CN114988770A - Extrusion curing type 3D printing fiber-alkali slag material and preparation method thereof - Google Patents
Extrusion curing type 3D printing fiber-alkali slag material and preparation method thereof Download PDFInfo
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- 239000003513 alkali Substances 0.000 title claims abstract description 110
- 239000000463 material Substances 0.000 title claims abstract description 78
- 238000010146 3D printing Methods 0.000 title claims abstract description 40
- 238000001125 extrusion Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000012190 activator Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims abstract description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 9
- 235000012207 sodium gluconate Nutrition 0.000 claims abstract description 9
- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000004576 sand Substances 0.000 claims description 23
- 238000007639 printing Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 235000019353 potassium silicate Nutrition 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 9
- 229940072033 potash Drugs 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- 235000015320 potassium carbonate Nutrition 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
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- 239000007787 solid Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000006004 Quartz sand Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
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- 239000010453 quartz Substances 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
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- 238000010276 construction Methods 0.000 description 8
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses an extrusion curing type 3D printing fiber-alkali slag material and a preparation method thereof, relates to the field of buildings, and aims to solve the technical problem of 3D printing of fiber-alkali (like) slag. The material of the invention comprises, by mass, 35-55% of industrial slag or slag-like powder, 0.5-1% of fiber, 15-25% of MgO, 5-15% of expanding agent CaO, 10-25% of fine aggregate, 0.05-0.08% of lithium carbonate, 0.02-0.05% of sodium gluconate, 10-20% of alkali activator of the industrial slag or slag-like powder, and 40-45% of water of the industrial slag or slag-like powder. The fiber-alkali slag material is obtained by optimizing and proportioning by adopting an extrusion curing type 3D printing technology and changing the types and the mixing amount of an exciting agent, the water using amount, the fiber types and the mixing amount, the MgO mixing amount, the expanding agent mixing amount and the admixture mixing amount.
Description
Technical Field
The invention belongs to the field of buildings, and particularly relates to an extrusion curing type 3D printing fiber-alkali slag material and a preparation method thereof.
Background
At present, the three-dimensional (3D) printing construction technology of the building engineering is an efficient means which can realize the digitization, the intellectualization and the automation of construction. Compared with the traditional construction industry, 3D printing is used as an automatic material increase industrial technology, the problem of labor shortage in the construction industry is greatly relieved, the construction cost is reduced, the efficiency is improved, the production construction period is shortened, and meanwhile, large-area damage to the environment is prevented in the construction process.
Two techniques are currently well-established for 3D printing in construction engineering, one being powder-based spray molding and the other being selective material deposition techniques, also commonly known as extrusion curing, both of which are typical additive techniques. However, the key point of the 3D printing technology lies in the parameters of the base material, and the traditional cement-based concrete material can barely meet the requirements of 3D printing on extrudability, constructability and workability through the adjustment of the mixing ratio. But the cured finished product has the problems of local pore defects, anisotropic mechanical property, layered appearance and the like caused by stacking and is difficult to solve. Meanwhile, the cement-based concrete material is a traditional high-energy-consumption building material and generates a large amount of noise, smoke dust and greenhouse gas CO 2 (China emits CO in cement production every year 2 In an amount close to 7% of the total global volume) and toxic gases (SO) 2 NOx), which severely pollutes the environment, consuming a lot of fuel (coal), electric energy and mineral resources (limestone, clay, etc.).
The main raw materials of the fiber-alkali (like) slag cementing material are slag and like slag, and the slag becomes an industrial byproduct with huge yield along with the rapid development of the steel industry in China. The annual slag yield of China is 2.4 hundred million tons, which accounts for 50 percent of the total global yield. In addition, even in coastal areas and inland islands, appropriate addition of CaO and Al to sea sand is performed 2 O 3 Similar slag similar to industrial slag can be formed through the processes of calcining, water quenching, grinding and the like, local materials are obtained, and the slag is large in sizeGreatly reduces the transportation cost, and if the industrial waste residue (such as slag, slag-like and the like) is excited by using alkali compounds or alkali-containing industrial waste (such as water glass) and the like as an exciting agent, the alkali slag cementing material can be obtained. The alkali (type) slag cementing material is a hydraulic cementing material (the hydraulic cementing material refers to concrete which can be hardened in air and water better, can keep and continue to develop the strength), can be cured in a normal temperature environment, has the compressive strength not lower than C50, and does not reduce the compressive strength after 600 ℃. In addition, the alkali slag material has the characteristics of quick setting and early strength, the slurry is viscous colloid after being fully stirred, and the slump completely meets the requirement of 3D printing.
Disclosure of Invention
The invention aims to solve the technical problem of fiber-alkali (like) slag as 3D printing. And provides an extrusion curing type 3D printing fiber-alkali slag material and a preparation method thereof.
The invention relates to an extrusion curing type 3D printing fiber-alkali slag material which comprises, by mass, 35% -55% of industrial slag or slag-like powder, 0.5% -1% of fiber, 15% -25% of MgO, 5% -15% of expanding agent CaO, 10% -25% of fine aggregate, 0.05% -0.08% of lithium carbonate, 0.02% -0.05% of sodium gluconate, 10% -20% of alkali activator of the industrial slag or slag-like powder and 40% -45% of water of the industrial slag or slag-like powder.
Further, the fiber-alkali slag material is composed of, by mass, 35% -55% of industrial slag or slag-like powder, 0.5% -1% of fiber, 15% -25% of MgO, 5% -15% of an expanding agent CaO, 10% -25% of fine aggregate, 0.05% -0.08% of lithium carbonate, 0.02% -0.05% of sodium gluconate, 10% -20% of an alkali activator in the industrial slag or slag-like powder, and 40% -45% of water in the industrial slag or slag-like powder.
Further, the fine aggregate is any one or a mixture of more than two of quartz sand, river sand, sea sand, mountain sand and machine-made sand; the diameter of the aggregate is 0.5 mm-5 mm.
Further, the alkali activator is prepared by dissolving solid alkali in potassium water glass with a modulus of 0.8-1.4.
Further, the preparation method of the slag-like powder comprises the following steps: adding an oxide into sea sand, calcining until the sea sand is molten, keeping a slag-water ratio of 1: 10-15, carrying out water quenching granulation, crushing water quenching slag, drying, grinding and sieving until the rest is no more than 10% of powder, and obtaining slag-like powder; the oxide is SiO 2 CaO or Al 2 O 3 One or more of them.
Further, the main mineral component of the sea sand is quartz (SiO) 2 ) Hebei (RAlSi) 3 O 8 ) Wherein R represents an alkali metal element), can provide rich SiO 2 And Al 2 O 3 . In addition, in the seabed sediment, certain substances such as biological debris, authigenic minerals and the like exist, and a large amount of calcium components are contained in the substances.
Furthermore, the sea sand contains, by mass, not more than 0.03% of water-soluble chloride ions, not more than 1.0% of mud, not more than 0.5% of mud blocks, not more than 8.0% of firmness index, not more than 1.5% of mica, not more than 1.0% of light substances, and not more than 1.0% of sulfides and sulfates.
Furthermore, the fiber is one or a mixture of more than two of plant fiber, polyethylene fiber, polypropylene fiber and fine steel fiber.
Further, the fiber is obtained by adopting a water treatment mode: shearing, then putting into water, stirring to disperse, and standing for 4-5 hours to obtain the product.
The invention discloses a preparation method of an extrusion curing type 3D printing fiber-alkali slag material, which is carried out according to the following steps:
(1) preparing mixed powder: grinding 35-55% of industrial slag or slag-like powder, 15-25% of MgO, 5-15% of expanding agent CaO and 10-25% of fine aggregate according to mass fraction according to the claim 1 for standby;
(2) preparing an alkali activator solution: dissolving solid alkali in potash water glass to prepare a mixed solution with a specified modulus as an alkali activator solution for later use;
(3) and (2) placing the mixed powder prepared in the step (1), the alkali activator solution prepared in the step (2) and 0.5-1% of fiber in a mixer, stirring and mixing uniformly, adding the alkali activator solution prepared in the step (2), continuing to stir, adding 0.05-0.08% of lithium carbonate and 0.02-0.05% of sodium gluconate, continuing to stir, mixing uniformly, then pouring into a 3D printer, and printing the material according to a 3D printer custom program.
The invention adopts an extrusion curing type 3D printing technology, optimizes the proportion by changing the types and the mixing amount of the exciting agent, the water consumption, the fiber types and the mixing amount, the MgO mixing amount, the expanding agent (CaO) mixing amount and the admixture mixing amount, and tests the basic mechanical properties (compressive strength, tensile strength and flexural strength) and the working properties (setting time, fluidity, extrudability, constructability and cohesiveness) of the fiber-alkali (type) slag. Tests show that potassium water glass has stronger excitation effect than sodium water glass. When the test block is excited by sodium silicate, the curing age is 28d, and the MgO mixing amount is 40%, the breaking strength of the test block is the highest, namely 11.9MPa, and the compressive strength is the highest, namely 90.2 MPa. When the test block is excited by potassium water glass, the bending strength of the test block can reach 28MPa maximally, the compression resistance can reach 145MPa maximally, and the mechanical property of each stage is generally superior to that of sodium water glass. When the water consumption is 35%, the mechanical property of the test block is more excellent, but the working performance is lower than that when the water consumption is 42%. Because the fibers are easy to be unevenly distributed in the test block, the method is improved by adopting a fiber layering method and a water treatment method. When the fibers are laid in the test block in a layered manner, the mechanical property of the test block is obviously reduced, and when the fibers are placed in water firstly and then are subjected to tests after being dispersed automatically, the uniformity of the fibers can be obviously improved; meanwhile, the fibers are directionally distributed due to the space effect of the spray head during extrusion, 60-70% of the fibers can be directionally distributed by using the method, and the uniform distribution of the fibers effectively improves the problems that the mechanical properties are anisotropic and the appearance is layered after curing.
The slag adopted by the invention comprises industrial slag and slag-like slag, and the application of the slag-like slag is applied to coastal areas and inland islands and other sea areas, and the principle is to add the slag into sea sand raw materialsAdding a proper amount of oxide to prepare slag with different chemical compositions. Grinding a certain amount of sandstone to 80um fineness by vibration, analyzing chemical components by X-ray fluorescence spectrum analysis (XRF), and adding different amounts of oxide (SiO) into the existing sandstone material according to the analysis result 2 、CaO、Al 2 O 3 One or more) for melting. The raw materials for melting were put into a graphite crucible of a melting furnace, and calcined to a molten state. Then pouring the mixture into a water pool to carry out water quenching and granulation, and keeping the slag-water ratio at 1: 10. Crushing and drying the water-quenched slag, and then grinding the water-quenched slag into powder with the sieve residue of an 80-micron square-hole sieve being not more than 10% by using a ball mill, thus preparing the slag-like powder. Selecting water glass (sodium silicate solution) as alkali activator, and using NaOH to adjust modulus (NaO) of water glass 2 ·nSiO 2 N) to adjust the modulus to 1.8. The alkali-activated slag pure cementing material can be prepared by using the alkali-activated slag as an activator to excite the slag. Adding sand into the developed alkali-activated slag pure cementing material slurry, wherein the mass ratio of the slag to the sand is selected to be 1: 2, preparing alkali-activated slag mortar. The effects of the fluidity, consistency and setting time of the slag-like mortar are optimal.
The characteristic of quick setting and early strength of the alkali (type) slag is identical with the characteristic of the 3D printing material, but the alkali (type) slag has large shrinkage and is easy to crack, and MgO and a swelling agent (CaO) are adopted in the test to improve the performance of the alkali (type) slag. Experiments show that the shrinkage performance can be improved by adding MgO and an expanding agent (CaO), the bending resistance of the test block can be greatly improved, and the compression resistance is also improved to a certain extent. The change of the mixing amount of MgO and the expanding agent (CaO) shows that the high mixing amount of MgO can deteriorate the fluidity of the slurry, the high mixing amount of the expanding agent (CaO) can improve the burst during the damage, and the comparison of the shrinkage of different proportions shows that when the modulus of the potash water glass is 1.0, the alkali content is 14 percent, the water content is 35 percent, the MgO content is 30 percent, and the fiber mixing amount is 1 percent after the water treatment, the shrinkage of the test block is minimum.
Flowability refers to the property of a concrete mixture that is easily pumped, transported, and extruded from the outlet of a print head. According to the invention, the fluidity of the mixture can be tested by using the method through the influence of the water reducing agent and the retarder on the fluidity of the mixture, and the fluidity is recommended to be controlled to be 170-200 mm. The slump is 4-8 mm, and the printing performance is better;
extrudability refers to the ability of the concrete mixture to be sufficiently fluid to be extruded uniformly and continuously by the printhead. The nozzle at the front end extrudes the slurry for printing, so the size of the caliber of the nozzle determines the size of slurry particles. In order to ensure that the slurry is extruded smoothly and the conveying pipeline is not blocked, the particle size in the slurry is not more than 1/10 of the caliber of the printing head. The group of the invention evaluated the extrudability of the mix according to the apparent mass of a strip extruded from a circular nozzle with a diameter of 50mm and with a total length of 2000 mm;
the constructability refers to the performance that during the process of stacking the 3D printed concrete layer by layer, allowable compression deformation occurs in the stacking direction, allowable expansion deformation occurs in the width direction of the printing strip, the 3D printed product formed by stacking does not bend or collapse, and the whole size does not change along with the time. The inventive group prints 20 layers of 300mm x 500mm tape with extruded tape remaining non-collapsing for 10min as a criterion to meet the constructivity.
Setting time in order to provide good flow and extrusion of the printed material during the effective printing time, the setting time of the slurry should be tightly controlled. Since the adhesion between each layer of the printing material is important for the hardening performance of the whole member, in order to improve the cohesion between the printing layers, the setting time must be controlled within a reasonable range (adjustable within 0-30min of initial setting, adjustable within 30-60min of final setting). The alkali (type) slag prepared as described above is modified to have a suitable setting speed and early strength by using a set accelerator and a set retarder. Lithium carbonate is selected as a coagulant, and sodium gluconate is selected as a retarder to modify the setting time and the mechanical properties of the prepared alkali (type) slag.
The strength is that the material needs to bear the self-weight load of a subsequent printing structure without deformation, and compared with the traditional forming process, the 3D printed material has the defect of compactness due to lack of vibration, so that the building printing material is required to have higher mechanical strength, namely the 2h compressive strength is 10-20MPa, and the 28D compressive strength is in the range of 50-60MPa, and has good printability.
The invention adopts a Scanning Electron Microscope (SEM) method to analyze the change of the microscopic morphology of the printed fiber-alkali (like) slag test piece and reveals the influence of the microscopic morphology on the mechanical property of the test piece. And analyzing the influence of the fiber mixing amount after printing on the pore structure of the test piece by adopting a mercury intrusion Method (MIP) to determine the change rule of the porosity and the pore diameter along with the temperature. The influence of different fiber and additive mixing amounts on the change of the printed alkaline slag material product is analyzed by an X-ray diffraction (XRD) method, and the influence rule of the product change on the degradation of the macroscopic mechanical property of the printed alkaline slag material is revealed.
The invention has the following beneficial effects:
(1) at present, most of extrusion curing type 3D printing materials take cement base as raw materials, and the defects of large energy consumption, serious pollution, energy shortage and the like in cement production are difficult to overcome. The invention applies the alkali slag to the 3D printing technology, uses the fiber to improve the toughness and tensile strength of the alkali slag, inhibits the material shrinkage, limits the crack expansion, and solves the problems of material appearance layering, anisotropic mechanical property and the like, thereby improving the mechanical property of the fiber-alkali slag, not only effectively utilizing the slag and the sea sand, reducing the cost, but also obviously improving the working properties (cohesive force, printing performance and later strength) of the fiber-alkali slag.
(2) At present, sand and stones are added into the alkali-activated slag pure cementing material, and the alkali-activated slag concrete can be prepared by taking a proper mortar-to-sand ratio and sand ratio. Because the alkali-activated slag concrete contains more gel-phase products, the modulus of the gel-phase products is relatively low, the deformation coordination is good in the concrete hardening process, and the compressive strength of the alkali-activated slag cementing material is relatively high, the alkali-activated slag concrete has unique stress performance and deformation performance compared with common concrete and high-strength concrete.
(3) The invention discloses the stress performance, optimized proportion, setting time and failure mechanism by considering the influence of changing key parameters (exciting agent type and mixing amount, slag grade, fiber type and mixing amount, MgO mixing amount and mixing amount of expanding agent (CaO), additive and the like) on the working performance and mechanical property of fiber reinforced alkali (type) slag, and solves the problems of local pore defect, anisotropic mechanical property, layered material appearance and the like caused by stacking in the 3D printing technology.
Drawings
FIG. 1 is a graph of stress-strain curves for fiber-alkali slag materials under different fibers; (a) the figure is that no fiber is added, (b) the figure is that plant fiber is added, (c) the figure is that polypropylene fiber is added, (d) the figure is that steel fiber is added;
FIG. 2 is a graph of initial fiber contrast for a fiber-alkali slag material;
FIG. 3 is a comparison of fiber layering of fiber-alkali slag material;
FIG. 4 is a comparison graph of fiber-alkali slag material fiber water treatment;
FIG. 5 is a graph showing a comparison of the MgO content of the fiber-alkali slag material;
FIG. 6 is a diagram of a printing process of an extrusion curing type 3D printer;
FIG. 7 is a schematic diagram of a zigzag printing circuit of the extrusion curing type 3D printer;
FIG. 8 is a schematic view of an extrusion curing 3D printer printing member;
FIG. 9 is a schematic view of the interior of the melting furnace and a temperature control cabinet; (a) picture of the interior of the melting furnace, (b) picture of the temperature control cabinet;
FIG. 10 is an SEM photograph of different fiber-alkali (type) slags; (a) the figure shows the addition of plant fiber, (b) the figure shows the addition of polypropylene fiber, and (c) the figure shows the addition of steel fiber.
Detailed Description
For the purpose of promoting an understanding of the objects, aspects and advantages of the embodiments of the invention, reference will now be made in detail to the embodiments of the invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout the several views.
The exemplary embodiments of the present invention and the description thereof are provided to explain the present invention and not to limit the present invention.
Example 1
The preparation method of the extrusion curing type 3D printing fiber-alkali (type) slag material of the embodiment specifically includes the following steps:
putting slag, MgO, an expanding agent (CaO) and fine aggregate into a grinder to be ground to 0.5-1 um; the slag is used 40%, MgO is used 30%, fine aggregate is used 10% (the mixing amount with the fiber after water treatment is 1%, the mixture is mixed and stirred for 1min for standby, the modulus of potash water glass is 1.0, the alkali content is 14% of the slag powder, the alkali activator solution is prepared by fully stirring, the heat dissipation is carried out for 12 hours for standby, finally 35% of the water amount is added into the mixed powder, the standby alkali activator solution is added, and the mixture is mixed and stirred for 3min at normal temperature, so that the alkali (type) slag cementing material for 3D printing is obtained.
The fiber-alkali (like) slag material for 3D printing prepared in the embodiment is injected into a printer, and performance parameters are measured through a printing path in a shape like a Chinese character 'hui': the fluidity is 140-150 mm (the fluidity is too low), the initial setting time is 15-20 minutes, the final setting time is 100-110 minutes (the final setting time is too long), and the initial compressive strength can reach 85-90 MPa.
Example 2
The preparation method of the extrusion curing type 3D printing fiber-alkali (type) slag material of the embodiment specifically includes the following steps:
putting slag, MgO, an expanding agent (CaO) and fine aggregate into a grinder to be ground to 0.5-1 um; the slag dosage is 38%, the MgO dosage is 30%, the fine aggregate dosage is 10% (the mixing dosage with the fiber after water treatment is 1%, mixing and stirring are carried out for 1min for standby, the modulus of potash water glass is 1.0, the alkali content is 14% of the slag powder dosage, fully stirring is carried out to prepare alkali activator solution, heat dissipation is carried out for 12 hours for standby, finally 42% of water dosage is added into the mixed powder, standby alkali activator solution is added, mixing and stirring are carried out for 3min at normal temperature, and the alkali (type) slag cementing material used for 3D printing is obtained.
The fiber-alkali (like) slag material for 3D printing prepared in the embodiment is injected into a printer, and performance parameters are measured through a printing path in a shape like a Chinese character 'hui': the fluidity is 220-230 mm (the fluidity is too high), the initial setting time is 20-25 minutes, the final setting time is 115-120 minutes (the final setting time is too long), and the initial compressive strength can reach 55-60 MPa (slightly low).
Example 3
The preparation method of the extrusion curing type 3D printing fiber-alkali (type) slag material of the embodiment specifically includes the following steps:
putting slag, MgO, an expanding agent (CaO) and fine aggregate into a grinding machine to be ground to 0.5-1 um; mixing 40% of slag, 20% of MgO, 10% of expanding agent (CaO) and 10% of fine aggregate (with the mixing amount of the water-treated fiber being 1%, stirring for 1min for standby, 1.0 modulus of potash water glass and 14% of alkali content being slag powder, fully stirring to prepare an alkali activator solution, radiating for 12 hours for standby, finally adding 35% of water and 35% of slag powder into the mixed powder, adding the standby alkali activator solution, and mixing and stirring for 3min at normal temperature to obtain the alkali (type) slag cementing material for 3D printing.
The fiber-alkali (type) slag material for 3D printing prepared in the examples was injected into a printer, and through a "zigzag" printing path, the measured performance parameters were: the fluidity is 130-140 mm (the fluidity is too small), the initial setting time is 20-25 minutes, the final setting time is 110-115 minutes (the final setting time is too long), and the initial compressive strength can reach 70-85 MPa.
Example 4
The preparation method of the extrusion curing type 3D printing fiber-alkali (type) slag material of the embodiment specifically includes the following steps:
putting slag, MgO, an expanding agent (CaO) and fine aggregate into a grinding machine to be ground to 0.5-1 um; the slag dosage is 38%, the MgO dosage is 20%, the expanding agent (CaO) dosage is 10%, the fine aggregate dosage is 10% (mixing and stirring 1min with the fiber dosage after water treatment, the modulus of potash water glass is 1.0, the alkali content is 14% of the slag powder dosage, fully stirring to prepare alkali activator solution, radiating for 12 hours, standby, finally adding 42% of water dosage of the slag powder dosage into the mixed powder, adding standby alkali activator solution, mixing and stirring for 3min at normal temperature, and obtaining the alkali (type) slag cementing material used for 3D printing.
The fiber-alkali (type) slag material for 3D printing prepared in the examples was injected into a printer, and through a "zigzag" printing path, the measured performance parameters were: the fluidity is 180-190 mm, the initial setting time is 25-30 minutes, the final setting time is 115-120 minutes (the final setting time is too long), and the initial compressive strength can reach 70-75 MPa.
Example 5
The preparation method of the extrusion curing type 3D printing fiber-alkali (type) slag material of the embodiment specifically includes the following steps:
putting slag, MgO, an expanding agent (CaO) and fine aggregate into a grinder to be ground to 0.5-1 um; mixing and stirring 38% of slag, 20% of MgO, 10% of expanding agent (CaO), 10% of fine aggregate and 1% of fiber after water treatment for 1min for later use; the modulus of the potash water glass is 1.0, the alkali content is 14 percent of the amount of the slag powder, the alkali activator solution is prepared by fully stirring, and the heat dissipation is carried out for 12 hours for standby; and finally, adding 42% of water based on the slag powder into the mixed powder, adding a standby alkali excitation solution, adding 0.06% of lithium carbonate and 0.04% of sodium gluconate, and mixing and stirring for 3min at normal temperature to obtain the alkali (type) slag cementing material for 3D printing.
The fiber-alkali (type) slag material for 3D printing prepared by the embodiment is injected into a printer, and performance parameters are measured through a printing path in a shape like a Chinese character 'hui': the fluidity is 170-185 mm, the initial setting time is 15-25 minutes, the final setting time is 35-60 minutes, the initial compressive strength can reach 80-90 MPa, and all the requirements are met.
Compared with the existing 3D printing building material, the embodiment adopts the alkali (similar) slag cementing material, utilizes the material advantages, can overcome the defects of high energy consumption, serious pollution, energy shortage and the like in cement production, can effectively utilize slag and sea sand, and reduces the cost; and the fiber mode is adopted to increase the toughness and tensile strength of the alkali (like) slag, inhibit the shrinkage of the material, limit the expansion of cracks, greatly improve the problems of material appearance layering, mechanical property anisotropy and the like, improve the printability and the constructability of the fiber-alkali (like) slag and obviously improve the overall performance of the fiber-alkali (like) slag.
TABLE 1 comparison table of fluidity, setting time and strength at different ratios
Claims (10)
1. An extrusion curing type 3D printing fiber-alkali slag material is characterized by comprising, by mass, 35% -55% of industrial slag or slag-like powder, 0.5% -1% of fiber, 15% -25% of MgO, 5% -15% of an expanding agent CaO, 10% -25% of fine aggregate, 0.05% -0.08% of lithium carbonate, 0.02% -0.05% of sodium gluconate, 10% -20% of an alkali activator and 40% -45% of water.
2. The extrusion-curable 3D-printed fiber-alkali slag material according to claim 1, wherein the fiber-alkali slag material consists of, by mass, 35-55% of industrial slag or slag-like powder, 0.5-1% of fiber, 15-25% of MgO, 5-15% of an expanding agent CaO, 10-25% of fine aggregate, 0.05-0.08% of lithium carbonate, 0.02-0.05% of sodium gluconate, 10-20% of an alkali activator and 40-45% of water.
3. The extrusion-curable 3D-printed fiber-alkali slag material according to claim 1, wherein the fine aggregate is any one or a mixture of two or more of quartz sand, river sand, sea sand, mountain sand, and machine-made sand; the diameter of the aggregate is 0.5 mm-5 mm.
4. The extrusion-curable 3D-printed fiber-alkali slag material according to claim 1, wherein the alkali activator is prepared by dissolving a solid alkali in a potash water glass having a modulus of 0.8 to 1.4.
5. The extrusion-curable 3D-printed fiber-alkali slag material according to claim 1, wherein the mineral-like material is one of mineral-like, mineral-alkali-slag, mineral-alkali-slag, and mineral-alkali-slagThe preparation method of the slag powder comprises the following steps: adding an oxide into sea sand, calcining until the sea sand is molten, keeping a slag-water ratio of 1: 10-15, carrying out water quenching granulation, crushing water quenching slag, drying, grinding and sieving until the rest is no more than 10% of powder, and obtaining slag-like powder; the oxide is SiO 2 CaO or Al 2 O 3 One or more of them.
6. The extrusion-curable 3D-printable fiber-alkali slag material according to claim 5, wherein the main mineral components of the sea sand are quartz and RAlSi 3 O 8 Wherein R represents an alkali metal element.
7. The extrusion-curable 3D-printing fiber-alkali slag material according to claim 5 or 6, wherein the sea sand contains, by mass, not more than 0.03% of water-soluble chloride ions, not more than 1.0% of mud, not more than 0.5% of mud pieces, not more than 8.0% of firmness index, not more than 1.5% of mica, not more than 1.0% of light materials, and not more than 1.0% of sulfides and sulfates.
8. The extrusion curing type 3D printing fiber-alkali slag material as claimed in claim 1, wherein the fiber is one or a mixture of two or more of plant fiber, polyethylene fiber, polypropylene fiber and micro steel fiber.
9. The extrusion-curable 3D printing fiber-alkali slag material according to claim 8, wherein the fiber is obtained by water treatment: shearing, then putting into water, stirring to disperse, and standing for 4-5 hours to obtain the product.
10. A method of preparing the extrusion curable 3D printed fiber-alkali slag material according to claim 1, characterized in that it is performed according to the following steps:
(1) preparing mixed powder: grinding 35-55% of industrial slag or slag-like powder, 15-25% of MgO, 5-15% of expanding agent CaO and 10-25% of fine aggregate according to mass fraction according to the claim 1 for standby;
(2) preparing an alkali activator solution: dissolving solid alkali in potash water glass to prepare a mixed solution with a specified modulus as an alkali activator solution for later use;
(3) and (3) placing the mixed powder prepared in the step (1), the alkali activator solution prepared in the step (2) and 0.5-1% of fiber in a mixer, stirring and mixing uniformly, adding the alkali activator solution prepared in the step (2), continuing stirring, adding lithium carbonate with the mass fraction of 0.05-0.08% and sodium gluconate with the mass fraction of 0.02-0.05%, continuing stirring, mixing uniformly, then pouring into a 3D printer, and printing the material according to a 3D printer customized program.
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