CN117088652B - Active excitation copper slag concrete and preparation method thereof - Google Patents
Active excitation copper slag concrete and preparation method thereof Download PDFInfo
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- CN117088652B CN117088652B CN202311356892.4A CN202311356892A CN117088652B CN 117088652 B CN117088652 B CN 117088652B CN 202311356892 A CN202311356892 A CN 202311356892A CN 117088652 B CN117088652 B CN 117088652B
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- 239000002893 slag Substances 0.000 title claims abstract description 74
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000010949 copper Substances 0.000 title claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 66
- 239000004567 concrete Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000005284 excitation Effects 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 39
- 230000000694 effects Effects 0.000 claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004568 cement Substances 0.000 claims abstract description 22
- 239000011737 fluorine Substances 0.000 claims abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 19
- -1 polysiloxane Polymers 0.000 claims abstract description 19
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- VPKQPPJQTZJZDB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C VPKQPPJQTZJZDB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 8
- 239000011707 mineral Substances 0.000 claims abstract description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 8
- 239000004576 sand Substances 0.000 claims abstract description 7
- 239000004575 stone Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 9
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical group CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 claims description 3
- 229940053009 ethyl cyanoacrylate Drugs 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002910 solid waste Substances 0.000 abstract description 2
- 239000011083 cement mortar Substances 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 238000006703 hydration reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012190 activator Substances 0.000 description 8
- 230000036571 hydration Effects 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- JLDKGEDPBONMDR-UHFFFAOYSA-N calcium;dioxido(oxo)silane;hydrate Chemical compound O.[Ca+2].[O-][Si]([O-])=O JLDKGEDPBONMDR-UHFFFAOYSA-N 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 238000006664 bond formation reaction Methods 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052840 fayalite Inorganic materials 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000006227 byproduct 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 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
-
- 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
- C04B2111/00025—Aspects relating to the protection of the health, e.g. materials containing special additives to afford skin protection
-
- 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
- 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
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
-
- 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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The application provides an active excitation copper slag concrete and a preparation method thereof, wherein the preparation method comprises the following steps: the cement mortar is prepared by uniformly mixing 200-250 parts by weight of cement, 70-80 parts by weight of copper slag powder, 70-80 parts by weight of mineral powder, 880-930 parts by weight of sand, 1000-1100 parts by weight of crushed stone, 6.8-7.3 parts by weight of additive, 5-15 parts by weight of active exciting agent and 165 parts by weight of water, wherein the active exciting agent is prepared by the following steps: mixing perfluorohexyl ethyl acrylate and methyl silicone oil according to the weight ratio of 1:4.5-1:5, heating to 60-65 ℃, continuously stirring in the heating process, and reacting at constant temperature for 5 hours to obtain fluorine-containing polysiloxane; and adding a composite emulsifier into the fluorine-containing polysiloxane to obtain the activity excitant. The active excitation copper slag concrete provided by the application improves the utilization rate of copper tailing slag, and solves the problems of large occupied area and serious environmental pollution of waste copper slag solid waste.
Description
Technical Field
The application relates to the technical field of concrete, in particular to an active excitation copper slag concrete and a preparation method thereof.
Background
Copper slag is a byproduct of the pyrometallurgy copper smelting and refining process, and is industrial solid waste. Through researches, the copper slag powder can promote the hydration of cement, generate more hydrated calcium silicate gel and improve the early and later strength of concrete. The pore structure of the concrete is improved, the capillary porosity and average pore diameter are reduced, and the connectivity of the pores is increased, so that the compactness and durability of the concrete are improved. The water demand and the heat evolution rate of the concrete are reduced, the cement consumption and the hydration heat peak value are reduced, the shrinkage deformation and the temperature stress of the concrete are reduced, and the crack resistance of the concrete is improved. Replaces part of cement, reduces the cost and carbon emission of concrete, and realizes resource conservation and environmental protection.
The copper slag powder has lower activity, and needs higher water-cement ratio and more cement consumption to ensure the workability of the concrete. Because of the problems of low activity and high heavy metal content, the influence of the copper slag powder on the workability, mechanical property and durability of the concrete is much more complex than that of common additives such as slag, fly ash and the like, and the application of the copper slag powder as the additive in the concrete is hindered.
Disclosure of Invention
The present application aims to provide an activated copper slag concrete and a preparation method thereof, so as to improve at least one technical problem. The above object is achieved by the following technical solutions.
In a first aspect, embodiments of the present application provide a method for preparing an activated copper slag concrete, including:
uniformly mixing 200-250 parts of cement, 70-80 parts of copper slag powder, 70-80 parts of mineral powder, 880-930 parts of sand, 1000-1100 parts of crushed stone, 6.8-7.3 parts of additive, 5-15 parts of active exciting agent and 165 parts of water to obtain active excitation copper slag concrete, wherein the active exciting agent is prepared by the following steps of: mixing perfluorohexyl ethyl acrylate and methyl silicone oil according to the weight ratio of 1:4.5-1:5, heating to 60-65 ℃, continuously stirring in the heating process, and reacting at constant temperature for 5 hours to obtain fluorine-containing polysiloxane; and adding a composite emulsifier into the fluorine-containing polysiloxane to obtain the activity excitant.
In one embodiment, the preparation method of the activity excitant further comprises the steps of mixing perfluorohexyl ethyl acrylate and methyl silicone oil according to a weight ratio of 1:4.5-1:5, and adding 0.02 part of rhodium as a catalyst.
In one embodiment, the preparation method of the activity excitant further comprises heating to 60-65 ℃, continuously stirring during the heating process, reacting at constant temperature for 5 hours, and distilling the reactant under reduced pressure.
In one embodiment, the preparation method of the activity excitant further comprises the steps of adding 3-5 wt% of composite emulsifier after reduced pressure distillation to obtain fluorine-containing polysiloxane.
In one embodiment, the method of preparing the composite emulsifier is: mixing fatty alcohol polyoxyethylene ether sodium sulfate, sodium dodecyl sulfate and poly 4-pentenoic acid modified nano silicon dioxide according to the weight ratio of 3:2:0.1, and obtaining the composite emulsifier.
In one embodiment, the preparation method of the poly 4-pentenoic acid modified nano silicon dioxide comprises the following raw materials in parts by weight: nano silicon dioxide powder: 60 parts; a coherent mass: 40 parts; and (2) a binder: 0.3 parts; 0.5 parts of an oxidant; 0.3 part of stabilizer, 0.5 part of chain transfer agent and 100 parts of water.
In one embodiment, the binder is ethyl cyanoacrylate.
In one embodiment, the oxidizing agent is hydrogen peroxide and the stabilizing agent is ascorbic acid.
In one embodiment, the chain transfer agent is mercaptoethanol and the mucilage is 4-pentenoic acid.
In a second aspect, the application provides an activated copper slag concrete, comprising, by weight, 200-250 parts of cement, 70-80 parts of copper slag powder, 70-80 parts of mineral powder, 880-930 parts of sand, 1000-1100 parts of crushed stone, 6.8-7.3 parts of an additive, 5-15 parts of an activated activator and 165 parts of water, wherein the activated activator comprises fluorine-containing polysiloxane and a composite emulsifier.
The activity excitation copper slag concrete provided by the embodiment of the application increases the activity of copper slag powder through fluorine-containing and polyether-modified siloxane, and promotes hydration reaction or chemical bond formation between the copper slag powder and cement or other admixtures. Can carry out complexation or adsorption reaction with heavy metal components in the copper slag powder, reduce the content and activity of the heavy metal in the copper slag powder, and reduce the harm to the environment and human health. Meanwhile, the complexing and adsorption effects can also act on calcium ions in the cementing material to increase the dissolution rate of the calcium ions, so that the hydration of the cementing material is accelerated, the hydration degree of the cementing material is improved, and the gelation activity of the copper slag powder is further improved. The fluorine-containing polyether-modified siloxane can have a synergistic effect with cement or other additives to promote hydration reaction or chemical bond formation between the cement or other additives and copper slag powder, so that the strength, durability and impermeability of the concrete are improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Figure 1 shows the XRD pattern of copper slag as used herein.
Fig. 2 shows an infrared spectrum of the fluorine-containing polysiloxane of example 1 of the present application.
Fig. 3 shows a schematic representation of an activated copper slag concrete mix of example 1 of the present application.
Fig. 4 shows an SEM image of the activated copper slag concrete slurry of example 1 of the present application after hardening.
Fig. 5 shows a schematic diagram of the copper slag concrete mixture of comparative example 1 of the present application.
Fig. 6 shows an SEM image of copper slag concrete slurry of comparative example 1 of the present application after hardening.
Detailed Description
In order to better understand the present application, the following description will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Recent research results show that the copper slag powder can promote cement hydration to generate more hydrated calcium silicate gel, and improve early and later strength of concrete. The main mineral component of copper slag is fayalite, and the volcanic ash activity of the copper slag is low. In order to better exert the volcanic ash activity of the copper slag powder, a chemical activity activator can be added.
The application provides a preparation method of active excitation copper slag concrete, which comprises the following steps:
the method comprises the following steps of uniformly mixing 200-250 parts by weight of cement, 70-80 parts by weight of copper slag powder, 70-80 parts by weight of mineral powder, 880-930 parts by weight of sand, 1000-1100 parts by weight of broken stone, 6.8-7.3 parts by weight of additive, 5-15 parts by weight of active exciting agent and 165 parts by weight of water to obtain the active excitation copper slag concrete. Specifically, the activated copper slag concrete can comprise 200, 230, 250 parts of cement, 70, 75, 80 parts of copper slag powder, 70, 75, 80 parts of mineral powder, 880, 900, 930 parts of sand, 1000, 1050, 1100 parts of crushed stone, 6.8, 7.1, 7.3 parts of additive, 5, 7, 10, 15 parts of activated activator and 165 parts of water by weight.
Wherein the active excitant is prepared by the following steps: the perfluorohexyl ethyl acrylate and the methyl silicone oil are mixed in a weight ratio of 1:4.5 to 1:5, for example, the weight ratio of perfluorohexyl ethyl acrylate to methyl silicone oil can be 1:4.5, 1:4.6, 1:4.8 or 1:5, and the heating temperature can be 63 ℃ in particular. And in the heating process, a magnetic stirrer can be used for continuous stirring, the reaction is carried out for 5 hours at constant temperature, the fluorine-containing polysiloxane is obtained, and the composite emulsifying agent is added into the fluorine-containing polysiloxane after the reduced pressure distillation of the fluorine-containing polysiloxane, so that the activity excitant is obtained. For specific operation of the reduced pressure distillation reference is made to the parameters used for conventional reduced pressure distillation of the reactants.
In the embodiment of the application, the copper slag is from the southeast copper industry tailings of Fujian, the used chemical reagents are all analytically pure, and the used concrete raw materials are all from Tianshui concrete Co., yangsha.
With reference to FIG. 1, XRD analysis was performed on the copper slag used in the examples, the main phase of the copper slag being fayalite (Fe 2 SiO 4 ) The content is 44.5wtThe iron olivine is a silicate mineral, one of the iron-forsterite series, and the copper slag contains 35.5wt% of amorphous glass bodies.
Preparation example
The composite emulsifier is prepared by the following preparation method:
mixing fatty alcohol polyoxyethylene ether sodium sulfate, sodium dodecyl sulfate and poly 4-pentenoic acid modified nano silicon dioxide according to the weight ratio of 3:2:0.1, and obtaining the composite emulsifier. The preparation method of the poly 4-pentenoic acid modified nano silicon dioxide comprises the following raw materials in parts by weight: nano silicon dioxide powder: 60 parts; a coherent mass: 40 parts; and (2) a binder: 0.3 parts; 0.5 parts of an oxidant; 0.3 part of stabilizer, 0.5 part of chain transfer agent and 100 parts of water; wherein the binder is ethyl cyanoacrylate, the oxidant is hydrogen peroxide, the stabilizer is ascorbic acid, the chain transfer agent is mercaptoethanol, and the adhesive is 4-pentenoic acid.
Example 1
200 parts of cement, 70 parts of copper slag powder, 70 parts of mineral powder, 880 parts of sand, 1000 parts of broken stone, 6.8 parts of additive, 7 parts of active exciting agent and 165 parts of water are uniformly mixed to obtain the active excitation copper slag concrete.
The active excitant is prepared by the following steps: and mixing perfluorohexyl ethyl acrylate and methyl silicone oil according to the weight ratio of 1:4.5, adding 0.02 part of rhodium simple substance, heating to 60 ℃, continuously stirring in the heating process, reacting at constant temperature for 5 hours, performing reduced pressure distillation on the reactant, removing unreacted raw materials and catalyst to obtain fluorine-containing polysiloxane, and adding 3wt% of composite emulsifier into the fluorine-containing polysiloxane to obtain the activity excitant.
Referring to fig. 2, fig. 2 shows the results of infrared spectroscopic analysis of fluorine-containing polysiloxanes (without complex emulsifiers). Detailed infrared active group analysis is shown in the following table, and the high molecular infrared spectrum is more complex, so that other explanation possibilities are not excluded.
Table 1:
the sample has a small amount of residual moisture, and the infrared spectrum can indicate that the structural design of the polymer meets the design expectation, and each monomer is effectively polymerized. Referring to fig. 3, fig. 3 shows a photograph of a concrete mix after the addition of an activation agent, and after the mix is turned over, it can be seen that there is no apparent black substrate turned over underneath.
With continued reference to fig. 4, fig. 4 shows SEM pictures of cement paste after 28 days of hardening of activated copper slag concrete after drying and grinding, with a magnification of 3 ten thousand times, and a significant increase in the amount of C-S-H gel was seen. It was thus determined that the activity activator promoted the formation of C-S-H gel.
Example 2
This example differs from example 1 only in that 15 parts of the active exciting agent is included in the active exciting copper slag concrete.
Example 3
This example differs from example 1 only in that perfluorohexyl ethyl acrylate and methyl silicone oil are mixed in a weight ratio of 1:5.
Example 4
This example differs from example 1 only in that 5wt% of a complex emulsifier was added to the fluorine-containing polysiloxane to obtain an activity activator.
Comparative example 1
The comparative example differs from example 1 only in that no active activator was added to the copper slag concrete.
Referring to fig. 5, fig. 5 shows a photograph of a concrete mix without an active activator added, after the mix is turned over, it can be seen that there is a clear black substrate turned over underneath. The black copper slag powder is sunk due to poor dispersibility and high density of the copper slag powder. With continued reference to fig. 6, fig. 6 shows an SEM image of the hardened cement slurry of the slag powder concrete of comparative example 1 after drying and grinding, at a magnification of 3 ten thousand times, with a smaller amount of C-S-H gel.
The contents of heavy metals contained in the copper slag leachate made according to standard GB/T30810-2014 are shown in the following table:
table 2:
from the above table, the content of heavy metal in the copper slag added with the activity excitant is reduced, which is probably because fluorine-containing siloxane modified by polyether can be subjected to complexation or adsorption reaction with heavy metal components in the copper slag powder, thereby reducing the content of heavy metal in the copper slag powder and reducing the harm to the environment and human health. Meanwhile, the complexing and adsorption effects can also act on calcium ions in the cementing material to increase the dissolution rate of the calcium ions, so that the hydration of the cementing material is accelerated, the hydration degree of the cementing material is improved, and the gelation activity of the copper slag powder is further improved. When the activity excitant is introduced, the irregular chain structure of O-Si-O-Al-O in the copper slag is broken, siO 2 、CaO、MgO、Al 2 O 3 The active ions in the components are dissolved out to promote the pozzolan reaction, namely, the reaction of the components such as the active silicon dioxide, the calcium oxide and the like with the calcium hydroxide is carried out smoothly, and the gel substances such as calcium silicate hydrate (C-S-H) gel and the like with strength are generated, so that the strength of the cement-based material is improved.
Comparative example 2
The comparative example differs from example 1 only in that 15 parts of polysiloxane as an activation initiator was included in the copper slag concrete.
Comparative example 3
This comparative example differs from example 1 only in that 3wt% sodium fatty alcohol polyoxyethylene ether sulfate was added to the fluorine-containing polysiloxane as an emulsifier.
The compressive strength of each group of concrete at each age is measured according to GB/T50081-2019 Standard of test method for physical and mechanical properties of concrete, and the measurement results are shown in the following table:
table 3:
from the table above, the addition of the active exciting agent significantly improves the strength of the copper slag applied to concrete, because the copper slag powder is excited by the active exciting agent, the hydration degree of the copper slag powder is increased, and more C-S-H gel is generated. Meanwhile, the addition of the composite emulsifier plays a great role in the exciting agent, and the effect of the active exciting agent without the composite emulsifier is obviously inferior to that of the active exciting agent with the composite emulsifier. In addition, the method and the material proportion in the synthesis process of the activity excitant influence the strength exertion of the concrete.
The fluorine-containing polyether-modified siloxane can form a layer of film on the surface of the copper slag powder, reduce the surface energy and hydrophilicity of the copper slag powder, and increase the hydrophobicity and oleophobicity of the copper slag powder, so that the mutual adsorption and permeation between the copper slag powder and water or oil phase are reduced, and the dispersibility and stability of the copper slag powder are improved. The fluorine and polyether modified siloxane can have synergistic effect with cement or other additives to promote hydration reaction or chemical bond formation between the cement or other additives and copper slag, so that the strength, durability and impermeability of the concrete are improved.
The active excitation copper slag concrete provided by the embodiment of the application effectively reduces the water-cement ratio and viscosity of the concrete and improves the workability and fluidity of the concrete. Inhibit the generation of alkali aggregate reaction and reduce the cracking risk of concrete. The waterproof and antifouling capacity of the concrete is improved, and the service life of the concrete is prolonged.
Furthermore, the descriptions of the terms "some embodiments," "other embodiments," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this application, the schematic representations of the above terms are not necessarily for the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples described herein, as well as features of various embodiments or examples, may be combined and combined by those skilled in the art without conflict.
The above embodiments are only for illustrating the technical solution of the present application, and are not limiting thereof; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the embodiments of the present application, and are intended to be included within the scope of the present application.
Claims (4)
1. The preparation method of the active excitation copper slag concrete is characterized by comprising the following steps of:
uniformly mixing 200-250 parts of cement, 70-80 parts of copper slag powder, 70-80 parts of mineral powder, 880-930 parts of sand, 1000-1100 parts of crushed stone, 6.8-7.3 parts of additive, 5-15 parts of active exciting agent and 165 parts of water to obtain active excitation copper slag concrete, wherein the active exciting agent is prepared by the following steps of: mixing perfluorohexyl ethyl acrylate and methyl silicone oil according to the weight ratio of 1:4.5-1:5, adding 0.02 part of rhodium as a catalyst, heating to 60-65 ℃, continuously stirring in the heating process, reacting at constant temperature for 5 hours, and performing reduced pressure distillation on reactants to obtain fluorine-containing polysiloxane; 3-5 wt% of composite emulsifier is added into the fluorine-containing polysiloxane to obtain the activity excitant; the preparation method of the composite emulsifier comprises the following steps: mixing fatty alcohol polyoxyethylene ether sodium sulfate, sodium dodecyl sulfate and poly 4-pentenoic acid modified nano silicon dioxide according to the weight ratio of 3:2:0.1 to obtain the composite emulsifier; the preparation method of the poly 4-pentenoic acid modified nano silicon dioxide comprises the following raw materials in parts by weight: 60 parts of nano silicon dioxide powder, 40 parts of a sticky polymer, 0.3 part of a binder, 0.5 part of an oxidant, 0.3 part of a stabilizer, 0.5 part of a chain transfer agent and 100 parts of water, wherein the binder is ethyl cyanoacrylate, and the sticky polymer is 4-pentenoic acid.
2. The method according to claim 1, wherein the oxidizing agent is hydrogen peroxide and the stabilizer is ascorbic acid.
3. The process of claim 1 wherein the chain transfer agent is mercaptoethanol.
4. An activated copper slag concrete prepared by the method of any one of claims 1 to 3.
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