benefits in the field of coastal special-shaped structure rapid manufacturing.
本发明第一方面，提供一种滨海异型结构3D打印混凝土，所述滨海异型结构3D打印混凝土由以下重量份的原料组成：复配水泥1份、再生砂1-2份、粉煤灰(FA)0.05-0.2份、聚乙烯醇(PVA)0.005-0.05份、氧化石墨烯(GO)0.0002-0.002份、钢纤维0.01-0.05份、有机纤维0.005-0.02份、减水剂0.005-0.01份、调凝剂0.005-0.01份、矿物掺合料0-0.05份和水0.3-0.5份；所述PVA中还具有氧化剂和催化剂。In a first aspect of the present invention, there is provided a 3D printing concrete of a coastal special-shaped structure, the 3D printing concrete of a coastal special-shaped structure is composed of the following parts by weight of raw materials: 1 part of compound cement, 1-2 parts of recycled sand, fly ash (FA) ) 0.05-0.2 part, polyvinyl alcohol (PVA) 0.005-0.05 part, graphene oxide (GO) 0.0002-0.002 part, steel fiber 0.01-0.05 part, organic fiber 0.005-0.02 part, water reducing agent 0.005-0.01 part, 0.005-0.01 part of setting modifier, 0-0.05 part of mineral admixture and 0.3-0.5 part of water; the PVA also has an oxidant and a catalyst.
优选的，所述复配水泥由高贝利特硫铝酸盐水泥(HBSC)、硅酸盐水泥、石膏以1：(0.65-1.25)：(0-0.15)重量份数比混合而成。Preferably, the compound cement is prepared by mixing high Belite sulfoaluminate cement (HBSC), Portland cement and gypsum in a ratio of 1:(0.65-1.25):(0-0.15) by weight.
该配方得到的复配水泥具有快凝早强特点，配合FA的滚珠润滑特点有助于相应纳米再生混凝土可打印与可建造功能实现。The compound cement obtained by this formula has the characteristics of fast setting and early strength, and the ball lubrication characteristics of FA are helpful for the realization of the printable and buildable functions of the corresponding nano-regenerated concrete.
优选的，所述再生砂中包括粗砂、中砂、细砂及超细砂；其中，所述中砂率为27％-33％。Preferably, the reclaimed sand includes coarse sand, medium sand, fine sand and ultra-fine sand; wherein, the medium sand ratio is 27%-33%.
进一步优选的，所述粗砂为细度模数为3.7-3.1，平均粒径为0.5mm以上的粗砂。Further preferably, the coarse sand is coarse sand with a fineness modulus of 3.7-3.1 and an average particle size of 0.5 mm or more.
进一步优选的，所述中砂为细度模数为3.0-2.3，平均粒径为0.5mm-0.35mm的中砂。Further preferably, the medium sand is medium sand with a fineness modulus of 3.0-2.3 and an average particle size of 0.5mm-0.35mm.
进一步优选的，所述细砂为细度模数为2.2-1.6，平均粒径为0.35mm-0.25mm的细砂。Further preferably, the fine sand is fine sand with a fineness modulus of 2.2-1.6 and an average particle size of 0.35mm-0.25mm.
进一步优选的，所述超细砂为细度模数为1.5-0.7，平均粒径为0.25mm以下的超细砂。Further preferably, the ultrafine sand is ultrafine sand with a fineness modulus of 1.5-0.7 and an average particle size of 0.25 mm or less.
进一步优选的，所述粗砂、中砂、细砂及超细砂的质量比为1：(1.1-2.0)：(1-1.5)：(1-1.5)；该配比下的组分混合后能够实现拥有良好颗粒级配曲线。Further preferably, the mass ratio of the coarse sand, medium sand, fine sand and ultra-fine sand is 1:(1.1-2.0):(1-1.5):(1-1.5); the components under this ratio are mixed Afterwards, a good particle gradation curve can be achieved.
本发明中再生砂的具体类型并不作特殊的限定，在一些实施例中，所述再生砂为拆除建筑垃圾或工业废渣经破碎与颗粒整形后，满足JC/T2548-2019规范中的再生砂。利用再生砂有效提升纳米再生混凝土浆料自养护效应，同步拓宽固废资源化利用。The specific type of reclaimed sand in the present invention is not particularly limited. In some embodiments, the reclaimed sand is reclaimed sand that meets the JC/T2548-2019 specification after crushing and particle shaping of construction waste or industrial waste. The use of recycled sand can effectively improve the self-maintenance effect of nano-recycled concrete slurry, and simultaneously expand the utilization of solid waste resources.
优选的，所述FA为GB/T 1596-2017标准中规定的烧失量≤5％的I级FA，以获得较优的滚珠润滑效应。Preferably, the FA is a grade I FA with a loss on ignition ≤5% specified in the GB/T 1596-2017 standard, so as to obtain a better ball lubrication effect.
优选的，所述PVA为平均聚合度为500～600、醇解度为88％的PVA水溶液；将GO分散在PVA水溶液，形成稳定的GO-PVA预聚体液。Preferably, the PVA is a PVA aqueous solution with an average polymerization degree of 500-600 and an alcoholysis degree of 88%; GO is dispersed in the PVA aqueous solution to form a stable GO-PVA prepolymer solution.
优选的，所述PVA氧化剂、PVA催化剂分别为中国专利CN103450489或CN105885064A中所提及的高碘酸钠、高锰酸钾或氯酸钾，浓盐酸、稀硫酸、稀硝酸或硼酸中的一种，以通过原位聚合插层工艺，在GO片层结构插层PVA预聚体。Preferably, the PVA oxidant and the PVA catalyst are respectively sodium periodate, potassium permanganate or potassium chlorate mentioned in Chinese patent CN103450489 or CN105885064A, one of concentrated hydrochloric acid, dilute sulfuric acid, dilute nitric acid or boric acid, with The PVA prepolymer was intercalated in the GO sheet structure through an in-situ polymerization intercalation process.
优选的，所述GO为单层率≥90％、含氧量35～45％的GO粉料或浓度0.05～10mg/mL的水分散液；其中用GO水分散液时，按浓度比例计算水分散液中的GO质量，相应水分散液中的水计算到所述3D打印混凝土所用水总量中。Preferably, the GO is a GO powder with a monolayer rate of ≥90% and an oxygen content of 35-45% or an aqueous dispersion with a concentration of 0.05-10 mg/mL; when using a GO aqueous dispersion, the water is calculated according to the concentration ratio. The mass of GO in the dispersion, the water in the corresponding aqueous dispersion was calculated into the total amount of water used in the 3D printed concrete.
本发明中对减水剂的具体类型并不作特殊的限定，市面销售产品均可满足本 发明中所述制备滨海异型结构的使用要求。在一些具体实施方式中，所述减水剂为聚羧酸类高效减水剂、早强型聚羧酸类减水剂、萘系磺酸钠高效减水剂或密胺树脂类高效减水剂其中的一种或几种的优化组合。In the present invention, the specific type of the water-reducing agent is not particularly limited, and the commercially available products can all meet the use requirements for preparing the coastal special-shaped structure described in the present invention. In some specific embodiments, the water reducing agent is a polycarboxylate superplasticizer, an early-strength polycarboxylate superplasticizer, a sodium naphthalene sulfonate superplasticizer or a melamine resin superplasticizer One or more optimal combinations of the agents.
优选的，所述调凝剂为无水硫酸钠、三乙醇胺、纳米C-S-H晶核其中的一种。本发明提供的滨海异型3D打印混凝土通过调凝剂等外加剂有利于混凝土速凝，将有效保障纳米再生混凝土快速凝结功能的实现。Preferably, the coagulation adjusting agent is one of anhydrous sodium sulfate, triethanolamine, and nano-C-S-H crystal nucleus. The coastal special-shaped 3D printing concrete provided by the invention is conducive to the rapid setting of concrete through admixtures such as setting modifiers, and will effectively ensure the realization of the rapid setting function of the nano-recycled concrete.
本发明采用钢纤维，其具体来源并无特殊限定，所述钢纤维材料一般采用钢加工产业的生产废料。出于购买方便，节约成本的考虑，在本发明的一些实施方式中，所述钢纤维为切断钢纤维、剪切钢纤维、铣削型钢纤维、熔抽钢纤维其中的一种或几种的组合。The present invention uses steel fibers, the specific source of which is not particularly limited, and the steel fiber materials generally use the production wastes of the steel processing industry. For the sake of convenience of purchase and cost saving, in some embodiments of the present invention, the steel fibers are one or a combination of cutting steel fibers, shearing steel fibers, milling steel fibers, and melting and drawing steel fibers. .
本发明中所述有机纤维的具体来源同样并无特别限定，在一些实施方式中，所述有机纤维为短切类聚乙烯醇纤维、聚丙烯纤维、高密度聚乙烯纤维其中的一种或几种的组合。The specific source of the organic fibers in the present invention is also not particularly limited. In some embodiments, the organic fibers are one or more of chopped polyvinyl alcohol fibers, polypropylene fibers, and high-density polyethylene fibers. combination of species.
优选的，所述矿物掺合料为再生微粉、磨细矿渣、粉煤灰、火山灰或硅粉其中的一种或几种的组合。本发明对于上述再生微粉等原料的来源没有特别限定。Preferably, the mineral admixture is one or a combination of regenerated fine powder, ground slag, fly ash, pozzolan or silica fume. In the present invention, the source of the raw materials such as the above-mentioned regenerated fine powder is not particularly limited.
优选的，所述水为包括但不限于蒸馏水、去离子水、自来水或电解水中的一种，技术人员可根据施工情况进行选择。Preferably, the water includes, but is not limited to, distilled water, deionized water, tap water or electrolyzed water, which can be selected by technicians according to construction conditions.
本发明第二方面，提供一种滨海异型结构3D打印混凝土的加工工艺，所述加工工艺包括：将第一方面所述3D打印混凝土原料通过3D打印技术将所述混凝土干混料打印成型。A second aspect of the present invention provides a processing technology for 3D printing concrete with a coastal special-shaped structure. The processing technology includes: printing the concrete dry mix with the 3D printing concrete raw material described in the first aspect through a 3D printing technology.
优选的，所述混凝土干混料制备工艺具体步骤如下：将PVA与GO、氧化剂通过原位聚合插层法制成GO-PVA预聚体液；将FA、减水剂、催化剂及所述GO-PVAH预聚体液混合均匀，形成FA外裹GO-PVAH预聚体液，形成GO-PVAH@FA；将GO-PVAH@FA分散在含减水剂、调凝剂的溶液中，形成GO-PVAH@FA悬浮液；Preferably, the specific steps of the concrete dry mix preparation process are as follows: make PVA, GO and oxidant into a GO-PVA prepolymer liquid by in-situ polymerization and intercalation method; mix FA, water reducing agent, catalyst and the GO-PVAH The prepolymer solution is mixed evenly to form FA wrapped with GO-PVAH prepolymer solution to form GO-PVAH@FA; GO-PVAH@FA is dispersed in a solution containing water reducing agent and coagulant to form GO-PVAH@FA suspension;
将复配水泥、再生砂、钢纤维、有机纤维、矿物掺合料在料仓内机械混匀，形成纳米再生混凝土干混料。The composite cement, recycled sand, steel fiber, organic fiber and mineral admixture are mechanically mixed in the silo to form a nano-recycled concrete dry mix.
进一步优选的，所述GO-PVAH@FA悬浮液与所述纳米再生混凝土干混料在3D打印头内快速混合，设定3D机器臂打印规格(速度、流量及层厚)，逐层打印出不同层厚的纳米再生混凝土薄层，从而得到滨海异型结构。Further preferably, the GO-PVAH@FA suspension and the nano-recycled concrete dry mix are rapidly mixed in the 3D printing head, and the printing specifications (speed, flow rate and layer thickness) of the 3D robotic arm are set, and the printing is performed layer by layer. Thin layers of nano-recycled concrete with different layer thicknesses, resulting in a coastal special-shaped structure.
本发明提供的滨海异型结构3D打印混凝土的加工工艺，在效果较好的一些实施例方式中，所述加工工艺具体操作如下：The processing technology of the coastal special-shaped structure 3D printing concrete provided by the present invention, in some embodiments with better effects, the specific operations of the processing technology are as follows:
S1：将所述PVA溶于热水中配制PVA水溶液；在有所述PVA氧化剂存在条件下，将所述GO粉料或水分散液混入PVA水溶液，采用原位聚合插层工艺，在GO片层结构插层PVA预聚体，得到GO-PVA预聚体液；S1: Dissolve the PVA in hot water to prepare an aqueous PVA solution; in the presence of the PVA oxidant, mix the GO powder or water dispersion into the PVA aqueous solution, and use the in-situ polymerization intercalation process to prepare the GO sheet on the GO sheet. Layer structure intercalation PVA prepolymer to obtain GO-PVA prepolymer liquid;
S2：将所述FA、部分所述减水剂、所述PVA催化剂加入GO-PVA预聚体液，进一步采用热超声工艺，在所述FA颗粒表面外裹GO-PVA水凝胶(GO-PVAH)，得到GO-PVAH@FA并密封备用；S2: adding the FA, part of the water reducing agent and the PVA catalyst into the GO-PVA prepolymer solution, and further using a thermosonic process to coat the surface of the FA particles with GO-PVA hydrogel (GO-PVA ), get GO-PVAH@FA and seal it for later use;
S3：将上述GO-PVAH@FA加入剩余所述减水剂、所述调凝剂形成的外加剂水溶液中，高速搅匀，得到GO-PVAH@FA悬浮液；与此同时，将所述复配水泥、所述再生砂、所述钢纤维、所述有机纤维、所述矿物掺合料在料仓内机械混匀，形成纳米再生混凝土干混料；S3: adding the above GO-PVAH@FA into the admixture aqueous solution formed by the remaining water reducing agent and the coagulant, and stirring at high speed to obtain a GO-PVAH@FA suspension; at the same time, the compounded The mixed cement, the regenerated sand, the steel fiber, the organic fiber, and the mineral admixture are mechanically mixed in the silo to form a nano-regenerative concrete dry mix;
S4：确定不同规格尺寸、材料参数的滨海异型结构模型，确定3D机器臂打印规格要求(速度、流量及层厚)，采用本领域所熟知的方法将GO-PVAH@FA悬浮液与纳米再生混凝土干混料在3D打印头快速混合，逐层打印出不同层厚的纳米再生混凝土薄层，最终快速制造出滨海异型结构。S4: Determine the coastal special-shaped structure models of different sizes and material parameters, determine the printing specifications (speed, flow and layer thickness) of the 3D robotic arm, and use methods well-known in the art to combine GO-PVAH@FA suspension with nano-recycled concrete The dry mixture is quickly mixed in the 3D printing head, and the nano-recycled concrete thin layers with different layer thicknesses are printed layer by layer, and finally the coastal special-shaped structure is quickly produced.
在步骤S1中，可结合自动滴定法、旋转粘度计、UV-Vis分光度法、微观形貌法分析GO-PVA预聚体液中PVA插层效率及GO分散效果。In step S1, the PVA intercalation efficiency and GO dispersion effect in the GO-PVA prepolymer solution can be analyzed by combining automatic titration, rotational viscometer, UV-Vis spectrophotometry, and microtopography.
在步骤S2中，可分别结合冷冻干燥法、UV-Vis分光度法、TG-DSC综合热分析法、微观形貌法测GO-PVAH平衡溶胀率，透光度、结构交联度、微观分布形貌及致密度；结合乙醇排水法、TG-DSC综合热分析法、剥离强度法及膜厚仪法分别测GO-PVAH@FA的整体密度、含水量及有机物含量、界面抗剥离力及裹层厚度。In step S2, the GO-PVAH equilibrium swelling rate, light transmittance, structural cross-linking degree, and microscopic distribution can be measured in combination with freeze-drying method, UV-Vis spectrophotometry, TG-DSC comprehensive thermal analysis method, and microscopic topography method. Morphology and density; combined with ethanol drainage method, TG-DSC comprehensive thermal analysis method, peel strength method and film thickness meter method, the overall density, water content and organic content of GO-PVAH@FA, interfacial peel resistance and coating were measured respectively. layer thickness.
在步骤S4中，可以采用本领域技术人员所熟知的3D打印用纳米再生混凝土常规制备方法制备纳米再生混凝土，通过纳米再生混凝土流变仪(粘滞系数、剪切应力、触变环、触变面积)，全自动混凝土凝结时间及稠度测定仪(凝结时间、稠度、经时流变性)等来优选相应减水剂、调凝剂的类型及掺量。可结合本领域技术人员所熟知的纳米再生混凝土规模化可打印性及海洋耐久性能(抗冻融性能、抗氯离子侵蚀性能、抗硫酸盐腐蚀性能)测试方法开展该纳米再生混凝土的各项性能表征。可结合本领域技术人员所熟知含钢纤维的纳米再生混凝土电化学 性能表征方法开展其钢纤维腐蚀电位、极化电阻、腐蚀电流密度、电化学阻抗谱等电化学参数。采用本领域所熟知的方法，依照3D机器臂打印规格要求(速度、流量及层厚)，表征不同层厚的纳米再生混凝土薄层的层间粘结拉伸及层间剪切力等性能参数。并可以通过本领域技术人员所熟悉的超声回波或雷达波无损探测等方法评价不同层数纳米再生混凝土的施工质量以及冻融循环、离子侵蚀、硫酸盐腐蚀作用下层间结合力劣化状况。In step S4, nano-regenerative concrete can be prepared by the conventional preparation method of nano-regenerative concrete for 3D printing well-known to those skilled in the art. Area), automatic concrete setting time and consistency tester (setting time, consistency, rheology with time), etc. to optimize the type and dosage of the corresponding water reducer and setting modifier. Various properties of the nano-recycled concrete can be carried out in combination with the large-scale printability and marine durability (freeze-thaw resistance, chloride ion resistance, sulfate corrosion resistance) test methods of nano-recycled concrete well-known to those skilled in the art characterization. Electrochemical parameters such as steel fiber corrosion potential, polarization resistance, corrosion current density, electrochemical impedance spectroscopy, etc. Using methods well known in the art, according to the 3D robotic arm printing specifications (speed, flow rate and layer thickness), the performance parameters such as interlayer bonding and tensile force and interlayer shear force of nano-recycled concrete thin layers with different layer thicknesses are characterized . The construction quality of nano-reclaimed concrete with different layers and the deterioration of interlayer bonding force under the action of freeze-thaw cycles, ion erosion, and sulfate corrosion can be evaluated by methods such as ultrasonic echoes or radar waves that are familiar to those skilled in the art.
本发明第三方面，提供第一方面所述滨海异型结构3D打印混凝土在制备滨海异型结构中的应用。A third aspect of the present invention provides an application of the coastal special-shaped structure 3D printing concrete described in the first aspect in the preparation of a coastal special-shaped structure.
优选的，所述滨海异型结构包括但不限于井盖、雨水篦子、地下管廊、卵型水槽、地铁管片、蜂窝梁、叠合梁/板等。Preferably, the coastal special-shaped structures include, but are not limited to, manhole covers, rainwater grate, underground pipe gallery, egg-shaped water tank, subway segment, honeycomb beam, laminated beam/slab, and the like.
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案，以下将结合具体的实施例详细说明本发明的技术方案，以下实施例中所述原料均为市售产品。In order to enable those skilled in the art to understand the technical solutions of the present invention more clearly, the technical solutions of the present invention will be described in detail below with reference to specific embodiments, and the raw materials described in the following examples are all commercially available products.
实施例1Example 1
本实施例中，提供一种滨海异型结构3D打印混凝土，所述滨海异型结构3D打印混凝土，包括以下组分：复配水泥、再生砂、粉煤灰(FA)、聚乙烯醇(PVA)、氧化石墨烯(GO)、钢纤维、有机纤维、减水剂、调凝剂、矿物掺合料和水；上述各组分的质量比为1：1：0.05：0.005：0.0002：0.01：0.005：(0.005-0.01)：0.005：0.01：0.3。In this embodiment, a 3D printing concrete for a special-shaped coastal structure is provided. The 3D printing concrete for a special-shaped coastal structure includes the following components: compound cement, recycled sand, fly ash (FA), polyvinyl alcohol (PVA), Graphene oxide (GO), steel fiber, organic fiber, water reducer, coagulant, mineral admixture and water; the mass ratio of the above components is 1:1:0.05:0.005:0.0002:0.01:0.005: (0.005-0.01): 0.005: 0.01: 0.3.
其中，复配水泥包括以下组分：高贝利特硫铝酸盐水泥(HBSC)、硅酸盐水泥、石膏，各组分的质量比为1：0.65：0.1；复配水泥快凝早强特点以及FA的滚珠润滑特点有助于相应纳米再生混凝土可打印与可建造功能实现。Among them, the compound cement includes the following components: high belite sulfoaluminate cement (HBSC), Portland cement, gypsum, the mass ratio of each component is 1:0.65:0.1; compound cement has quick setting and early strength The characteristics and the ball lubrication characteristics of FA contribute to the realization of the printable and buildable functions of the corresponding nano-recycled concrete.
所述再生砂中粗砂、中砂、细砂、超细砂的质量比为1：1.1：1：1。The mass ratio of coarse sand, medium sand, fine sand and ultrafine sand in the reclaimed sand is 1:1.1:1:1.
所述FA为GB/T 1596-2017标准中规定的烧失量≤5％的I级FA。The FA is Class I FA with loss on ignition ≤ 5% specified in the GB/T 1596-2017 standard.
所述PVA为平均聚合度为500～600、醇解度为88％的PVA水溶液；所述GO分散在PVA水溶液，形成稳定的GO-PVA预聚体液。The PVA is a PVA aqueous solution with an average polymerization degree of 500-600 and an alcoholysis degree of 88%; the GO is dispersed in the PVA aqueous solution to form a stable GO-PVA prepolymer solution.
所述PVA氧化剂、PVA催化剂分别为高碘酸钠、浓盐酸。The PVA oxidant and PVA catalyst are respectively sodium periodate and concentrated hydrochloric acid.
所述GO单层率≥90％、含氧量为40％的GO粉料。The GO powder with a GO monolayer rate of ≥90% and an oxygen content of 40%.
所述减水剂为聚羧酸类高效减水剂。The water reducing agent is a high-efficiency water reducing agent of polycarboxylic acid type.
所述调凝剂为无水硫酸钠。The coagulation regulator is anhydrous sodium sulfate.
所述钢纤维为切断钢纤维。The steel fibers are cut steel fibers.
所述有机纤维为高密度聚乙烯纤维。The organic fibers are high-density polyethylene fibers.
所述矿物掺合料为再生微粉、磨细矿渣以质量比1:1混合。The mineral admixture is regenerated fine powder and ground slag mixed in a mass ratio of 1:1.
所述水为自来水。The water is tap water.
实施例2Example 2
本实施例中，提供一种滨海异型结构3D打印混凝土，所述滨海异型结构3D打印混凝土，包括以下组分：复配水泥、再生砂、粉煤灰(FA)、聚乙烯醇(PVA)、氧化石墨烯(GO)、钢纤维、有机纤维、减水剂、调凝剂、矿物掺合料和水；上述各组分的质量比为1：2：0.2：0.05：0.002：0.05：0.02：0.01：0.01：0.05：0.5。In this embodiment, a 3D printing concrete for a special-shaped coastal structure is provided. The 3D printing concrete for a special-shaped coastal structure includes the following components: compound cement, recycled sand, fly ash (FA), polyvinyl alcohol (PVA), Graphene oxide (GO), steel fiber, organic fiber, water reducing agent, coagulant, mineral admixture and water; the mass ratio of the above components is 1:2:0.2:0.05:0.002:0.05:0.02: 0.01:0.01:0.05:0.5.
其中，复配水泥包括以下组分：高贝利特硫铝酸盐水泥(HBSC)、硅酸盐水泥、石膏，各组分的质量比为1：1.25：0.15。Wherein, the compound cement includes the following components: high Belite sulfoaluminate cement (HBSC), Portland cement, and gypsum, and the mass ratio of each component is 1:1.25:0.15.
所述再生砂中粗砂、中砂、细砂、超细砂的质量比为1：2.0：1.5：1.5。The mass ratio of coarse sand, medium sand, fine sand and ultrafine sand in the reclaimed sand is 1:2.0:1.5:1.5.
所述FA为GB/T 1596-2017标准中规定的烧失量≤5％的I级FA。The FA is Class I FA with loss on ignition ≤ 5% specified in the GB/T 1596-2017 standard.
所述PVA为平均聚合度为500～600、醇解度为88％的PVA水溶液；所述GO分散在PVA水溶液，形成稳定的GO-PVA预聚体液。The PVA is a PVA aqueous solution with an average polymerization degree of 500-600 and an alcoholysis degree of 88%; the GO is dispersed in the PVA aqueous solution to form a stable GO-PVA prepolymer solution.
所述PVA氧化剂、PVA催化剂分别为高锰酸钾、稀硫酸。The PVA oxidant and PVA catalyst are potassium permanganate and dilute sulfuric acid respectively.
所述GO单层率≥90％、含氧量为35％的GO粉料。The GO powder with a GO monolayer rate of ≥90% and an oxygen content of 35%.
所述减水剂为早强型聚羧酸类减水剂。The water-reducing agent is an early-strength polycarboxylic acid water-reducing agent.
所述调凝剂为三乙醇胺。The coagulation regulator is triethanolamine.
所述钢纤维为剪切钢纤维与铣削型钢纤维以质量比0.5：1混合。The steel fibers are sheared steel fibers and milled steel fibers mixed in a mass ratio of 0.5:1.
所述有机纤维为聚丙烯纤维。The organic fibers are polypropylene fibers.
所述矿物掺合料为粉煤灰。The mineral admixture is fly ash.
所述水为去离子水。The water is deionized water.
实施例3Example 3
本实施例中，提供一种滨海异型结构3D打印混凝土的加工工艺，具体包括以下步骤：In this embodiment, a processing technology for 3D printing concrete of a coastal special-shaped structure is provided, which specifically includes the following steps:
S1：将所述0.25kgPVA溶于5L、温度为70℃的热水中配制浓度为5％、平均 聚合度为500～600、醇解度为88％的PVA水溶液；在含有0.02kg的高碘酸钠(PVA氧化剂)的条件下，将0.025kg GO粉料混入上述PVA水溶液，采用原位聚合插层工艺，在GO片层结构插层PVA预聚体，得到GO-PVA预聚体液；S1: Dissolve the 0.25kg PVA in 5L of hot water with a temperature of 70°C to prepare a PVA aqueous solution with a concentration of 5%, an average degree of polymerization of 500-600, and an alcoholysis degree of 88%; Under the condition of sodium (PVA oxidant), 0.025kg of GO powder was mixed into the above-mentioned PVA aqueous solution, and the in-situ polymerization intercalation process was adopted to intercalate the PVA prepolymer in the GO sheet structure to obtain the GO-PVA prepolymer solution;
S2：将1.0kg的FA、0.1kg聚羧酸类高效减水剂、0.01kg浓盐酸(PVA催化剂)加入上述GO-PVA预聚体液，进一步采用油浴锅热超声分散工艺(油温100℃、频率10kHz、功率50W、超声时间30min)，在所述FA颗粒表面外裹GO-PVA水凝胶(GO-PVAH)，得到GO-PVAH@FA并密封备用；S2: Add 1.0kg of FA, 0.1kg of polycarboxylate superplasticizer, and 0.01kg of concentrated hydrochloric acid (PVA catalyst) to the above-mentioned GO-PVA prepolymer solution, and further adopt an oil bath thermoultrasonic dispersion process (oil temperature 100° C. , frequency 10kHz, power 50W, ultrasonic time 30min), wrap GO-PVA hydrogel (GO-PVAH) on the surface of the FA particles, obtain GO-PVAH@FA and seal it for later use;
S3：将上述GO-PVAH@FA加入剩余0.15kgPCA-I型聚羧酸类高效减水剂(购自江苏苏博特新材料股份有限公司)、0.3kg无水硫酸钠(市售)形成的外加剂水溶液中，高速搅匀，得到GO-PVAH@FA悬浮液；与此同时，将20kg复配水泥(由10kg的525型HBSC、9.5kg的P.O-52.5型硅酸盐水泥及0.5kg石膏组成)、40kg II类花岗岩质再生砂(取自青岛当地C40、28年龄期混凝土结构拆除建筑垃圾经破碎、颗粒整形制得，其平均表观密度为2860kg/m 3)(由8kg粗砂、12kg中砂、10kg细砂及10kg超细砂组成)、0.5kg磨细矿渣粉(取自表观密度为2930kg/m 3的本钢高炉重矿渣，并经球磨而得)，并加入1.0kg/m 3的剪切型钢纤维(长度为3-15mm，直径为0.12-0.25mm，抗拉强度≥2850MPa，莱芜市金恒通工程材料有限公司产)、0.5kg/m 3的聚乙烯醇纤维(线密度1.9g/cm 3、干断裂强度≥11.5MPa、干断裂伸长率≥4.0-9.0％、初始模量≥280MPa、长度6mm、当量直径≤14μm，山东菖源新材料科技有限公司产)，在HC-3DPRT型混凝土(砂浆)3D打印***(建研华测(杭州)科技有限公司产)的料仓内机械混匀，形成相应纳米再生混凝土干混料； S3: The above-mentioned GO-PVAH@FA is added to the remaining 0.15kg PCA-I type polycarboxylate superplasticizer (purchased from Jiangsu Subote New Materials Co., Ltd.), 0.3kg anhydrous sodium sulfate (commercially available) to form In the admixture aqueous solution, stir at high speed to obtain GO-PVAH@FA suspension; at the same time, mix 20kg of compound cement (consisting of 10kg of 525 type HBSC, 9.5kg of PO-52.5 type Portland cement and 0.5kg of gypsum). composition), 40kg Class II granite reclaimed sand (obtained from local C40, 28-year-old concrete structure demolition construction waste in Qingdao, crushed and reshaped, with an average apparent density of 2860kg/m 3 ) (from 8kg coarse sand, 12kg of sand, fine sand and 10kg 10kg ultra fine sand), 0.5kg powder slag (from an apparent density of 2930kg / m 3 BX blast furnace slag weight and obtained by ball milling), and added 1.0kg / m shear steel fiber 3 (length of 3-15mm, the diameter of 0.12-0.25mm, tensile strength ≥2850MPa, Laiwu City Hengtong Engineering materials Co. yield), 0.5kg / m 3 of polyvinyl alcohol fibers ( Linear density 1.9g/cm 3 , dry breaking strength ≥11.5MPa, dry breaking elongation ≥4.0-9.0%, initial modulus ≥280MPa, length 6mm, equivalent diameter ≤14μm, produced by Shandong Changyuan New Material Technology Co., Ltd.) , Mechanically mix in the silo of the HC-3DPRT concrete (mortar) 3D printing system (produced by Jianyan Huachen (Hangzhou) Technology Co., Ltd.) to form the corresponding nano-regenerative concrete dry mix;
S4：将上述GO-PVAH@FA悬浮液及依照水灰比0.45计算剩余蒸馏水加入相应3D打印用纳米再生混凝土干混料中，在HC-3DPRT型混凝土(砂浆)3D打印***料仓内机械混匀，制成可以3D打印用的纳米再生混凝土浆料。S4: Add the above GO-PVAH@FA suspension and the remaining distilled water calculated according to the water-cement ratio of 0.45 into the corresponding dry mix of nano-recycled concrete for 3D printing, and mechanically mix it in the silo of the HC-3DPRT type concrete (mortar) 3D printing system. The nano-recycled concrete slurry can be prepared for 3D printing.
确定混凝土(砂浆)3D打印***的打印头规格(喷嘴等效直径2.5cm)，平面打印速度为5cm/s、竖向提升速度为1.5cm/s、层厚2cm，结合雨水篦子结构参数(300mm×450mm×60mm)将上述制成的纳米再生混凝土拌合料逐层打印出滨海雨水篦子结构，***评价其快速制造、层间粘结与海洋耐久性能。Determine the print head specifications of the concrete (mortar) 3D printing system (nozzle equivalent diameter is 2.5cm), the plane printing speed is 5cm/s, the vertical lifting speed is 1.5cm/s, and the layer thickness is 2cm. Combined with the structural parameters of the rain grate (300mm × 450 mm × 60 mm) The above-mentioned nano-recycled concrete mixture was printed layer by layer to form a coastal rainwater grate substructure, and its rapid manufacturing, interlayer bonding and marine durability were systematically evaluated.
在步骤S1中，GO-PVA预聚体液中PVA插层效率及GO分散效果，如图1所 示。在步骤S2中，GO-PVAH@FA的溶胀率、裹层厚度分别为30％、65μm，；在步骤S4中，雨水篦子结构3D打印用纳米再生混凝土快速制造、层间粘结与海洋耐久性能如表1所示。In step S1, the PVA intercalation efficiency and GO dispersion effect in the GO-PVA prepolymer solution are shown in Figure 1. In step S2, the swelling rate and coating thickness of GO-PVAH@FA were 30% and 65 μm, respectively; in step S4, the nano-recycled concrete for 3D printing rain grate substructure was rapidly fabricated, interlayer bonding and marine durability. As shown in Table 1.
附图1展示了所述GO-PVA聚合插层及GO-PVAH@FA包覆结构示意图，GO-PVA水凝胶层包覆在FA颗粒表面，PVA聚合体有效插层GO片层结构，形成微电容器正负双电层，有效提升纳米再生混凝土海洋防腐性能。Figure 1 shows the schematic diagram of the GO-PVA polymer intercalation and GO-PVAH@FA coating structure. The GO-PVA hydrogel layer is coated on the surface of FA particles, and the PVA polymer effectively intercalates the GO sheet structure to form The positive and negative electric double layers of microcapacitors can effectively improve the marine anti-corrosion performance of nano-recycled concrete.
实施例4Example 4
本实施例的3D打印用纳米再生混凝土的制备工艺具体步骤如下：The specific steps of the preparation process of the nano-recycled concrete for 3D printing of the present embodiment are as follows:
S1：将所述0.5kg PVA溶于5L、温度为80℃的热水中配制浓度为10％、平均聚合度为500～600、醇解度为88％的PVA水溶液；在含有0.015kg的高锰酸钾(PVA氧化剂)的条件下，将10mg/mL的2L GO水分散液混入上述PVA水溶液，采用原位聚合插层工艺，在GO片层结构插层PVA预聚体，得到GO-PVA预聚体液；S1: Dissolve the 0.5kg PVA in 5L of hot water with a temperature of 80°C to prepare a PVA aqueous solution with a concentration of 10%, an average degree of polymerization of 500-600, and an alcoholysis degree of 88%; Under the condition of potassium manganate (PVA oxidant), 10mg/mL of 2L GO aqueous dispersion was mixed into the above PVA aqueous solution, and the in-situ polymerization intercalation process was used to intercalate PVA prepolymer in the GO sheet structure to obtain GO-PVA prepolymer fluid;
S2：将1.5kg的FA、0.2kg
Figure PCTCN2020105896-appb-000001
-510型早强型聚羧酸类减水剂(购自江苏苏博特新材料股份有限公司)、0.01kg稀硫酸(PVA催化剂)加入上述GO-PVA预聚体液，进一步采用油浴锅热超声分散工艺(油温120℃、频率20kHz、功率50W、超声时间45min)，在所述FA颗粒表面外裹GO-PVA水凝胶(GO-PVAH)，得到GO-PVAH@FA并密封备用； S2: 1.5kg of FA, 0.2kg
Figure PCTCN2020105896-appb-000001
-510 type early-strength polycarboxylate water-reducing agent (purchased from Jiangsu Subote New Materials Co., Ltd.), 0.01kg of dilute sulfuric acid (PVA catalyst) were added to the above GO-PVA prepolymer solution, and further heated in an oil bath. Ultrasonic dispersion process (oil temperature 120°C, frequency 20kHz, power 50W, ultrasonic time 45min), wrap GO-PVA hydrogel (GO-PVAH) on the surface of the FA particles to obtain GO-PVAH@FA and seal it for later use;
S3：将上述GO-PVAH@FA加入剩余0.1kg
Figure PCTCN2020105896-appb-000002
-510型早强型聚羧酸类减水剂、0.25kg柠檬酸形成的外加剂水溶液中，高速搅匀，得到GO-PVAH@FA悬浮液；与此同时，将25kg复配水泥(由12kg的525型HBSC、12kg的P.O 52.5硅酸盐水泥及1kg石膏组成)、35kgII类再生砂(取自表观密度为3160kg/m 3的本钢钢渣尾矿砂，其化学组成CaO＝35～38％，Fe 2O 3＝20～24％，SiO 2＝18～21％，Al 2O 3＝5～8％，MgO＝5～7％)(由8kg粗砂、12kg中砂、8kg细砂及7kg超细砂组成)、1kg粉煤灰(I级、青岛四方发电厂产)，并加入0.8kg/m 3的铣削型钢纤维(长度为10-60mm，直径为0.2-0.6mm，抗拉强度≥850MPa，莱芜市金恒通工程材料有限公司产)、0.6kg/m 3的聚丙烯纤维(线密度0.91g/cm 3、抗拉强度≥450MPa、极限伸长率≥10％、弹性模量≥3500MPa、长度12mm、当量直径≤100μm，山东菖源新材料科技有限公司产)，机械混合形成相应纳米再生混凝土干混料； S3: Add the above GO-PVAH@FA to the remaining 0.1kg
Figure PCTCN2020105896-appb-000002
-510 type early-strength polycarboxylate superplasticizer and 0.25kg citric acid in the admixture aqueous solution, stir at high speed to obtain GO-PVAH@FA suspension; at the same time, mix 25kg of compound cement (from 12kg the 525 HBSC, 12kg of PO 52.5 Portland cement and gypsum compositions 1kg), 35kgII class reclaimed sand (BX from an apparent density of slag tailing 3160kg / m 3, the chemical composition CaO = 35 ~ 38% , Fe 2 O 3 =20~24%, SiO 2 =18~21%, Al 2 O 3 =5~8%, MgO=5~7%) (consisting of 8kg coarse sand, 12kg medium sand, 8kg fine sand and 7kg ultra fine sand), ash 1kg (I grade, Qingdao four production plants), and added 0.8kg / m 3 milling steel fibers (length of 10-60mm, a diameter of 0.2-0.6 mm, a tensile strength ≥850MPa, produced by Laiwu Jinhengtong Engineering Materials Co., Ltd.), 0.6kg/m 3 polypropylene fiber (linear density 0.91g/cm 3 , tensile strength ≥ 450MPa, ultimate elongation ≥ 10%, elastic modulus ≥ 3500MPa, length 12mm, equivalent diameter ≤100μm, produced by Shandong Changyuan New Material Technology Co., Ltd.), mechanically mixed to form the corresponding nano-recycled concrete dry mix;
S4：将上述GO-PVAH@FA悬浮液及依照水灰比0.42计算剩余去离子水加入相 应3D打印用纳米再生混凝土干混料中，在HC-3DPRT型混凝土(砂浆)3D打印***料仓内机械混匀，制成可以3D打印用的纳米再生混凝土浆料。S4: Add the above GO-PVAH@FA suspension and the remaining deionized water calculated according to the water-cement ratio of 0.42 into the corresponding 3D printing nano-recycled concrete dry mix, in the HC-3DPRT type concrete (mortar) 3D printing system silo Mixing mechanically to make nano-recycled concrete slurry that can be used for 3D printing.
确定混凝土(砂浆)3D打印***的打印头规格(喷嘴等效直径3cm)，平面打印速度为6cm/s、竖向提升速度为2cm/s、层厚3cm，结合滨海井盖结构参数(Φ600mm×50mm)将上述制成的纳米再生混凝土拌合料逐层打印出滨海井盖结构，***评价其快速制造、层间粘结与海洋耐久性能。Determine the print head specifications of the concrete (mortar) 3D printing system (the equivalent diameter of the nozzle is 3cm), the plane printing speed is 6cm/s, the vertical lifting speed is 2cm/s, and the layer thickness is 3cm. Combined with the structural parameters of the coastal manhole cover (Φ600mm×50mm) ) The above-mentioned nano-recycled concrete mixture was printed layer by layer out of the coastal manhole cover structure, and its rapid manufacturing, interlayer bonding and marine durability were systematically evaluated.
在步骤S2中GO-PVAH@FA的溶胀率、裹层厚度分别为40％、50μm。在步骤S4中，圆形井盖结构该3D打印用纳米再生混凝土的快速制造、层间粘结与海洋耐久性能亦如表1所示。In step S2, the swelling ratio and coating thickness of GO-PVAH@FA were 40% and 50 μm, respectively. In step S4, the rapid manufacturing, interlayer bonding and marine durability of the nano-recycled concrete for 3D printing of the circular manhole cover structure are also shown in Table 1.
实施例5Example 5
本实施例的3D打印用纳米再生混凝土的制备工艺具体步骤如下：The specific steps of the preparation process of the nano-recycled concrete for 3D printing of the present embodiment are as follows:
S1：将所述0.3kgPVA溶于5L、温度为65℃的热水中配制浓度为6％、平均聚合度为500～600、醇解度为88％的PVA水溶液；在含有0.02kg的氯酸钾(PVA氧化剂)的条件下，将浓度为4mg/mL、5L的GO水分散液混入上述PVA水溶液，采用原位聚合插层工艺，在GO片层结构插层PVA预聚体，得到GO-PVA预聚体液；S1: dissolve the 0.3kg PVA in 5L of hot water with a temperature of 65°C to prepare a PVA aqueous solution with a concentration of 6%, an average degree of polymerization of 500 to 600, and an alcoholysis degree of 88%; in a solution containing 0.02kg of potassium chlorate ( Under the condition of PVA oxidant), a GO aqueous dispersion with a concentration of 4 mg/mL and 5 L was mixed into the above PVA aqueous solution, and the in-situ polymerization intercalation process was used to intercalate the PVA prepolymer in the GO sheet structure to obtain a GO-PVA prepolymer. polymer fluid;
S2：将1.2kg的FA、0.15kg的SBTJM-9型聚羧酸类与密胺树脂类组合高效减水剂(购自江苏苏博特新材料股份有限公司)、0.01kg硼酸(PVA催化剂)加入上述GO-PVA预聚体液，进一步采用油浴锅热超声分散工艺(油温100℃、频率20kHz、功率50W、超声时间60min)，在所述FA颗粒表面外裹GO-PVA水凝胶(GO-PVAH)，得到GO-PVAH@FA，其溶胀率、裹层厚度分别为50％、100μm，并密封备用；S2: Combine 1.2kg of FA, 0.15kg of SBTJM-9 type polycarboxylic acids and melamine resins as a superplasticizer (purchased from Jiangsu Subote New Materials Co., Ltd.), 0.01kg of boric acid (PVA catalyst) The above-mentioned GO-PVA prepolymer solution was added, and the thermal ultrasonic dispersion process in an oil bath was further adopted (oil temperature 100 °C, frequency 20 kHz, power 50 W, ultrasonic time 60 min), and GO-PVA hydrogel ( GO-PVAH) to obtain GO-PVAH@FA, whose swelling ratio and coating thickness were 50% and 100 μm, respectively, and sealed for use;
S3：将上述GO-PVAH@FA加入剩余0.15kg的SBTJM-9型聚羧酸类与密胺树脂类组合高效减水剂、0.3kg酒石酸形成的外加剂水溶液中，高速搅匀，得到GO-PVAH@FA悬浮液；与此同时，将25kg复配水泥(由12kg的625型HBSC、12kg的P.I 42.5硅酸盐水泥及1kg石膏组成)、40kg金尾矿II类再生砂(表观密度为2670kg/m 3，以SiO 2、Al 2O 3为主的莱州矿业有限公司金尾矿，并经破碎、颗粒整形而得)(由10kg粗砂、10kg中砂、10kg细砂及10kg超细砂组成)、1kg火山灰(100目，市售)，并加入1.0kg/m 3的熔抽型钢纤维(长度为13mm、直径为0.3mm、抗拉强度≥850MPa、弹性模量≥210GPa，保定市鑫火钢纤维制造有限 公司产)、0.5kg/m 3的高密度聚乙烯纤维(密度0.97g/cm 3、抗拉强度＝2.8-4N/tex，弹性模量＝91-140N/tex，伸长率＝3.5-3.7％，东莞市索维特特殊线带有限公司产)，在HC-3DPRT型混凝土(砂浆)3D打印***(建研华测(杭州)科技有限公司产)的料仓内机械混匀，形成相应纳米再生混凝土干混料； S3: Add the above GO-PVAH@FA into the admixture aqueous solution formed by the remaining 0.15kg of SBTJM-9 type polycarboxylic acid and melamine resin combination superplasticizer and 0.3kg tartaric acid, and stir at high speed to obtain GO- PVAH@FA suspension; at the same time, 25kg of compound cement (composed of 12kg of 625 type HBSC, 12kg of PI 42.5 Portland cement and 1kg of gypsum), 40kg of gold tailings type II reclaimed sand (apparent density of 2670kg/m 3 , gold tailings of Laizhou Mining Co., Ltd. mainly composed of SiO 2 and Al 2 O 3 , and obtained by crushing and particle shaping) (from 10kg coarse sand, 10kg medium sand, 10kg fine sand and 10kg ultrafine sand) composition sand), ash 1kg (100 mesh, commercially available), and added to 1.0kg / m 3 of steel melt pumping fibers (length 13mm, diameter 0.3mm, tensile strength ≥850MPa, elastic modulus ≥210GPa, Baoding Xinhuo Steel Fiber Manufacturing Co., Ltd.), 0.5kg/m 3 high-density polyethylene fiber (density 0.97g/cm 3 , tensile strength=2.8-4N/tex, elastic modulus=91-140N/tex, elongation Length = 3.5-3.7%, produced by Dongguan Sowert Special Wire and Belt Co., Ltd.), mechanically mixed in the silo of the HC-3DPRT type concrete (mortar) 3D printing system (produced by Jianyan Huachen (Hangzhou) Technology Co., Ltd.). to form the corresponding nano-recycled concrete dry mix;
S4：将上述GO-PVAH@FA悬浮液及依照水灰比0.35计算剩余电解水加入相应3D打印用纳米再生混凝土干混料中，在HC-3DPRT型工业级混凝土(砂浆)3D打印***料仓内机械混匀，制成可以3D打印用的纳米再生混凝土浆料。S4: Add the above GO-PVAH@FA suspension and the remaining electrolyzed water calculated according to the water-cement ratio of 0.35 into the corresponding dry mix of nano-recycled concrete for 3D printing. Internal mechanical mixing to make nano-recycled concrete slurry that can be used for 3D printing.
确定工业级混凝土(砂浆)3D打印***的打印头规格(喷嘴等效直径5cm)，平面打印速度为4cm/s、竖向提升速度为1.2cm/s、层厚1cm，结合卵形水槽结构参数(1500mm×450mm×300mm)将上述制成的纳米再生混凝土拌合料逐层打印出卵形水槽结构，***评价其快速制造、层间粘结与海洋耐久性能。Determine the print head specifications (nozzle equivalent diameter of 5cm) of the industrial-grade concrete (mortar) 3D printing system, the plane printing speed is 4cm/s, the vertical lifting speed is 1.2cm/s, and the layer thickness is 1cm, combined with the structural parameters of the oval water tank (1500mm×450mm×300mm) The oval water tank structure was printed layer by layer from the nano-recycled concrete mixture prepared above, and its rapid manufacturing, interlayer bonding and marine durability were systematically evaluated.
在步骤S2中GO-PVAH@FA溶胀率、裹层厚度分别为40％、50μm。在步骤S4中，卵形水槽结构该3D打印用纳米再生混凝土的快速制造、层间粘结与海洋耐久性能亦如表1所示。In step S2, the swelling ratio and coating thickness of GO-PVAH@FA were 40% and 50 μm, respectively. In step S4, the rapid fabrication, interlayer bonding and marine durability of the nano-recycled concrete for 3D printing of the oval water tank structure are also shown in Table 1.
实施例6Example 6
本实施例的制备方法同实施例3，不同之处在于，S3步骤中20kg复配水泥由10kg的525型HBSC、10kg的P.O 52.5硅酸盐水泥两部分组成，未含有石膏，相应矿物掺合料掺量为0kg。The preparation method of this example is the same as that of Example 3, the difference is that in step S3, 20kg of compound cement is composed of 10kg of 525 type HBSC and 10kg of PO 52.5 Portland cement, does not contain gypsum, and the corresponding minerals are blended The dosage of the material is 0kg.
在步骤S2中，GO-PVAH@FA的溶胀率、裹层厚度分别为30％、65μm。在步骤S4中，该3D打印用纳米再生混凝土的相关性能如表1所示。In step S2, the swelling ratio and coating thickness of GO-PVAH@FA were 30% and 65 μm, respectively. In step S4, the relevant properties of the nano-recycled concrete for 3D printing are shown in Table 1.
表1 实施例3-6中3D打印用纳米再生混凝土性能测试对比结果Table 1 Comparative results of performance testing of nano-recycled concrete for 3D printing in Examples 3-6
Figure PCTCN2020105896-appb-000003
Figure PCTCN2020105896-appb-000003
Figure PCTCN2020105896-appb-000004
Figure PCTCN2020105896-appb-000004
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种滨海异型结构3D打印混凝土，其特征在于，所述滨海异型结构3D打印混凝土由以下重量份的原料组成：复配水泥1份、再生砂1-2份、粉煤灰0.05-0.2份、聚乙烯醇0.005-0.05份、氧化石墨烯0.0002-0.002份、钢纤维0.01-0.05份、有机纤维0.005-0.02份、减水剂0.005-0.01份、调凝剂0.005-0.01份、矿物掺合料0-0.05份和水0.3-0.5份；所述PVA中还具有氧化剂和催化剂。A coastal special-shaped structure 3D printing concrete, characterized in that the coastal special-shaped structure 3D printing concrete is composed of the following parts by weight of raw materials: 1 part of compound cement, 1-2 parts of recycled sand, 0.05-0.2 parts of fly ash, 0.005-0.05 part of polyvinyl alcohol, 0.0002-0.002 part of graphene oxide, 0.01-0.05 part of steel fiber, 0.005-0.02 part of organic fiber, 0.005-0.01 part of water reducing agent, 0.005-0.01 part of coagulation modifier, mineral admixture 0-0.05 part and 0.3-0.5 part of water; the PVA also has an oxidant and a catalyst.
  2. 如权利要求1所述滨海异型结构3D打印混凝土，其特征在于，所述复配水泥由高贝利特硫铝酸盐水泥、硅酸盐水泥、石膏以1：(0.65-1.25)：(0-0.15)重量份数比混合而成。The 3D printing concrete for coastal special-shaped structures according to claim 1, wherein the compound cement is made of high belite sulfoaluminate cement, Portland cement, and gypsum in the form of 1:(0.65-1.25):(0 -0.15) The ratio of parts by weight is mixed.
  3. 如权利要求1所述滨海异型结构3D打印混凝土，其特征在于，所述再生砂中包括粗砂、中砂、细砂及超细砂；其中，所述中砂率为27％-33％；The 3D printing concrete for coastal special-shaped structures according to claim 1, wherein the reclaimed sand includes coarse sand, medium sand, fine sand and ultra-fine sand; wherein, the medium sand ratio is 27%-33%;
    优选的，所述粗砂为细度模数为3.7-3.1，平均粒径为0.5mm以上的粗砂；Preferably, the coarse sand is coarse sand with a fineness modulus of 3.7-3.1 and an average particle size of 0.5 mm or more;
    优选的，所述中砂为细度模数为3.0-2.3，平均粒径为0.5mm-0.35mm的中砂；Preferably, the medium sand is medium sand with a fineness modulus of 3.0-2.3 and an average particle size of 0.5mm-0.35mm;
    优选的，所述细砂为细度模数为2.2-1.6，平均粒径为0.35mm-0.25mm的细砂；Preferably, the fine sand is fine sand with a fineness modulus of 2.2-1.6 and an average particle size of 0.35mm-0.25mm;
    优选的，所述超细砂为细度模数为1.5-0.7，平均粒径为0.25mm以下的超细砂；Preferably, the ultrafine sand is ultrafine sand with a fineness modulus of 1.5-0.7 and an average particle size of less than 0.25mm;
    优选的，所述粗砂、中砂、细砂及超细砂的质量比为1：(1.1-2.0)：(1-1.5)：(1-1.5)。Preferably, the mass ratio of the coarse sand, medium sand, fine sand and ultrafine sand is 1:(1.1-2.0):(1-1.5):(1-1.5).
  4. 如权利要求1所述滨海异型结构3D打印混凝土，其特征在于，所述FA为GB/T 1596-2017标准中规定的烧失量≤5％的I级FA；The 3D printing concrete for coastal special-shaped structures according to claim 1, wherein the FA is a grade I FA with a loss on ignition ≤ 5% specified in the GB/T 1596-2017 standard;
    或所述PVA为平均聚合度为500～600、醇解度为88％的PVA水溶液；Or the PVA is a PVA aqueous solution with an average degree of polymerization of 500-600 and an alcoholysis degree of 88%;
    或所述PVA氧化剂、PVA催化剂分别为高碘酸钠、高锰酸钾或氯酸钾，浓盐酸、稀硫酸、稀硝酸或硼酸中的一种；Or described PVA oxidant, PVA catalyst are respectively sodium periodate, potassium permanganate or potassium chlorate, a kind of in concentrated hydrochloric acid, dilute sulfuric acid, dilute nitric acid or boric acid;
    或所述GO为单层率≥90％、含氧量35～45％的GO粉料或浓度0.05～10mg/mL的水分散液。Or the GO is a GO powder with a monolayer rate of ≥90% and an oxygen content of 35-45% or an aqueous dispersion with a concentration of 0.05-10 mg/mL.
  5. 如权利要求1所述滨海异型结构3D打印混凝土，其特征在于，所述减水剂为聚羧酸类高效减水剂、早强型聚羧酸类减水剂、萘系磺酸钠高效减水剂或密胺树脂类高效减水剂其中的一种或几种的组合；The 3D printing concrete of coastal special-shaped structures according to claim 1, wherein the water reducing agent is a polycarboxylate superplasticizer, an early-strength polycarboxylate superplasticizer, and a sodium naphthalene sulfonate superplasticizer. One or a combination of water agent or melamine resin superplasticizer;
    或，所述调凝剂为无水硫酸钠、三乙醇胺、纳米C-S-H晶核其中的一种。Or, the coagulation adjusting agent is one of anhydrous sodium sulfate, triethanolamine, and nano-C-S-H crystal nucleus.
  6. 如权利要求1所述滨海异型结构3D打印混凝土，其特征在于，所述钢纤维 为切断钢纤维、剪切钢纤维、铣削型钢纤维、熔抽钢纤维其中的一种或几种的组合；The coastal special-shaped structure 3D printing concrete according to claim 1, wherein the steel fiber is one or more combinations of cutting steel fiber, shearing steel fiber, milling steel fiber, and melting and drawing steel fiber;
    或，所述有机纤维为短切类聚乙烯醇纤维、聚丙烯纤维、高密度聚乙烯纤维其中的一种或几种的组合。Or, the organic fibers are one or a combination of chopped polyvinyl alcohol fibers, polypropylene fibers, and high-density polyethylene fibers.
  7. 如权利要求1所述滨海异型结构3D打印混凝土，其特征在于，所述矿物掺合料为再生微粉、磨细矿渣、粉煤灰、火山灰或硅粉其中的一种或几种的组合；The 3D printing concrete for coastal special-shaped structures according to claim 1, wherein the mineral admixture is one or a combination of regenerated fine powder, ground slag, fly ash, pozzolan or silica fume;
    或，所述水为包括但不限于蒸馏水、去离子水、自来水或电解水中的一种。Or, the water is one including but not limited to distilled water, deionized water, tap water or electrolyzed water.
  8. 一种滨海异型结构3D打印混凝土的加工工艺，其特征在于，所述加工工艺包括：将权利要求1-7任一项所述3D打印混凝土原料通过3D打印技术将所述混凝土干混料打印成型。A processing technology for 3D printing concrete of coastal special-shaped structures, characterized in that, the processing technology comprises: printing the dry concrete mixture with the 3D printing concrete raw material according to any one of claims 1-7 through 3D printing technology .
  9. 如权利要求8所述滨海异型结构3D打印混凝土的加工工艺，其特征在于，所述混凝土干混料制备工艺具体步骤如下：将PVA与GO、氧化剂通过原位聚合插层法制成GO-PVA预聚体液；将FA、减水剂、催化剂及所述GO-PVAH预聚体液混合均匀，形成FA外裹GO-PVAH预聚体液，形成GO-PVAH@FA；将GO-PVAH@FA分散在含减水剂、调凝剂的溶液中，形成GO-PVAH@FA悬浮液；将复配水泥、再生砂、钢纤维、有机纤维、矿物掺合料在料仓内机械混匀，形成纳米再生混凝土干混料；The processing technology of 3D printing concrete of coastal special-shaped structure according to claim 8, characterized in that, the specific steps of the concrete dry mix preparation process are as follows: PVA, GO, and oxidant are prepared by in-situ polymerization and intercalation method to prepare GO-PVA pre- polymer liquid; mix FA, water reducing agent, catalyst and the GO-PVAH prepolymer liquid evenly to form FA wrapped with GO-PVAH prepolymer liquid to form GO-PVAH@FA; disperse GO-PVAH@FA in the GO-PVAH@FA suspension is formed in the solution of water reducer and coagulant; the composite cement, recycled sand, steel fiber, organic fiber and mineral admixture are mechanically mixed in the silo to form nano-recycled concrete dry mix;
    优选的，所述GO-PVAH@FA悬浮液与纳米再生混凝土干混料在3D打印头内快速混合，设定3D机器臂打印规格，逐层打印出不同层厚的纳米再生混凝土薄层，从而得到滨海异型结构。Preferably, the GO-PVAH@FA suspension and the nano-recycled concrete dry mix are rapidly mixed in the 3D printing head, the printing specifications of the 3D robotic arm are set, and the nano-recycled concrete thin layers with different thicknesses are printed layer by layer, thereby Get a seaside profile.
  10. 权利要求1-7任一项所述滨海异型结构3D打印混凝土在制备滨海异型结构中的应用；The application of the 3D printing concrete of the coastal special-shaped structure according to any one of claims 1-7 in the preparation of the coastal special-shaped structure;
    优选的，所述滨海异型结构包括但不限于井盖、雨水篦子、地下管廊、卵型水槽、地铁管片、蜂窝梁、叠合梁/板等。Preferably, the coastal special-shaped structures include, but are not limited to, manhole covers, rainwater grate, underground pipe gallery, egg-shaped water tank, subway segment, honeycomb beam, laminated beam/plate and the like.
PCT/CN2020/105896 2020-07-10 2020-07-30 Coastal special-shaped structure 3d printing concrete, processing technology and use thereof WO2022007063A1 (en)

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