CN113264744A - Nano graphene concrete material for building 3D printing and preparation method thereof - Google Patents
Nano graphene concrete material for building 3D printing and preparation method thereof Download PDFInfo
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- CN113264744A CN113264744A CN202110750089.3A CN202110750089A CN113264744A CN 113264744 A CN113264744 A CN 113264744A CN 202110750089 A CN202110750089 A CN 202110750089A CN 113264744 A CN113264744 A CN 113264744A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 138
- 239000000463 material Substances 0.000 title claims abstract description 94
- 238000010146 3D printing Methods 0.000 title claims abstract description 76
- 239000004567 concrete Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004568 cement Substances 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 23
- 239000011707 mineral Substances 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 20
- 230000008719 thickening Effects 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 18
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011398 Portland cement Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
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- 239000011324 bead Substances 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000010881 fly ash Substances 0.000 claims description 3
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- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
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- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- 239000012802 nanoclay Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
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- 229920000570 polyether Polymers 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 35
- 238000000034 method Methods 0.000 abstract description 16
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- 239000002086 nanomaterial Substances 0.000 description 5
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- 238000005054 agglomeration Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
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- 125000003636 chemical group Chemical group 0.000 description 2
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- AGWMJKGGLUJAPB-UHFFFAOYSA-N aluminum;dicalcium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Ca+2].[Ca+2].[Fe+3] AGWMJKGGLUJAPB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 229910001653 ettringite Inorganic materials 0.000 description 1
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- 238000005469 granulation Methods 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 238000010257 thawing Methods 0.000 description 1
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- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/022—Carbon
- C04B14/026—Carbon of particular shape, e.g. nanotubes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention provides a nano graphene concrete material for 3D printing of a building and a preparation method thereof, wherein the nano graphene concrete material for 3D printing of the building comprises, by weight, 100 parts of cement, 0.1-50 parts of dense filler, 0.1-30 parts of mineral admixture, 0.01-0.15 part of graphene oxide, 0.1-2.5 parts of dispersing agent, 0.1-3.0 parts of thixotropic agent, 0.1-1.5 parts of accelerating agent, 0.1-2.0 parts of thickening and water-retaining agent, 0.01-0.1 part of defoaming agent and 0.1-2.0 parts of fiber. The nano graphene concrete material for building 3D printing provided by the invention has adjustable setting time and better fluidity, and can obtain early strength in the printing process so as to ensure the continuous printing; the waterproof performance is high; the printing precision is better, and the high-precision building component can be printed.
Description
Technical Field
The invention relates to the technical field of building 3D printing materials, in particular to a nano graphene concrete material for building 3D printing and a preparation method thereof.
Background
3D printing is a technique for manufacturing three-dimensional products by adding material layer by a 3D printing device according to a designed 3D model, and this layer-by-layer build-up molding technique is also called additive manufacturing.
The 3D printing material is an important material basis for the development of the 3D printing technology, and the development of the material determines whether the 3D printing can be widely applied or not to some extent. The concrete is used as a building material with the largest usage amount, and the research on the application of the high-performance concrete to building 3D printing has great practical significance. The nanometer material is the most vigorous research direction in the current new material research field, and has very important influence on future social development, economic happiness and national strength. The nano material is a microscopic material with the particle size of nano level (1-100nm), and the particle size of the microscopic material is larger than that of the atomic cluster particles and smaller than that of the micro powder particles. Has surface effect, quantum granulation effect, small size effect and macroscopic tunnel effect which are not possessed by macroscopic material.
Graphene is a nanomaterial with a special two-dimensional structure, and is widely used in composite materials due to good physicochemical properties. Due to the in-plane sp2 hybrid structure of graphene, the bonding capability with the matrix is weaker, and graphene oxide is used as a reinforcing phase of the matrix more often. Graphene Oxide (GO) is a two-dimensional lamellar nanostructure with ultra-large specific surface area, ultra-strong mechanical properties and flexibility. Contains a large number of reactive groups in its structure: hydroxyl (-OH), carboxyl (-COOH) and epoxy (-O-). The existence of the active groups enables the graphene oxide to have good hydrophilicity, the graphene oxide can be easily dispersed in water to prepare nano dispersion liquid, and the graphene oxide can be easily compounded with other compounds to form an intercalation compound.
The existing cementing material for 3D printing of buildings generally has long or too short bonding time, and the setting time cannot be freely regulated so as to meet the requirement of printing and curing a lamination or is cured at an extrusion head in the printing process to cause blockage; the fluidity of the existing mixed gel material for printing is not coordinated with that of extrusion printing, and the excessive or insufficient fluidity of the existing mixed gel material for printing causes obstacles of different degrees on the extrusion printing; the existing gel material for printing can not obtain early strength in a short time in the printing process, and the continuous printing is difficult to ensure; because extrusion printing is a lamination accumulation mode, the adhesive force between printing layers of the existing cementing material for printing is too low in the printing operation, and the printed matter cannot be ensured to have leakage prevention water and higher interlayer adhesive force strength (namely the tensile strength in the vertical direction of printing); the existing cementing material for printing has poor printing precision and cannot print high-precision building components.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a nano graphene concrete material for building 3D printing and a preparation method thereof, and aims to solve the problem that the setting time of the existing cementing material for 3D printing cannot be freely regulated.
The technical scheme of the invention is as follows:
the nano graphene concrete material for 3D printing of buildings comprises, by weight, 100 parts of cement, 0.1-50 parts of dense filler, 0.1-30 parts of mineral admixture, 0.01-0.15 part of graphene oxide, 0.1-2.5 parts of dispersing agent, 0.1-3.0 parts of thixotropic agent, 0.1-1.5 parts of accelerating agent, 0.1-2.0 parts of water retention agent for thickening, 0.01-0.1 part of defoaming agent and 0.1-2.0 parts of fiber.
The nano graphene concrete material for 3D printing of buildings comprises, by weight, 100 parts of cement, 0.1-40 parts of dense filler, 0.1-20 parts of mineral admixture, 0.01-0.10 part of graphene oxide, 0.1-2.0 parts of dispersing agent, 0.1-2.5 parts of thixotropic agent, 0.1-1.2 parts of accelerating agent, 0.1-2.0 parts of water retention agent for thickening, 0.01-0.05 part of defoaming agent and 0.1-2.0 parts of fiber.
The nano graphene concrete material for building 3D printing is characterized in that the cement is one or more of composite portland cement, sulphoaluminate cement and high aluminate cement.
The nano graphene concrete material for building 3D printing is characterized in that the dense filler is one or two of quartz sand or glass beads with a 60-mesh sieve.
The nano graphene concrete material for 3D printing of the building is characterized in that the mineral admixture is one or more of fly ash, wollastonite powder and aluminum slag powder.
The nano graphene concrete material for building 3D printing is characterized in that the average number of graphene oxide layers is 5-6, and the specific surface area is 40-60m2/g。
The nano graphene concrete material for building 3D printing is characterized in that the dispersant is one or two of a polycarboxylic acid water reducer and lignosulfonate; and/or the thixotropic agent is one or more of nano clay, organic bentonite and magnesium aluminum silicate.
The nano graphene concrete material for building 3D printing is characterized in that the accelerating agent is one or more of calcium fluoroaluminate, aluminum oxide clinker and polyacrylic acid; and/or the thickening and water-retaining agent is one or more of carboxymethyl hydroxyethyl cellulose, polyacrylamide and hydroxypropyl methyl cellulose ether.
The nano graphene concrete material for building 3D printing is characterized in that the defoaming agent is one or two of polyether and higher alcohol; and/or the fiber is one or more of carbon fiber, polyvinyl alcohol fiber and polypropylene fiber.
The preparation method of the nano graphene concrete material for building 3D printing comprises the following steps:
dispersing graphene oxide powder into deionized water to prepare a graphene oxide solution;
adding a dispersing agent into the graphene oxide solution, and mixing to obtain a graphene oxide dispersion liquid;
sequentially adding a thickening water-retaining agent and a defoaming agent into the graphene oxide dispersion liquid, and uniformly stirring to obtain a mixed graphene oxide solution;
mixing and uniformly stirring cement, a dense filler, a mineral admixture, a thixotropic agent, an accelerator and fibers to obtain a powdery cement-based material;
and adding the mixed graphene oxide solution into the powdery cement-based material and stirring to prepare the nano graphene concrete material for 3D printing of the building.
Has the advantages that: according to the invention, the graphene oxide nano material is added into the concrete material for 3D printing of the building, and is a lamellar substance with the thickness of nano grade, which is obtained by oxidizing and ultrasonically dispersing graphite, so that the graphene oxide nano material has an ultra-large specific surface area and good flexibility, and the lamellar layer contains chemical groups such as hydroxyl, carboxyl, epoxy and the like, and can chemically react with cement; the graphene oxide has a regulation function on cement hydration products and aggregation states, has a tendency of promoting the formation of regular cement hydration products and aggregation structures, can greatly improve the mechanical property of a cement-based composite material, and can regulate and control the setting time by controlling the addition amount of the graphene oxide; the graphene oxide surface and the cement-based surface have good bonding effect, can be uniformly dispersed in the cement-based material, and cannot generate slurry agglomeration.
Drawings
Fig. 1 is a flowchart of a preferred embodiment of a preparation method of a nano graphene concrete material for building 3D printing according to the present invention.
Detailed Description
The invention provides a nano graphene concrete material for building 3D printing and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a nano graphene concrete material for 3D printing of buildings, which comprises, by weight, 100 parts of cement, 0.1-50 parts of dense filler, 0.1-30 parts of mineral admixture, 0.01-0.15 part of graphene oxide, 0.1-2.5 parts of dispersing agent, 0.1-3.0 parts of thixotropic agent, 0.1-1.5 parts of accelerating agent, 0.1-2.0 parts of thickening and water-retaining agent, 0.01-0.1 part of defoaming agent and 0.1-2.0 parts of fiber.
The nano graphene concrete material for 3D printing in the building provided by the embodiment has wide raw material sources and low cost, and the main components of the nano graphene concrete material are cement, dense filler and mineral admixture, wherein the cement is one or more of composite portland cement, sulphoaluminate cement and high aluminate cement, but not limited thereto; the dense filler is one or two of quartz sand or glass beads of a 60-mesh sieve, but is not limited to the above; the mineral admixture is one or more of fly ash, wollastonite powder and aluminum slag powder, but is not limited thereto.
Taking the sulphoaluminate cement as an example, the anhydrous calcium sulphoaluminate and dicalcium silicate in the sulphoaluminate cement mineral can be hydrated quickly to form a large amount of hydrate with lower solubility, namely high-sulfur hydrated calcium sulphoaluminate (ettringite), and simultaneously, the dicalcium silicate of another mineral generates Ca (OH) after hydration2And calcium silicate hydrate (C-S-H gel), the two-mineral hydration process being:
3CaO·3Al2O3·CaSO4+2(CaSO4·H20)+34H20→3CaO·A1203·3CaSO4·32H2O+2(Al2O3·3H2O)；
2CaO·SiO2+2H2O→CaO-SiO2-H2O+Ca(OH)2；
Al2O3·3H2O+3Ca(OH)2+3CaSO4·H2O+20H2O→3CaO·Al2O3·3CaSO4·32H2O。
taking portland cement as an example, the main mineral composition of the portland cement is as follows: tricalcium silicate, dicalcium silicate, tricalcium aluminate and tetracalcium aluminoferrite; the hydration speed of various clinker minerals is C3A>C3S>C4AF>C2S, the later strength change after solidification is as follows in sequence: c2S>C3S>C4AF>C3A。
In this embodiment, the average number of graphene oxide layers added to the nano graphene concrete material for building 3D printing is5-6 layers with average thickness of 3nm, lamella size of 5-15 μm, and specific surface area of 40-60m2(ii) in terms of/g. The graphene oxide is a lamellar substance with the thickness of nano grade obtained by oxidizing and ultrasonically dispersing graphite, has an ultra-large specific surface area and good flexibility, contains chemical groups such as hydroxyl, carboxyl, epoxy and the like on a lamellar layer, and can chemically react with cement; researches find that the graphene oxide has a regulating effect on cement hydration products and aggregation states, has a tendency of promoting the formation of regular cement hydration products and aggregation structures, can greatly improve the mechanical property of the cement-based composite material, and can regulate and control the setting time by controlling the addition amount of the graphene oxide. The graphene oxide surface and the cement-based surface have good bonding effect, can be uniformly dispersed in the cement-based material, and cannot generate the phenomenon of slurry agglomeration. In addition, the graphene oxide is added into the concrete, so that additional secondary pollution is not generated, and the graphene oxide is harmless to human bodies.
In this embodiment, the dispersant added to the nano graphene concrete material for building 3D printing is one or two of a polycarboxylic acid water reducer and a lignosulfonate, but is not limited thereto. The dispersing agent is also used as a water reducing agent in concrete, and the graphene oxide can be uniformly dispersed in a cement-based material without agglomeration and precipitation under the action of the dispersing agent; as the water reducing agent, molecules of the water reducing agent are directionally adsorbed on the surfaces of cement particles, so that the surfaces of the cement particles normally carry a negative charge to form an electrostatic repulsion effect, the cement particles are mutually dispersed, a flocculation structure is destroyed, and wrapped part of water is released to participate in flowing. Secondly, the dispersant has strong hydrophilicity, the formed adsorption film can form a stable intermolecular film with water molecules, the extrusion friction force is reduced, the fluidity and the workability are improved, the continuous extrusion performance is good, and the phenomenon of material breakage can be avoided due to continuous feeding.
In this embodiment, the thickening and water-retaining agent added to the nano graphene concrete material for building 3D printing is one or more of carboxymethyl hydroxyethyl cellulose, polyacrylamide and hydroxypropyl methyl cellulose ether, but is not limited thereto. The main action mechanism of the thickening and water-retaining agent is as follows: the hydrophobic main chain is associated with the surrounding water molecules through hydrogen bonds, so that the fluid volume of the polymer is increased, the free movement space of particles is reduced, and the viscosity of the system is increased. The increase in viscosity can also be achieved by entanglement of the molecular chains, as indicated by high viscosity at static and low shear, and low viscosity at high shear. The material has good plastic deformation resistance and bonding performance, and the phenomena of lateral deformation and large gaps among layers cannot occur in the printing process, so that potential safety hazards for buildings are avoided.
In this embodiment, the thixotropic agent added to the nano graphene concrete material for building 3D printing is one or more of nano clay, organic bentonite and magnesium aluminum silicate, but is not limited thereto. The thixotropic agent can form a hydrogen bond or a large specific surface area of some other structure with a polymer, and is characterized in that concrete slurry becomes thin under the action of shearing force, and is thickened by standing without the shearing force, so that the thixotropic agent plays a role of a lubricant, reduces the relative viscosity, improves the rheological property of a system, can improve the yield value of the system, and has obvious thixotropic thickening effect. The thixotropic agent additive increases the pumpability and the constructability of the concrete for 3D printing of buildings, prevents the paste from deforming and collapsing after extrusion printing, and ensures the volume stability of products.
In this embodiment, the fibers added into the nano graphene concrete material for building 3D printing are one or more of carbon fibers, polyvinyl alcohol fibers and polypropylene fibers, but are not limited thereto. The fiber can wrap more aggregates, has tight binding force with a cement matrix, has a disorderly distribution form which is greatly beneficial to weakening the stress of the cement matrix during plastic shrinkage and freeze thawing, and the shrinkage energy is dispersed to the fiber monofilament with high tensile strength and relatively low elastic modulus, so that the generation and development of micro cracks are inhibited, and the toughness and the crack resistance of the neat paste are effectively enhanced.
In some embodiments, the accelerating agent is one or more of calcium fluoroaluminate, aluminoxy clinker, and polyacrylic acid, but is not limited thereto; the defoaming agent is one or two of polyethers and higher alcohols, but is not limited thereto.
In some embodiments, the nano graphene concrete material for 3D printing of buildings comprises, by weight, 100 parts of cement, 0.1 to 40 parts of dense filler, 0.1 to 20 parts of mineral admixture, 0.01 to 0.10 part of graphene oxide, 0.1 to 2.0 parts of dispersing agent, 0.1 to 2.5 parts of thixotropic agent, 0.1 to 1.2 parts of accelerating agent, 0.1 to 2.0 parts of thickening water-retaining agent, 0.01 to 0.05 part of defoaming agent and 0.1 to 2.0 parts of fiber.
In some embodiments, there is also provided a method for preparing the nano graphene concrete material for 3D printing in buildings as described above, as shown in fig. 1, which includes the steps of:
s10, dispersing the graphene oxide powder into deionized water to prepare a graphene oxide solution;
s20, adding a dispersing agent into the graphene oxide solution, and mixing to obtain a graphene oxide dispersion liquid;
s30, sequentially adding a thickening water-retaining agent and a defoaming agent into the graphene oxide dispersion liquid, and uniformly stirring to obtain a mixed graphene oxide solution;
s40, mixing and uniformly stirring cement, a dense filler, a mineral admixture, a thixotropic agent, an accelerator and fibers to obtain a powdery cement-based material;
s50, adding the mixed graphene oxide solution into the powdery cement-based material, and stirring to obtain the nano graphene concrete material for building 3D printing.
In this embodiment, after the preparation of the nano graphene concrete material for 3D printing of the building is completed, a computer drawing software is used to draw a model drawing, then a special slicing software is used to introduce the drawing into a printer, and then the nano graphene concrete material for 3D printing of the building is remotely conveyed to a printing nozzle to perform 3D printing operation of the building, and after printing and forming, product maintenance is performed.
The following provides a further explanation of the nano graphene concrete material for building 3D printing, the preparation method and the performance thereof by specific examples:
example 1
Preparing the following substances in parts by weight:
the preparation method comprises the following steps: weighing 0.465 part of graphene oxide powder, adding 42 parts of deionized water to dilute and prepare a graphene oxide solution, slowly pouring a dispersing agent into the graphene oxide solution, and uniformly dispersing in an ultrasonic dispersion instrument to obtain a graphene oxide dispersion liquid;
adding a thickening water-retaining agent and a defoaming agent into the graphene oxide dispersion liquid in sequence, and uniformly stirring by using a magnetic stirrer to obtain a mixed graphene oxide solution;
sequentially adding cement, a dense filler, a mineral admixture, a thixotropic agent, an accelerator and fibers into a paste mixer, and fully and uniformly mixing for 3min to obtain a powdery graphene oxide cement-based material;
slowly adding the uniformly stirred mixed graphene oxide solution into the powdery graphene oxide cement-based material, and forcibly and uniformly stirring for 3min to prepare graphene oxide concrete slurry for 3D printing of the building;
drawing a model drawing by using computer drawing software, guiding the drawing paper into a printer by using special slicing software, remotely conveying the slurry to a printing nozzle, carrying out building 3D printing operation, and carrying out product maintenance after printing and forming.
The nano graphene oxide concrete material for building 3D printing is prepared by the component material process, has excellent operable time and good early strength. The extrusion is continuous, uniform and smooth, the lamination constructability is good, the printing surface is fine and smooth and has no crack, the damaged section is dense and has few air holes, and the method can be used for 3D printing building components and small building finished products with larger and higher precision at the room temperature of 15-45 ℃. The nano graphene oxide concrete material for 3D printing of the building is subjected to performance detection, and the result is as follows,
the initial setting time is 25min, and the final setting time is 45 min.
Compressive strength R3d＝37.9MPa，R7d＝51.8MPa，R28d＝70.6MPa。
Flexural strength R3d＝6.7MPa，R7d＝10.2MPa，R28d＝14.5MPa。
Example 2
Preparing the following substances in parts by weight:
the preparation method comprises the following steps: weighing 0.0700 part of graphene oxide powder, adding 44.8 parts of deionized water to dilute and prepare a graphene oxide solution, slowly pouring a dispersing agent into the graphene oxide solution, and uniformly dispersing in an ultrasonic dispersion instrument to obtain a graphene oxide dispersion solution;
adding a thickening water-retaining agent and a defoaming agent into the graphene oxide dispersion liquid in sequence, and uniformly stirring by using a magnetic stirrer to obtain a mixed graphene oxide solution;
sequentially adding cement, a dense filler, a mineral admixture, a thixotropic agent, an accelerator and fibers into a paste mixer, and fully and uniformly mixing for 3min to obtain a powdery graphene oxide cement-based material;
slowly adding the uniformly stirred mixed graphene oxide solution into the powdery graphene oxide cement-based material, and forcibly and uniformly stirring for 3min to prepare graphene oxide concrete slurry for 3D printing of the building;
drawing a model drawing by using computer drawing software, guiding the drawing paper into a printer by using special slicing software, remotely conveying the slurry to a printing nozzle, carrying out building 3D printing operation, and carrying out product maintenance after printing and forming.
The nano graphene oxide concrete material for building 3D printing is prepared by the component material process, has excellent operable time and good early strength. The extrusion is continuous, uniform and smooth, the lamination constructability is good, the printing surface is fine and smooth and has no crack, the damaged section is dense and has few air holes, and the method can be used for 3D printing building components and small building finished products with larger and higher precision at the room temperature of 15-45 ℃. The nano graphene oxide concrete material for 3D printing of the building is subjected to performance detection, and the result is as follows,
the initial setting time is 10min, and the final setting time is 25 min.
Compressive strength R3d＝44.5MPa，R7d＝59.7MPa，R28d＝74.1MPa。
Flexural strength R3d＝7.2MPa，R7d＝9.8MPa，R28d＝15.3MPa。
Example 3
Preparing the following substances in parts by weight:
the preparation method comprises the following steps: weighing 0.0945 part of graphene oxide powder, adding 43.2 parts of deionized water to dilute the graphene oxide powder to prepare a graphene oxide solution, slowly pouring a dispersing agent into the graphene oxide solution, and uniformly dispersing the graphene oxide solution in an ultrasonic dispersion instrument to obtain a graphene oxide dispersion liquid;
adding a thickening water-retaining agent and a defoaming agent into the graphene oxide dispersion liquid in sequence, and uniformly stirring by using a magnetic stirrer to obtain a mixed graphene oxide solution;
sequentially adding cement, a dense filler, a mineral admixture, a thixotropic agent, an accelerator and fibers into a paste mixer, and fully and uniformly mixing for 3min to obtain a powdery graphene oxide cement-based material;
slowly adding the uniformly stirred mixed graphene oxide solution into the powdery graphene oxide cement-based material, and forcibly and uniformly stirring for 3min to prepare graphene oxide concrete slurry for 3D printing of the building;
drawing a model drawing by using computer drawing software, guiding the drawing paper into a printer by using special slicing software, remotely conveying the slurry to a printing nozzle, carrying out building 3D printing operation, and carrying out product maintenance after printing and forming.
The nano graphene oxide concrete material for building 3D printing is prepared by the component material process, has excellent operable time and good early strength. The extrusion is continuous, uniform and smooth, the lamination constructability is good, the printing surface is fine and smooth and has no crack, the damaged section is dense and has few air holes, and the method can be used for 3D printing building components and small building finished products with larger and higher precision at the room temperature of 15-45 ℃. The nano graphene oxide concrete material for 3D printing of the building is subjected to performance detection, and the result is as follows,
the initial setting time is 15min, and the final setting time is 35 min.
Compressive strength R3d＝39.8MPa，R7d＝52.7MPa，R28d＝62.5MPa。
Flexural strength R3d＝6.1MPa，R7d＝8.5MPa，R28d＝12.3MPa。
Example 4
Preparing the following substances in parts by weight:
the preparation method comprises the following steps: weighing 0.0675 parts of graphene oxide powder, adding 43.2 parts of deionized water to dilute the graphene oxide powder to prepare a graphene oxide solution, slowly pouring a dispersing agent into the graphene oxide solution, and uniformly dispersing the graphene oxide solution in an ultrasonic dispersion instrument to obtain a graphene oxide dispersion liquid;
adding a thickening water-retaining agent and a defoaming agent into the graphene oxide dispersion liquid in sequence, and uniformly stirring by using a magnetic stirrer to obtain a mixed graphene oxide solution;
sequentially adding cement, a dense filler, a mineral admixture, a thixotropic agent, an accelerator and fibers into a paste mixer, and fully and uniformly mixing for 3min to obtain a powdery graphene oxide cement-based material;
slowly adding the uniformly stirred mixed graphene oxide solution into the powdery graphene oxide cement-based material, and forcibly and uniformly stirring for 3min to prepare graphene oxide concrete slurry for 3D printing of the building;
drawing a model drawing by using computer drawing software, guiding the drawing paper into a printer by using special slicing software, remotely conveying the slurry to a printing nozzle, carrying out building 3D printing operation, and carrying out product maintenance after printing and forming.
The nano graphene oxide concrete material for building 3D printing is prepared by the component material process, has excellent operable time and good early strength. The extrusion is continuous, uniform and smooth, the lamination constructability is good, the printing surface is fine and smooth and has no crack, the damaged section is dense and has few air holes, and the method can be used for 3D printing building components and small building finished products with larger and higher precision at the room temperature of 15-45 ℃. The nano graphene oxide concrete material for 3D printing of the building is subjected to performance detection, and the result is as follows,
the initial setting time is 8min, and the final setting time is 20 min.
Compressive strength R3d＝45.9MPa，R7d＝66.8MPa，R28d＝82.9MPa。
Flexural strength R3d＝8.1MPa，R7d＝11.2MPa，R28d＝15.7MPa。
It is to be understood that the foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The example embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various example embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. The nano graphene concrete material for 3D printing of buildings is characterized by comprising, by weight, 100 parts of cement, 0.1-50 parts of dense filler, 0.1-30 parts of mineral admixture, 0.01-0.15 part of graphene oxide, 0.1-2.5 parts of dispersing agent, 0.1-3.0 parts of thixotropic agent, 0.1-1.5 parts of accelerating agent, 0.1-2.0 parts of thickening and water-retaining agent, 0.01-0.1 part of defoaming agent and 0.1-2.0 parts of fiber.
2. The nano graphene concrete material for 3D printing in building according to claim 1, which comprises, by weight, 100 parts of cement, 0.1-40 parts of dense filler, 0.1-20 parts of mineral admixture, 0.01-0.10 part of graphene oxide, 0.1-2.0 parts of dispersing agent, 0.1-2.5 parts of thixotropic agent, 0.1-1.2 parts of accelerating agent, 0.1-2.0 parts of thickening and water-retaining agent, 0.01-0.05 part of defoaming agent and 0.1-2.0 parts of fiber.
3. The nano graphene concrete material for 3D printing in construction according to any one of claims 1 to 2, wherein the cement is one or more of composite portland cement, sulphoaluminate cement and homoaluminate cement.
4. The nano graphene concrete material for 3D printing in buildings according to any one of claims 1 to 2, wherein the dense filler is one or two of quartz sand or glass beads with a 60-mesh sieve.
5. The nano graphene concrete material for 3D printing in buildings according to any one of claims 1 to 2, wherein the mineral admixture is one or more of fly ash, wollastonite powder and aluminum slag powder.
6. The nano graphene concrete material for 3D printing in buildings according to any one of claims 1 to 2, wherein the average number of graphene oxide layers is 5 to 6, and the specific surface area is 40 to 60m2/g。
7. The nano graphene concrete material for 3D printing of buildings according to any one of claims 1 to 2, wherein the dispersant is one or two of a polycarboxylic acid water reducer and a lignosulfonate; and/or the thixotropic agent is one or more of nano clay, organic bentonite and magnesium aluminum silicate.
8. The nano graphene concrete material for 3D printing of buildings according to any one of claims 1 to 2, wherein the accelerating agent is one or more of calcium fluoroaluminate, aluminum oxide clinker and polyacrylic acid; and/or the thickening and water-retaining agent is one or more of carboxymethyl hydroxyethyl cellulose, polyacrylamide and hydroxypropyl methyl cellulose ether.
9. The nano graphene concrete material for 3D printing in buildings according to any one of claims 1 to 2, wherein the defoaming agent is one or two of polyether and higher alcohol; and/or the fiber is one or more of carbon fiber, polyvinyl alcohol fiber and polypropylene fiber.
10. The preparation method of the nano graphene concrete material for 3D printing in the building as claimed in any one of claims 1 to 9, characterized by comprising the following steps:
dispersing graphene oxide powder into deionized water to prepare a graphene oxide solution;
adding a dispersing agent into the graphene oxide solution, and mixing to obtain a graphene oxide dispersion liquid;
sequentially adding a thickening water-retaining agent and a defoaming agent into the graphene oxide dispersion liquid, and uniformly stirring to obtain a mixed graphene oxide solution;
mixing and uniformly stirring cement, a dense filler, a mineral admixture, a thixotropic agent, an accelerator and fibers to obtain a powdery cement-based material;
and adding the mixed graphene oxide solution into the powdery cement-based material and stirring to prepare the nano graphene concrete material for 3D printing of the building.
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