CN113636806B - Impervious corrosion-resistant concrete prepared from metallurgical solid waste and preparation method thereof - Google Patents
Impervious corrosion-resistant concrete prepared from metallurgical solid waste and preparation method thereof Download PDFInfo
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- CN113636806B CN113636806B CN202110825865.1A CN202110825865A CN113636806B CN 113636806 B CN113636806 B CN 113636806B CN 202110825865 A CN202110825865 A CN 202110825865A CN 113636806 B CN113636806 B CN 113636806B
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- fly ash
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- 239000004567 concrete Substances 0.000 title claims abstract description 89
- 230000007797 corrosion Effects 0.000 title claims abstract description 21
- 238000005260 corrosion Methods 0.000 title claims abstract description 21
- 239000002910 solid waste Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 93
- 239000000843 powder Substances 0.000 claims abstract description 58
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 47
- 238000003756 stirring Methods 0.000 claims abstract description 36
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002699 waste material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000005097 cold rolling Methods 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 52
- 239000010881 fly ash Substances 0.000 claims description 43
- 239000004576 sand Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 32
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 13
- 239000004568 cement Substances 0.000 claims description 12
- 239000002956 ash Substances 0.000 claims description 11
- 239000010878 waste rock Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000002893 slag Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000004575 stone Substances 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 claims description 6
- 230000003487 anti-permeability effect Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011435 rock Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 24
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000002689 soil Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- 239000011575 calcium Substances 0.000 description 15
- 238000006703 hydration reaction Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- 230000036571 hydration Effects 0.000 description 10
- 239000002086 nanomaterial Substances 0.000 description 10
- 230000010220 ion permeability Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000000378 calcium silicate Substances 0.000 description 5
- 229910052918 calcium silicate Inorganic materials 0.000 description 5
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910018516 Al—O Inorganic materials 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C04B28/04—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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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
- C04B2111/20—Resistance against chemical, physical or biological attack
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses an impervious corrosion-resistant concrete prepared by utilizing metallurgical solid wastes, a method thereof and a concreteThe soil comprises the following components: 100 parts of a cementing material, 196-370 parts of a coarse aggregate, 132-325 parts of a fine aggregate and 0.5-2.2 parts of a high-efficiency water reducing agent; and an additive consisting of 0.1-4 parts of nano calcium carbonate powder, 0.5-20 parts of cold rolling waste emulsion, 0.00625-0.0125 parts of iron oxide powder, 0.0125-0.025 parts of sodium sulfate, 0.0125-0.025 parts of ethylene glycol and 32-62 parts of water. The preparation method comprises the following steps: mixing coarse and fine aggregates according to the proportion of the raw materials, adding a cementing material, mixing, adding a high-efficiency water reducing agent and water, stirring uniformly, and adding the nano calcium carbonate powder subjected to dispersion treatment before or simultaneously adding the water reducing agent and the water. The concrete has the characteristics of less harmful pores, high strength, impermeability, chlorine ion absorption, corrosion resistance and the like, the mixing amount of metallurgical solid waste in the concrete is more than or equal to 75 percent, the high-valued utilization of the metallurgical solid waste is realized, and CO is reduced 2 And (5) discharging.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to impervious and corrosion-resistant concrete prepared by utilizing metallurgical solid wastes and a method thereof.
Background
In recent years, researchers continuously explore methods for modifying concrete by adding nano materials, and find that the nano materials can improve the mechanics and durability of the concrete mainly due to the mechanisms of promoting hydration, enabling hydration products to be uniform, enabling crystals to be refined and compact, improving an interface area, reducing porosity, refining microcracks under load and the like. By adopting a nano assembly technology, the nano material grows or is grafted on the micron-sized mineral admixture and the fiber to form the micro-nano multi-scale material, on one hand, the problem that the nano material can still be uniformly dispersed in concrete under a large doping amount can be solved, on the other hand, the microstructure of the concrete can be obviously improved through a fiber space network, a micro-nano scale effect and the treatment of the nano material on the surface of the fiber, and the deformability and the shock resistance of the nano material are far superior to those of common high-strength concrete. The nano material can enhance or modify the concrete mechanics and durability mainly because the nano material can promote hydration, so that hydration products are uniform, crystals are refined and compact, an interface area is improved, the porosity and the pore diameter are reduced, microcracks are refined under load, the concrete impermeability is enhanced, and the corrosion resistance effect is achieved.
Although the nano material can improve the performance indexes of the concrete such as compressive strength, impermeability and the like, the improvement degree of related indexes is limited due to factors such as content, uniformity and the like. If the specific performance of the reinforced concrete is required, the nano concrete needs to be further processed.
1. According to the invention, polyvinyl alcohol, epoxy resin, potassium tripolyphosphate and butyl methacrylate are added into concrete, so that the concrete has strong functions of seepage prevention and corrosion prevention, steel bars in the concrete can be effectively prevented from being corroded, the service life of the concrete is prolonged, and the crack resistance of the concrete can be improved by adding lace fibers and carbon fibers. The problem of corrosion of the steel bars can be solved in a short period by adding excessive organic substances, the long-term durability of the concrete can be affected, the organic substances have a gradual aging trend in long-term use, and the added fibers have high cost and no popularization value.
2. An impervious recycled concrete and a preparation method thereof (application number: CN201911354638.4), the method adopts an expanding agent to enhance the impermeability of the concrete, limestone, dolomite and high magnesium iron ore are used for grinding and calcining to obtain an expanded clinker; adding high-calcium fly ash, argil and redispersible latex powder into the expanded clinker, and grinding and heating to obtain the anti-permeability expanding agent. The invention can ensure continuous and stable expansion through the anti-permeability expanding agents of various expansion sources, thereby improving the anti-permeability performance of concrete. The expansion agent is used for improving the impermeability of concrete, so that the control of the impermeability and the dispersion uniformity are difficult, and excessive expansion is easily caused locally or wholly to form stress and cause cracks.
Disclosure of Invention
The invention aims to provide an impervious and corrosion-resistant concrete prepared by utilizing metallurgical solid wastes and a method thereof.
The sand and stone material used by the concrete prepared by the method can completely use metallurgical solid wastes, and the mixing amount of the metallurgical solid wastes in the concrete is more than or equal to 75 percent.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the impervious corrosion-resistant concrete prepared by utilizing metallurgical solid wastes comprises the following components in parts by weight: 100 parts of cementing material, 196-370 parts of coarse aggregate, 132-325 parts of fine aggregate, 0.3-2.2 parts of high-efficiency water reducing agent, an additive consisting of 0.1-4 parts of nano calcium carbonate powder, 0.5-20 parts of cold rolling waste emulsion, 0.00625-0.0125 part of iron oxide powder, 0.0125-0.025 part of sodium sulfate, 0.0125-0.025 part of ethylene glycol and 32-62 parts of water.
Further, the cementing material comprises 50-75 parts of cement, 13-7 parts of slag micro powder, 13-6 parts of steel slag micro powder, 12-6 parts of modified fly ash and 12-6 parts of iron tailing powder; the high-efficiency water reducing agent is one or a mixture of polycarboxylic acids and naphthyl; the water is used for proportioning concrete, and comprises water contained in cold rolling waste emulsion for dispersing nano calcium carbonate powder and supplementary water.
The cement is Portland cement (P. I, P. II), ordinary Portland cement (P.O), composite Portland cement (P.C), 42.5, 52.5. The fineness of the slag micro powder and the steel slag micro powder is more than 400 meshes, and the grade of S75 and above is recommended. The fly ash reaches more than II grade, and the granularity reaches more than 400 meshes. The iron tailing powder is prepared by grinding iron tailings, and the granularity reaches more than 400 meshes. The cement, slag micropowder and steel slag micropowder have hydraulic activity; the glass microspheres in the fly ash can improve and enhance the structural strength of concrete, improve homogeneity and compactness, and a large amount of active silicon dioxide, alumina and alkaline substances generate gelled substances such as calcium silicate hydrate and calcium aluminate hydrate and the like to block capillary tissues of the concrete and improve impermeability; the iron tailings powder has the characteristic of high interfacial activity, and the materials can participate or promote the formation of hydration products, so that the compressive strength and the flexural strength of the concrete are enhanced.
Further, the coarse aggregate is continuously graded mine waste stone, and the particle size range is 5-20 mm; the fine aggregate is mine waste rock artificial sand and iron tailing sand, wherein the proportion of the mine waste rock artificial sand is 90-10%, the proportion of the iron tailing sand is 10-90%, the mine waste rock artificial sand and the iron tailing sand are mixed to form continuous gradation, and the grain size is less than or equal to 5 mm.
The mine waste rock is waste rock after stripping and ore processing, which is discharged in the mining process, the Mohs hardness is 5-7, the broken stone strength reaches the hardness of limestone and basalt, the strength is high, and the skeleton and the supporting function are achieved in concrete.
Processing and crushing mine waste rocks into 20mm and below, wherein the artificial sand of the waste rocks with the size less than or equal to 5mm is used as fine aggregate; the size of the mine waste stone is 5-20 mm, the size of the mine waste stone is used as a coarse aggregate, the crushing value is less than or equal to 10%, the mine waste stone is in continuous gradation, and the mine waste stone is beneficial to strength improvement and pumping.
According to the relevant industry standards, the fine aggregate is divided according to the fineness modulus: 3.1-3.7 of coarse sand, 2.3-3.0 of medium sand and 1.6-2.2 of fine sand. The crushing value of the fine aggregate is less than or equal to 25 percent, wherein the fineness modulus of the artificial sand of the mine waste rock is 2.2-3.6, and the artificial sand belongs to the range of medium sand or coarse sand; the iron tailing sand in the fine aggregate is divided into two types of coarse and fine, wherein the coarse iron tailing sand is waste sandstone separated by a pre-selection process, the fineness modulus is 2.1-3.5, and the range of medium sand and even coarse sand is reached; the fine iron tailing sand is ore waste obtained by grinding magnetite and selecting iron by a magnetic separation process, is stirred and mixed with water, is discharged to a tailing pond through a pipeline, is settled to obtain sandstone, has the fineness modulus of 0.7-1.8, is smaller than the fineness modulus of the fine sand, belongs to extremely fine sand, and accounts for 8-20% of the fine iron tailing sand by the amount of the particle size d being less than or equal to 0.16 mm. The fine iron tailing sand has high interfacial activity and promotes the hydration reaction with the cementing material.
Further, the modified fly ash is formed by modifying power plant fly ash, wherein SiO in the power plant fly ash 2 And Al 2 O 3 More than or equal to 80 percent of Al 2 O 3 The content is more than or equal to 25 percent, and the grain diameter is less than or equal to 270 mu m.
Furthermore, the nano calcium carbonate powder has a particle size of 10-80 nm and is hydrophilic; the particle size of the iron oxide powder is 0.1 to 1 μm.
The preparation method of the modified fly ash in the cementing material comprises the following steps: firstly, weighing a certain mass of fly ash, and adding 1.5-1.8 mol/L HNO according to the amount of 8-12 mL/g fly ash 3 Standing the solution for reaction for 60-70 minutes, and adding CaCO accounting for 25-35% of the mass of the fly ash 3 Adding CaO which is 6-10% of the mass of the fly ash as a fluxing agent as a foaming agent, grinding the mixture to be uniform, adding 1-2% of the mass of the fly ash and hydrogen peroxide, stirring and drying the mixture, finally placing the mixture in a muffle furnace, heating the mixture to 880-900 ℃, calcining the mixture for 50-60 minutes, naturally cooling the mixture, and grinding the mixture to be below 50 meshes to obtain calcined ash; uniformly mixing nano calcium carbonate and nano aluminum oxide according to the mass ratio of (6-10) to 1 to obtain nano calcium-aluminum mixed ash; mixing 8-10 parts of calcined ash and 1 part of nano calcium-aluminum mixed ash, and shaking up to prepare the modified fly ash. The grain diameter of the nano alumina powder is 10-60 nm, and the crystal form is gamma-Al 2 O 3 。
After the fly ash is subjected to acid modification and high-temperature modification, the active sites are increased due to partial fracture of Si-O and Al-O, and the Cl content is improved - The adsorption capacity of (c); meanwhile, as the nano-alumina and the nano-calcium carbonate are added, chloride ions entering the concrete can react with calcium and active aluminum to generate Ca 4 Al 2 Cl 2 (OH) 12 The concrete is compacted while chlorine ions are blocked from continuously permeating the concrete.
After the concrete is doped with the nano calcium carbonate powder, the C-S-H gel can grow by taking nano calcium carbonate as a crystal nucleus due to the surface effect of nano particles, so that the calcium silicate hydrate gel forms a cluster-shaped and net-shaped structure taking the nano calcium carbonate as a core, plays a role in pinning in each direction in the concrete, reduces the porosity and cracks and increases the strength of the concrete; by adding the nano particles, the pore structure of the concrete is refined and Cl resistance is realized - The permeability is enhanced; the nano particles form hydration crystal nuclei after being doped, and Ca (is consumed)OH) 2 And calcium silicate hydrate gel is gradually generated on the surface of the concrete, so that the calcium silicate hydrate gel is promoted and participates in the secondary hydration reaction of the cement, and the generated gel grows by taking the nano particles as crystal nuclei and forms a net structure, so that the internal structure of the concrete is more compact. Meanwhile, due to hydration products Ca (OH) of C3S and C2S in cement 2 The crystals of (A) are coarse and have poor stability, and NaCl is liable to react with them to form CaCl-containing crystals 2 The complex of (1) promotes the secondary hydration of cement after the nano calcium carbonate is added, and reduces Ca (OH) in a transition region 2 The enrichment degree of (A) reduces the occurrence of the above-mentioned complex reaction, and inhibits Cl - The penetration of (2).
Because the modified fly ash is adsorbed with a large amount of nano calcium carbonate powder and nano alumina powder, when the concrete meets the penetrated Cl - When it reacts with calcium and active aluminum, Ca is formed 4 Al 2 Cl 2 (OH) 12 ,Ca 4 Al 2 Cl 2 (OH) 12 Is one of Freund's salts, is a layered compound, and blocks the continuous permeation of chloride ions into concrete. Because most of the reaction occurs in the fly ash, the internal space of the fly ash is enough to accommodate the increase of the volume after the reaction, and the concrete is further compacted. Meanwhile, the main components of the fly ash are quartz and mullite, wherein the quartz and the mullite are mainly made of SiO 2 The latter consisting of 3Al 2 O 3 ·2SiO 2 The composition is that after acid is added for high temperature and foaming treatment, Si-O bonds and Al-O bonds are opened, so that adsorption sites on the surface of the fly ash are increased, pores are increased, the particle size is reduced, the physical adsorption capacity of the fly ash on chloride ions and the like is enhanced, and the chloride ions are blocked from permeating into the concrete.
Further, in order to solve the problems of agglomeration and poor dispersibility of the nano calcium carbonate powder, a method for dispersing a nano material by using a cold rolling waste emulsion is adopted, and the nano calcium carbonate powder, the cold rolling waste emulsion and other medicaments are prepared according to the following mass parts of 0.1-4 parts of nano calcium carbonate, 0.5-20 parts of the cold rolling waste emulsion, 0.00625-0.0125 part of iron oxide powder, 0.0125-0.025 part of sodium sulfate and 0.0125-0.025 part of ethylene glycol. The specific dispersion method comprises the following steps: firstly, placing cold rolling waste emulsion into a stirring device, controlling the stirring speed at 800-1200 rpm, adding iron oxide powder, stirring for 2-3 minutes, dividing the nano calcium carbonate powder into 2-5 equal parts, adding in batches, and continuously stirring for 3-5 minutes; adding sodium sulfate, and continuously stirring for 3-5 minutes; and finally, adding ethylene glycol, stirring for 10-15 minutes, reducing the stirring speed to 100-150 rpm, stirring for 5-10 minutes, and stopping stirring to form uniformly and stably dispersed nano calcium carbonate slurry, wherein the nano calcium carbonate powder has good dispersibility in a concrete body and high integral performance of the concrete.
The cold rolling waste emulsion mainly contains water, the water content is 96.5-97.5%, the rest 2.5-3.5% of the cold rolling waste emulsion is composed of oil, an emulsifier, an anti-compression agent, an antioxidant and mechanical impurities, the cold rolling waste emulsion has good chemical stability, oil-water separation is difficult to carry out, the cold rolling waste emulsion belongs to oil-containing waste water which is difficult to treat, and active functional groups contained in the cold rolling waste emulsion can adsorb nano calcium carbonate powder and are beneficial to the dispersion of the nano calcium carbonate powder.
The particle size of the iron oxide powder is 0.1-1 μm, and the nano calcium carbonate powder is easy to adsorb and bond with the iron oxide powder due to large surface energy, and the iron oxide powder can promote the formation of calcium sulphoaluminate in concrete along with the dispersion and dispersion of the iron oxide powder in a solution.
The sodium sulfate and the nano calcium carbonate powder are dispersed together in the solution, so that the nano calcium carbonate powder is prevented from agglomerating in the concrete stirring process. The sodium sulfate can form calcium sulfoaluminate hydrate with cement, slag micropowder and steel slag micropowder in the cementing material more quickly in the concrete solidification process, the early strength of the concrete is improved, the hydration process of the cementing material is accelerated, and the two actions are mutually promoted.
The glycol can improve the stability of the nano calcium carbonate slurry; the ethylene glycol is used as a retarder of the cement, so that internal stress of shrinkage or expansion caused by hydration reaction can be released and cleared before the concrete is solidified, part of inorganic salt contained in the cement can be dissolved, salt in the cement is not easy to seep out, the concrete is more compact after being solidified, and the strength of the concrete is enhanced.
The invention relates to an impervious corrosion-resistant concrete prepared by utilizing metallurgical solid wastes and a preparation method thereof.
The anti-permeability and corrosion-resistant concrete prepared by utilizing metallurgical solid wastes according to the scheme has the following beneficial effects:
1. when preparing the C20-C60 strength concrete, curing under normal temperature and normal humidity conditions, and performing standard curing on the prepared concrete test piece to obtain 28d compressive strength of 26.3-80.2 MPa; the 28d flexural strength is 3.1-8.5 Mpa; permeability coefficient of chloride ion is 0.87X 10 -12 m 2 /s~1.23×10 -12 m 2 /s。
2. The adoption of the nano calcium carbonate powder can lead the calcium silicate hydrate gel to form a cluster-shaped and net-shaped structure taking the nano calcium carbonate as a core, reduce the porosity and the cracks of the concrete and increase the strength of the concrete; by adding the nano particles, the pore structure of the concrete is refined, and the corrosion resistance and the chloride ion permeability resistance are enhanced; meanwhile, the nano calcium carbonate promotes the secondary hydration of the cement, and reduces Ca (OH) in a transition region 2 The enrichment degree of the chlorine ion inhibitor reduces the occurrence of complex reaction with the chlorine ion and inhibits the penetration of the chlorine ion.
3. After the modified fly ash is doped, the modified fly ash reacts with internal calcium and activated aluminum when encountering permeating chloride ions to generate Ca 4 Al 2 Cl 2 (OH) 12 Blocking the continuous permeation of chloride ions to concrete and simultaneously reacting Ca 4 Al 2 Cl 2 (OH) 12 The volume is increased, the concrete is further compacted, and chloride ions are prevented from migrating into the concrete; after the coal ash is modified, the Si-O and the Al-O are partially broken, the active site positions are increased, the particle size is reduced, the physical adsorption capacity of the coal ash to chloride ions and the like is enhanced, and the penetration of the chloride ions is further prevented.
4. The prepared concrete has greatly reduced harmful pores, compact concrete structure, raised fracture toughness, raised strength and impermeability, raised corrosion resistance, especially raised chlorine ion absorbing and blocking capacity, and is suitable for constructing impervious and corrosion resistant concrete.
5. The metallurgical solid waste mixing amount in the concrete is more than or equal to 75 percent, and the usage amount of fine iron tailing sand with the grain diameter d less than or equal to 0.16mm accounting for 8 to 20 percent is increased; the manufacturing cost of the concrete is reduced by 20-70 yuan/m 3 。
Detailed Description
1. The raw materials used in the invention have the following component ranges:
table 1 mine waste rock composition ranges (unit:%):
composition (I) | SiO 2 | Al 2 O 3 | FeO | Fe 2 O 3 | TFe | CaO | MgO | K 2 O | Na 2 O |
Data of | 50~78 | 5~18 | 0.5~8 | 1~8 | 0.3~6 | 2~10 | 1~5 | 0~4 | 0~4 |
The Mohs hardness is 5-7.
Table 2 composition ranges (unit:%) of iron tailings (containing magnetic separation tailings and pre-separation process tailings):
composition (A) | SiO 2 | Al 2 O 3 | FeO | Fe 2 O 3 | TFe | CaO | MgO | K 2 O | Na 2 O |
Data of | 55~82 | 0.2~9 | 0.5~12 | 2~22 | 5~15 | 0~8 | 0~4 | 0~1.8 | 0~1.8 |
2. Technological parameters of the invention
1) The preparation method of the modified fly ash comprises the following steps: firstly, weighing a certain mass of fly ash, and adding 1.5-1.8 mol/L HNO according to the amount of 8-12 mL/g fly ash 3 Standing the solution for reaction for 60-70 minutes, and then adding CaCO accounting for 25% -35% of the mass of the fly ash 3 Adding CaO which is 6-10% of the mass of the fly ash as a fluxing agent as a foaming agent, grinding the mixture to be uniform, adding 1-2% of the mass of the fly ash and hydrogen peroxide, stirring and drying the mixture, finally placing the mixture in a muffle furnace, heating the mixture to 880-900 ℃, calcining the mixture for 50-60 minutes, naturally cooling the mixture, and grinding the mixture to be less than 50 meshes; uniformly mixing the nano calcium carbonate and the nano alumina according to the mass ratio of (6-10) to 1, and uniformly mixing and shaking 8-10 parts of ground fly ash, 1 part of nano calcium carbonate powder and a mixture of nano alumina powder to prepare the modified fly ash.
TABLE 3-1 calcined Ash Process parameters
TABLE 3-2 nanometer calcium-aluminum Mixed Ash Process parameters
Categories | Unit of | Number of | Number of | Number of |
Nano calcium carbonate | g | 600 | 800 | 1000 |
Nano alumina | g | 100 | 100 | 100 |
TABLE 3-3 modified fly ash Process parameters
Categories | Unit of | Number of | Number of | Number of |
Calcined lime | g | 400 | 450 | 500 |
Nano calcium-aluminum mixed ash | g | 50 | 50 | 50 |
2) The dispersion treatment of the nano calcium carbonate powder comprises the following steps: putting 0.5-25 parts of cold rolling waste emulsion into a stirring device, wherein the initial stirring speed of the stirring device is 800-1200 rpm, adding 0.00625-0.0125 parts of iron oxide powder, stirring for 2-3 minutes, dividing 0.1-4 parts of nano calcium carbonate powder into 2-5 equal parts, adding in batches at intervals of 3-5 minutes, and continuously stirring; and adding 0.0125-0.025 parts of sodium sulfate, continuously stirring for 3-5 minutes, finally adding 0.0125-0.025 parts of ethylene glycol, stirring for 10-15 minutes, reducing the stirring speed to 100-150 rpm, stirring for 5-10 minutes, and stopping stirring to form uniformly and stably dispersed nano calcium carbonate slurry. The detailed process parameters are shown in Table 4.
TABLE 4 Dispersion treatment Process parameters of nano calcium carbonate powder
3) Fine aggregate proportioning scheme
TABLE 5 Fine aggregate proportioning scheme (unit:%)
4) Water quantity of each part
0.1-4 parts of nano calcium carbonate powder and 0.5-25 parts of cold rolling waste emulsion (the average value of the water content of the cold rolling waste emulsion is 97%).
The water content is the water content of the cold rolling waste emulsion plus the water required to be supplemented (see table 6).
TABLE 6 Water volume of each part (unit: parts)
5) The adding mode of each raw material is as follows: and uniformly mixing the coarse aggregate, the fine aggregate and the cementing material according to the normal concrete stirring mode. When concrete is produced, the nano calcium carbonate after dispersion treatment is added before or simultaneously with the water reducing agent and the water (the nano calcium carbonate is added before examples 1-3, and the nano calcium carbonate is added simultaneously with examples 4-6). The slump is more than or equal to 160 mm.
3. The concrete proportion and the performance of the invention
Example 1: c20 (concrete proportioning in unit: part; 28d strength unit: MPa; 28d chloride ion permeability coefficient: x 10) -12 m 2 /s)
Example 2: c30 (concrete proportioning in unit: portion; 28d strength unit: MPa; 28d chloride ion permeability coefficient: x 10) -12 m 2 /s)
Example 3: c40 (concrete proportioning in unit: portion; 28d strength unit: MPa; 28d chloride ion permeability coefficient: x 10) -12 m 2 /s)
Example 4: c50 (concrete proportioning in unit: portion; 28d strength unit: MPa; 28d chloride ion permeability coefficient: x 10) -12 m 2 /s)
Example 5: c55 (concrete proportioning in unit: portion; 28d strength unit: MPa; 28d chloride ion permeability coefficient: x 10) -12 m 2 /s)
Example 6: c60 (concrete proportioning in unit: part; 28d strength unit: MPa; 28d chloride ion permeability coefficient: x 10) -12 m 2 /s)
Comparative example: c60 (concrete proportioning in unit: portion; 28d strength unit: MPa; 28d chloride ion permeability coefficient: x 10) -12 m 2 /s)
Note: the C20-C60 concrete artificial macadam refers to waste stones (5-20 mm); the artificial sand refers to mine waste rock artificial sand (less than or equal to 5 mm); the tailings powder refers to iron tailings powder; the iron tailing sand is formed by mixing coarse tailing sand and fine tailing sand according to a proportion.
By comparing example 6 with the comparative example, the compressive strength is improved by 9.41 percent, the breaking strength is improved by 11.84 percent, and the permeability coefficient of chloride ions is from 3.87 multiplied by 10 -12 m 2 The/s is reduced to 0.87 multiplied by 10 -12 m 2 /s。
Claims (7)
1. The impervious corrosion-resistant concrete prepared by utilizing metallurgical solid wastes is characterized by comprising the following components in parts by mass: 100 parts of a cementing material, 196-370 parts of a coarse aggregate, 132-325 parts of a fine aggregate, 0.3-2.2 parts of a high-efficiency water reducing agent, an additive consisting of 0.1-4 parts of nano calcium carbonate powder, 0.5-20 parts of cold rolling waste emulsion, 0.00625-0.0125 part of iron oxide powder, 0.0125-0.025 part of sodium sulfate and 0.0125-0.025 part of ethylene glycol, and 32-62 parts of water;
the cementing material comprises 50-75 parts of cement, 13-7 parts of slag micro powder, 13-6 parts of steel slag micro powder, 12-6 parts of modified fly ash and 12-6 parts of iron tailing powder; the high-efficiency water reducing agent is one or a mixture of two of polycarboxylic acid and naphthyl;
the preparation method of the modified fly ash in the cementing material comprises the following steps: firstly weighing fly ash, and adding 1.5-1.8 mol/L HNO according to the amount of 8-12 mL/g fly ash 3 Standing the solution for reaction for 60-70 minutes, and adding CaCO 25-35 wt% of the fly ash 3 Adding CaO with the mass being 6-10% of that of the fly ash, grinding the mixture to be uniform, adding hydrogen peroxide with the mass being 1-2% of that of the fly ash, stirring and drying the mixture, finally placing the mixture in a muffle furnace, heating the mixture to 880-900 ℃, calcining the mixture for 50-60 minutes, naturally cooling the mixture, and grinding the mixture to be below 50 meshes to obtain calcined ash; uniformly mixing nano calcium carbonate and nano aluminum oxide according to the mass ratio of (6-10) to 1 to obtain nano calcium-aluminum mixed ash; mixing 8-10 parts of calcined ash and 1 part of nano calcium-aluminum mixed ash, and shaking up to prepare the modified fly ash.
2. The method for preparing the impervious corrosion-resistant concrete by using the metallurgical solid wastes as the claim 1, wherein the modified fly ash is prepared by modifying power plant fly ash, and SiO in the power plant fly ash 2 And Al 2 O 3 More than or equal to 80 percent of Al 2 O 3 The content is more than or equal to 25 percent, and the particle size is less than or equal to 270 mu m.
3. The impervious corrosion-resistant concrete prepared by utilizing metallurgical solid wastes according to claim 1, which is characterized in that nano calcium carbonate powder has a particle size of 10-80 nm and is hydrophilic; the particle size of the iron oxide powder is 0.1-1 [ mu ] m.
4. The impervious corrosion-resistant concrete prepared by utilizing metallurgical solid wastes according to claim 1, wherein the coarse aggregate is a continuous graded mine waste stone, the particle size ranges from 5mm to 20mm, the Mohs hardness ranges from 5mm to 7, and the crushing value is less than or equal to 10%; the fine aggregate is mine waste rock artificial sand and iron tailing sand, the crushing value is less than or equal to 25%, the proportion of the mine waste rock artificial sand is 90-10%, the proportion of the iron tailing sand is 10-90%, the mine waste rock artificial sand and the iron tailing sand are mixed to form continuous gradation, and the grain size is less than or equal to 5 mm; the fineness modulus of the mine barren rock artificial sand in the fine aggregate is 2.2-3.6, the iron tailing sand is divided into two types of coarse and fine, the fineness modulus of the coarse iron tailing sand is 2.1-3.5, the fineness modulus of the fine iron tailing sand is 0.7-1.8, and the amount of the particle size d less than or equal to 0.16mm accounts for 8-20% of the amount of the fine iron tailing sand.
5. The impervious corrosion-resistant concrete prepared by using metallurgical solid wastes according to claim 1, wherein the nano alumina powder has a particle size of 10-60 nm and a crystal form of gamma-Al 2 O 3 。
6. The method for preparing the anti-permeability and corrosion-resistant concrete by using the metallurgical solid waste according to any one of claims 1 to 5, wherein the coarse aggregate and the fine aggregate are mixed in a stirring tank, the cementing material is added for mixing, then the high-efficiency water reducing agent and water are added for mixing, and the mixture is injected into a concrete transport vehicle after being uniformly stirred; the method is characterized in that the additive is a nano calcium carbonate mixture subjected to dispersion treatment, and is added into a stirring tank before or simultaneously with the high-efficiency water reducing agent and water; the nano calcium carbonate mixture is prepared by dispersing nano calcium carbonate powder, and the dispersing method comprises the following steps: and (2) putting 0.5-20 parts of cold rolling waste emulsion into a stirring device, starting stirring, adding 0.00625-0.0125 parts of iron oxide powder, and then sequentially adding 0.1-4 parts of nano calcium carbonate powder, 0.0125-0.025 parts of sodium sulfate and 0.0125-0.025 parts of ethylene glycol to form uniformly and stably dispersed nano calcium carbonate slurry.
7. The method for preparing the impervious corrosion-resistant concrete by utilizing the metallurgical solid wastes as claimed in claim 6, wherein the initial stirring speed of a stirring device is controlled to be 800-1200 rpm, the iron oxide powder is added and stirred for 2-3 minutes, the nano calcium carbonate powder is divided into 2-5 equal parts and added in batches, and each batch is separated by 3-5 minutes; adding sodium sulfate, and continuously stirring for 3-5 minutes; and finally, adding ethylene glycol, stirring for 10-15 minutes, reducing the stirring speed to 100-150 rpm, stirring for 5-10 minutes, and stopping stirring.
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