CN117658502A - Steel slag-based in-situ growth hybrid nano-particle and preparation method thereof - Google Patents
Steel slag-based in-situ growth hybrid nano-particle and preparation method thereof Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 360
- 239000002893 slag Substances 0.000 title claims abstract description 360
- 239000010959 steel Substances 0.000 title claims abstract description 360
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 146
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 47
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 44
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 37
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 28
- 239000000378 calcium silicate Substances 0.000 claims abstract description 27
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003763 carbonization Methods 0.000 claims abstract description 18
- 238000003980 solgel method Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims description 150
- 238000003756 stirring Methods 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 42
- 229910052710 silicon Inorganic materials 0.000 claims description 42
- 239000010703 silicon Substances 0.000 claims description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000005303 weighing Methods 0.000 claims description 20
- 239000001569 carbon dioxide Substances 0.000 claims description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 230000006911 nucleation Effects 0.000 claims description 6
- 238000010899 nucleation Methods 0.000 claims description 6
- 239000004568 cement Substances 0.000 abstract description 79
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 42
- 230000000694 effects Effects 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 15
- 238000001879 gelation Methods 0.000 abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 9
- 239000011707 mineral Substances 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 24
- 238000001878 scanning electron micrograph Methods 0.000 description 20
- 235000012241 calcium silicate Nutrition 0.000 description 19
- 239000011083 cement mortar Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 14
- 238000010998 test method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 235000019795 sodium metasilicate Nutrition 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- 239000004567 concrete Substances 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 7
- 239000002910 solid waste Substances 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- -1 silicate ions Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- AGWMJKGGLUJAPB-UHFFFAOYSA-N aluminum;dicalcium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Ca+2].[Ca+2].[Fe+3] AGWMJKGGLUJAPB-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 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
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
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- 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
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a steel slag-based in-situ growth hybrid nanoparticle and a preparation method thereof. The preparation method comprises the steps of preparing steel slag-based in-situ growth hybrid nano calcium silicate and nano silicon dioxide by a sol-gel method, and preparing steel slag-based in-situ growth hybrid nano calcium carbonate and nano silicon dioxide by a carbonization method. The invention can not only improve the dispersibility of the nano particles in the cement-based material, but also improve the gelation activity and volume stability of the steel slag. In addition, the invention can strengthen the binding force between the nano particles and the matrix, and ensure the use effect of the in-situ growth hybrid nano particles as nano additives or mineral admixtures.
Description
Technical Field
The invention relates to a steel slag-based composite material and a preparation method thereof, in particular to steel slag-based in-situ growth hybrid nano particles and a preparation method thereof.
Background
Currently, the nanomaterials commonly used for modifying cement-based materials are mainly: carbon nanomaterials (carbon nanotubes, graphene, etc.) and inorganic nanoparticles (nanosilica, and nanosilica, etc.). Among them, nano silica, nano calcium silicate hydrate and nano calcium carbonate are receiving much attention. However, the nanomaterial has a large specific surface area and a high specific surface energy, so that the nanomaterial is difficult to disperse and is extremely easy to agglomerate in a cement matrix, thereby limiting the exertion of the effects.
The patent 201711143543.9 and 201810226554.1 respectively disclose a preparation method for in-situ growth of nano particles on the surface of solid waste and a method for in-situ growth of calcium silicate hydrate on the surface of mineral admixture. Both patents take solid waste such as fly ash as a matrix, and nano-particles such as nano-silica, nano-calcium carbonate and nano-calcium silicate hydrate are grown on the surface of the matrix in situ, so that the high-efficiency nano-additive with good dispersion effect is obtained. In both of the above patents, the solid waste is pretreated prior to in situ growth of the nanoparticles to facilitate subsequent in situ growth of the nanoparticles. The method is mainly characterized in that the surfaces of solid wastes such as fly ash are smooth and inert, nucleation sites are difficult to provide for in-situ growth of the nanoparticles, and the adhesion growth of the nanoparticles on a solid waste substrate is not facilitated. In addition, the smooth surface weakens the binding force between the nano particles and the solid waste, so that the in-situ grown nano particles on the surface of the solid waste are easy to fall off in the use process (mixing process with cement and the like) and the use effect of the in-situ grown nano particles is affected.
On the other hand, the cement production process causes a large amount of carbon emissions. Obviously, this does not conform to the low-carbon, green environmental protection concept. The steel slag piled up in large quantity contains dicalcium silicate (C 2 S), tricalcium silicate (C) 3 S), tricalcium aluminate (C) 3 A) And tetracalcium aluminoferrite (C) 4 AF) and the like, thereby being used as mineral admixtures, partially replacing cement and reducing the use amount of cement in cement-based materials. However, the steel slag has the problems of low gelation activity and poor volume stability, which limits the large-scale recycling of the steel slag in cement-based materials. The prior method for improving the gelation activity and the volume stability of the steel slag mainly comprises physical modification (such as mechanical grinding), chemical modification (such as acetic acid modification), reconstruction of the mineral phase of the steel slag and the like.
Disclosure of Invention
The invention aims to: the invention aims to provide the steel slag-based in-situ growth hybrid nano-particles which have strong binding force between nano-particles and a steel slag matrix, good dispersibility of the nano-particles, high activity of steel slag gel and good volume stability;
the second object of the invention is to provide a preparation method of the steel slag-based in-situ growth hybrid nano-particles.
The technical scheme is as follows: the steel slag-based in-situ growth hybrid nanoparticle comprises a steel slag substrate, wherein calcium-containing nanoparticles are grown on the surface of the steel slag substrate in situ, and nano silicon dioxide is grown on the surface of the steel slag substrate in situ by taking the calcium-containing nanoparticles as nucleation sites.
Wherein the calcium-containing nano particles are nano calcium silicate hydrate or nano calcium carbonate.
The preparation method of the steel slag-based in-situ growth hybrid nano-particles comprises the following steps of:
(1) Mixing water, absolute ethyl alcohol, ammonia water and a surfactant to prepare a solution A, and keeping the solution A at a constant temperature; adding steel slag into the solution A, and stirring to obtain steel slag slurry A;
(2) Mixing a silicon source with absolute ethyl alcohol and separating into a solution B and a solution C;
(3) Dropwise adding the solution B into the steel slag slurry A, and stirring to obtain steel slag slurry B;
(4) Dropwise adding the solution C into the steel slag slurry B, and stirring to obtain steel slag slurry C; and washing and drying to obtain the steel slag-based in-situ growth hybrid nano particles.
In the step (1), the water, the absolute ethyl alcohol and the ammonia water are respectively in parts by volume: 45-5 parts, 5-45 parts and 0-2 parts of surfactant, wherein the mass part of the surfactant is 0-2 parts; the mass portion of the steel slag is 1-4 portions. The constant temperature of the solution is 30-60 ℃. In the step (2), the silicon source and the absolute ethyl alcohol are respectively 0.5-2 parts by volume and 5-10 parts by volume.
The principle of the sol-gel method is as follows: and (3) adding the silicon sources step by step, namely adding part of the silicon sources, reacting for a period of time, and then adding the rest silicon sources. Firstly, adding a silicon source, taking steel slag as a matrix under the action of alkaline environment and calcium ions released by hydration of the steel slag, and growing nano calcium silicate hydrate on the surface of the matrix in situ. And then adding a silicon source to be based on the silicon source, performing hydrolysis and condensation reaction in an alkaline environment, and growing nano silicon dioxide on the surface of the steel slag in situ to finally obtain the steel slag-based in situ growth hybrid nano calcium silicate hydrate and nano silicon dioxide. Specifically, the silicon source added first undergoes hydrolysis and condensation reactions under alkaline conditions to produce silicic acid polymers. In the process, calcium ions released by hydration of the steel slag are combined with silicic acid polymers to generate nano hydrated calcium silicate, and the surface of the steel slag and the hydrated calcium silicate on the surface of the steel slag are taken as nucleation sites to be attached and grown on the surface of the steel slag, so that the in-situ growth of calcium-containing nano particles on the surface of the steel slag is realized.
The preparation method of the steel slag-based in-situ growth hybrid nano-particles comprises the following steps of:
(1) Mixing water, absolute ethyl alcohol and a surfactant to prepare a solution A, and keeping the solution at a constant temperature; adding steel slag into the solution A, and stirring to obtain steel slag slurry A;
(2) Weighing a silicon source A and a silicon source B, and adding the silicon source A into the steel slag slurry A to obtain steel slag slurry B;
(3) Introducing carbon dioxide gas into the steel slag slurry B until the pH value of the steel slag slurry B is less than 8, so as to obtain steel slag slurry C;
(4) Adding a silicon source B into the steel slag slurry C to obtain steel slag slurry D; and introducing carbon dioxide gas into the steel slag slurry D until the pH value of the steel slag slurry D is less than 8, obtaining steel slag slurry E, washing and then truly drying to obtain the steel slag-based in-situ growth hybrid nano particles.
Wherein, in the step (1), the constant temperature of the solution is: 30-80 ℃; in the step (2), the volume ratio of the solution B to the solution C is as follows: 1-3:9-7. The steel slag, water, absolute ethyl alcohol and surfactant are respectively prepared from the following components in parts by weight: 10 to 50 parts, 100 to 200 parts, 50 to 150 parts and 0 to 10 parts.
In the step (3), the carbon dioxide gas is introduced at the following rate: 150-350 ml/min; the stirring speed is as follows: 200-400 rpm.
The principle of the carbonization method is as follows: the silicon source is added step by step and carbonization reaction is carried out step by step, namely, a part of silicon source is added first, then the first carbonization reaction is carried out, after a period of time, the rest silicon source is added, and then the second carbonization reaction is carried out.
The silicon source added first can carry out chemical coprecipitation reaction with calcium ions released by hydration of the steel slag, the steel slag is taken as a matrix, and nano calcium silicate hydrate grows on the surface of the matrix in situ. Thereafter, carbon dioxide gas was introduced thereinto to carry out a first carbonization reaction. Carbon dioxide gas is dissolved in water and is subjected to carbonization reaction with nano calcium silicate hydrate which grows on the surface of steel slag in situ, so that mixed nano calcium carbonate and nano silicon dioxide are generated. Meanwhile, carbon dioxide dissolved in water can also carry out carbonization reaction with calcium ions in water to generate nano calcium carbonate, and the nano calcium carbonate grows in situ on the surface of the nano calcium carbonate by taking steel slag as a nucleation site due to the existence of the steel slag. Thereafter, the remaining silicon source is added and carbon dioxide gas is introduced to carry out a second carbonization reaction. The silicate ions in the silicon source react with hydrogen ions generated by the dissolution of carbon dioxide in water to produce silicic acid. Along with the decrease of the pH value of the system, silicic acid is polymerized into silicic acid dimer, further polymerized into silicic acid multimers such as silicic acid trimer, silicic acid tetramer and the like, and finally spherical nano silicon dioxide is formed. And as the rough steel slag surface has chemical activity and has the first carbonization reaction to generate hybrid nano calcium carbonate and nano silicon dioxide, the hybrid nano calcium carbonate and nano silicon dioxide can be used as nucleation sites of the nano silicon dioxide generated by the second carbonization reaction, the nano silicon dioxide is promoted to grow on the nano silicon dioxide in situ, and finally the steel slag-based in-situ grown hybrid nano calcium carbonate and nano silicon dioxide are obtained.
The principle of the invention: the invention takes the calcium element in the steel slag as a calcium source, firstly grows an intermediate transition layer-calcium-containing nano-particle on the surface of the steel slag in situ, and then further grows nano-silicon dioxide in situ, thereby forming the steel slag-based in situ growth hybrid nano-particle. Namely, by means of the rough surface and the gelation activity of the steel slag, the binding force between the calcium-containing nano particles and the steel slag matrix is enhanced, the in-situ growth nano particles are prevented from being separated from the steel slag in the use process, and the use effect is ensured. Compared with the nano particles, the steel slag has large particle size, can be more uniformly dispersed in the cement matrix, and the nano particles growing on the steel slag matrix in situ can be uniformly dispersed in the cement matrix along with the steel slag matrix, so that the dispersing effect of the nano particles in the cement matrix is improved. The nano particles growing on the steel slag matrix in situ can promote hydration of cement and hydraulic mineral phases in the steel slag, so that the gelation activity of the steel slag can be improved, and the large-doping application of the steel slag is realized. When the nano-particles grown in situ are nano-silica, the nano-silica has high pozzolanic activity, so that the gelation activity of the steel slag is improved.
In addition, the steel slag-based in-situ growth hybrid nano particles can improve the volume stability of the steel slag by consuming the reaction of free calcium oxide f-CaO and volcanic ash in the steel slag. In the preparation process of the steel slag-based in-situ growth hybrid nano particles, part of f-CaO in the steel slag reacts with water, so that the f-CaO is consumed, and the f-CaO content in the steel slag is reduced. In the use process of the steel slag-based in-situ growth hybrid nano particles, f-CaO reacts with water to generate calcium hydroxide CH along with the progress of hydration, but nano silicon dioxide growing on a steel slag substrate in situ has high volcanic ash activity, and can react with CH generated by the f-CaO when meeting water to generate calcium silicate hydrate C-S-H gel, so that the negative influence of f-CaO in the steel slag on the volume stability of the hardened cement-based material is reduced. The two are combined to promote the volume stability of the steel slag.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable effects: (1) The gelation activity and the volume stability of the steel slag are improved, and the steel slag is favorable for realizing the large-doping application of the steel slag as a mineral admixture; the binding force of the nano particles and the steel slag matrix is enhanced, and the use effect of the steel slag matrix in-situ growth hybrid nano particles as nano additives or mineral admixtures is ensured; (2) The controllable preparation of the steel slag-based in-situ growth hybrid nano calcium silicate hydrate and nano silicon dioxide is realized by a sol-gel method; (3) The high-efficiency and green preparation of the steel slag-based in-situ growth hybrid nano calcium carbonate and nano silicon dioxide is realized by a carbonization method; (4) The dispersibility of the nano particles in the cement-based material is improved, and the popularization and application of the nano additive in the cement-based material are facilitated.
Drawings
FIG. 1 is an SEM image of the raw steel slag of example 1 at 40000 Xmagnification;
FIG. 2 is an SEM image at a magnification of 150000 times after drying the steel slag slurry A obtained in the step (2) of example 1;
FIG. 3 is an SEM image at a magnification of 150000 times after drying the steel slag slurry B obtained in the step (4) of example 1;
FIG. 4 is an EDS spectrum of the steel slag slurry B obtained in the step (4) of example 1 after drying;
FIG. 5 is an SEM image at magnification of 150000 times of the steel slag-based in-situ grown hybrid nanoparticle obtained in example 1;
FIG. 6 is an FT-IR diagram of steel slag-based in-situ grown hybrid nanoparticles obtained in example 1;
FIG. 7 is an SEM image at magnification of 150000 magnification of steel slag-based in-situ grown hybrid nanoparticles obtained in example 2;
FIG. 8 is an SEM image at 300000 magnification of the steel slag based in-situ grown hybrid nanoparticle obtained in example 3;
FIG. 9 is an SEM image at 40000 magnification of steel slag-based in-situ grown hybrid nanoparticles obtained in example 4;
FIG. 10 is an SEM image at a magnification of 80000 of the steel slag slurry C obtained in the step (5) of example 5 after being dried;
FIG. 11 is an SEM image at 300000 magnification of the steel slag based in-situ grown hybrid nanoparticle obtained in example 5;
FIG. 12 is an XRD pattern of the steel slag-based in-situ grown hybrid nanoparticles obtained in example 5;
FIG. 13 is an SEM image at magnification of 80000 of the steel slag based in situ grown hybrid nano-particles obtained by example 6;
FIG. 14 is an SEM image at 300000 magnification of steel slag based in-situ grown hybrid nanoparticles obtained in example 7;
fig. 15 is an SEM image of the steel slag-based in-situ grown hybrid nanoparticles obtained in example 8 at 300000 x magnification.
Detailed Description
The present invention is described in further detail below.
Example 1
The sol-gel method for preparing the steel slag based in-situ growth hybrid nano calcium silicate hydrate and nano silicon dioxide comprises the following steps:
(1) According to the volume parts, 35 parts of water, 5 parts of absolute ethyl alcohol and 1 part of ammonia water are measured, 1 part of polyethylene glycol is weighed according to the weight parts, and is prepared into a solution A, so that the solution A is kept at a constant temperature of 40 ℃;
(2) Weighing 2 parts of steel slag according to the parts by weight, adding the steel slag into the solution A obtained in the step (1) while stirring the solution A at a rotating speed of 300rpm, and stirring for 5min to obtain steel slag slurry A;
(3) According to the volume parts, 1 part of tetraethoxysilane and 10 parts of absolute ethyl alcohol are measured and uniformly mixed, and then the mixture is divided into a solution B and a solution C according to the volume ratio of 3:7;
(4) Dropwise adding the solution B into the steel slag slurry A obtained in the step (2) while stirring the steel slag slurry A at a rotating speed of 300rpm, and continuously stirring for 30min after the completion of dropwise adding to obtain steel slag slurry B;
(5) Stirring the steel slag slurry B obtained in the step (4), dropwise adding the solution C into the steel slag slurry B, and continuously stirring for 3 hours after the dropwise adding is completed to obtain the steel slag slurry C;
(6) And (3) centrifugally washing the steel slag slurry C obtained in the step (5), and drying the steel slag slurry C to constant weight in vacuum at 60 ℃ to obtain steel slag-based in-situ growth hybrid nano-calcium silicate and nano-silica.
Example 2
The sol-gel method for preparing the steel slag based in-situ growth hybrid nano calcium silicate hydrate and nano silicon dioxide comprises the following steps:
(1) According to the volume parts, 35 parts of water, 5 parts of absolute ethyl alcohol and 1 part of ammonia water are measured, 1 part of polyethylene glycol is weighed according to the weight parts, and is prepared into a solution A, so that the solution A is kept at a constant temperature of 40 ℃;
(2) Weighing 2 parts of steel slag according to the parts by weight, adding the steel slag into the solution A obtained in the step (1) while stirring the solution A at a rotating speed of 300rpm, and stirring for 5min to obtain steel slag slurry A;
(3) According to the volume parts, 0.5 part of tetraethoxysilane and 10 parts of absolute ethyl alcohol are measured and uniformly mixed, and then the mixture is divided into a solution B and a solution C according to the volume ratio of 3:7;
(4) Dropwise adding the solution B into the steel slag slurry A obtained in the step (2) while stirring the steel slag slurry A at a rotating speed of 300rpm, and continuously stirring for 30min after the completion of dropwise adding to obtain steel slag slurry B;
(5) Stirring the steel slag slurry B obtained in the step (4), dropwise adding the solution C into the steel slag slurry B, and continuously stirring for 1.5h after the dropwise adding is completed to obtain steel slag slurry C;
(6) And (3) centrifugally washing the steel slag slurry C obtained in the step (5), and drying the steel slag slurry C to constant weight in vacuum at 60 ℃ to obtain steel slag-based in-situ growth hybrid nano-calcium silicate and nano-silica.
Example 3
The sol-gel method for preparing the steel slag based in-situ growth hybrid nano calcium silicate hydrate and nano silicon dioxide comprises the following steps:
(1) According to the volume parts, 10 parts of water, 30 parts of absolute ethyl alcohol and 2 parts of ammonia water are measured, 2 parts of polyethylene glycol is weighed according to the weight parts, and is prepared into a solution A, so that the solution A is kept at a constant temperature of 30 ℃;
(2) Weighing 1 part of steel slag according to the parts by weight, adding the steel slag into the solution A obtained in the step (1) while stirring the solution A at a rotating speed of 300rpm, and stirring for 5min to obtain steel slag slurry A;
(3) According to the volume parts, 1 part of tetraethoxysilane and 10 parts of absolute ethyl alcohol are measured and uniformly mixed, and then the mixture is divided into a solution B and a solution C according to the volume ratio of 1:9;
(4) Dropwise adding the solution B into the steel slag slurry A obtained in the step (2) while stirring the steel slag slurry A at a rotating speed of 200rpm, and continuously stirring for 60min after the completion of dropwise adding to obtain the steel slag slurry B;
(5) Stirring the steel slag slurry B obtained in the step (4), dropwise adding the solution C into the steel slag slurry B, and continuously stirring for 8 hours after the dropwise adding is completed to obtain the steel slag slurry C;
(6) And (3) centrifugally washing the steel slag slurry C obtained in the step (5), and drying the steel slag slurry C to constant weight in vacuum at 60 ℃ to obtain steel slag-based in-situ growth hybrid nano-calcium silicate and nano-silica.
Example 4
The sol-gel method for preparing the steel slag based in-situ growth hybrid nano calcium silicate hydrate and nano silicon dioxide comprises the following steps:
(1) Weighing 40 parts of water and 0.5 part of ammonia water according to the parts by volume, weighing 0.5 part of polyethylene glycol according to the parts by weight, and preparing a solution A, so that the solution A is kept at a constant temperature of 60 ℃;
(2) Weighing 4 parts of steel slag according to the parts by weight, adding the steel slag into the solution A obtained in the step (1) while stirring the solution A at a rotation speed of 400rpm, and stirring the solution A for 5min to obtain steel slag slurry A;
(3) According to the volume parts, 2 parts of tetraethoxysilane and 10 parts of absolute ethyl alcohol are measured and uniformly mixed, and then the mixture is divided into a solution B and a solution C according to the volume ratio of 2:8;
(4) Dropwise adding the solution B into the steel slag slurry A obtained in the step (2) while stirring the steel slag slurry A at a rotating speed of 300rpm, and continuously stirring for 10min after the completion of dropwise adding to obtain the steel slag slurry B;
(5) Stirring the steel slag slurry B obtained in the step (4), dropwise adding the solution C into the steel slag slurry B, and continuously stirring for 1h after the dropwise adding is completed to obtain steel slag slurry C;
(6) And (3) centrifugally washing the steel slag slurry C obtained in the step (5), and drying the steel slag slurry C to constant weight in vacuum at 60 ℃ to obtain steel slag-based in-situ growth hybrid nano-calcium silicate and nano-silica.
Example 5
The carbonization method for preparing the steel slag-based in-situ growth hybrid nano calcium carbonate and nano silicon dioxide comprises the following steps:
(1) Weighing 200 parts of water, 50 parts of absolute ethyl alcohol and 5 parts of polyethylene glycol according to parts by weight, and preparing a solution A, so that the solution A is kept at a constant temperature of 40 ℃;
(2) Weighing 25 parts of steel slag according to parts by weight, adding the steel slag into the solution A obtained in the step (1) while stirring the solution A at a rotation speed of 400rpm, and stirring the solution A for 5min to obtain steel slag slurry A;
(3) Weighing 15 parts of zero water sodium metasilicate according to the weight ratio of 1:9, and dividing the zero water sodium metasilicate into a silicon source A and a silicon source B;
(4) Adding the silicon source A obtained in the step (3) into the steel slag slurry A obtained in the step (2) to obtain steel slag slurry B;
(5) Stirring the steel slag slurry B obtained in the step (4) at a rotating speed of 400rpm, and introducing carbon dioxide gas into the steel slag slurry B at a flow speed of 250ml/min until the pH value of the steel slag slurry B is less than 8, so as to obtain steel slag slurry C;
(6) Adding the silicon source B obtained in the step (3) into the steel slag slurry C obtained in the step (5) to obtain steel slag slurry D;
(7) Stirring the steel slag slurry D obtained in the step (6) at a rotating speed of 400rpm, and introducing carbon dioxide gas into the steel slag slurry D at a flow speed of 250ml/min until the pH value of the steel slag slurry D is less than 8, so as to obtain steel slag slurry E;
(8) And (3) centrifugally washing the steel slag slurry E obtained in the step (7), and drying the steel slag slurry E to constant weight in vacuum at 60 ℃ to obtain steel slag-based in-situ growth hybrid nano-particles, namely steel slag-based in-situ growth hybrid nano-calcium carbonate and nano-silica.
Example 6
The carbonization method for preparing the steel slag-based in-situ growth hybrid nano calcium carbonate and nano silicon dioxide comprises the following steps:
(1) Weighing 200 parts of water, 50 parts of absolute ethyl alcohol and 5 parts of polyethylene glycol according to parts by weight, and preparing a solution A, so that the solution A is kept at a constant temperature of 40 ℃;
(2) Weighing 25 parts of steel slag according to parts by weight, adding the steel slag into the solution A obtained in the step (1) while stirring the solution A at a rotation speed of 400rpm, and stirring the solution A for 5min to obtain steel slag slurry A;
(3) Weighing 5 parts of zero water sodium metasilicate according to the weight ratio of 1:9, and dividing the zero water sodium metasilicate into a silicon source A and a silicon source B;
(4) Adding the silicon source A obtained in the step (3) into the steel slag slurry A obtained in the step (2) to obtain steel slag slurry B;
(5) Stirring the steel slag slurry B obtained in the step (4) at a rotating speed of 400rpm, and introducing carbon dioxide gas into the steel slag slurry B at a flow speed of 250ml/min until the pH value of the steel slag slurry B is less than 8, so as to obtain steel slag slurry C;
(6) Adding the silicon source B obtained in the step (3) into the steel slag slurry C obtained in the step (5) to obtain steel slag slurry D;
(7) Stirring the steel slag slurry D obtained in the step (6) at a rotating speed of 400rpm, and introducing carbon dioxide gas into the steel slag slurry D at a flow speed of 250ml/min until the pH value of the steel slag slurry D is less than 8, so as to obtain steel slag slurry E;
(8) And (3) centrifugally washing the steel slag slurry E obtained in the step (7), and drying the steel slag slurry E to constant weight in vacuum at 60 ℃ to obtain steel slag-based in-situ growth hybrid nano-particles, namely steel slag-based in-situ growth hybrid nano-calcium carbonate and nano-silica.
Example 7
The carbonization method for preparing the steel slag-based in-situ growth hybrid nano calcium carbonate and nano silicon dioxide comprises the following steps:
(1) Weighing 100 parts of water, 150 parts of absolute ethyl alcohol and 5 parts of cetyl trimethyl ammonium bromide according to parts by weight, and preparing a solution A, so that the solution A is kept at a constant temperature of 30 ℃;
(2) Weighing 25 parts of steel slag according to parts by weight, adding the steel slag into the solution A obtained in the step (1) while stirring the solution A at a rotation speed of 400rpm, and stirring the solution A for 5min to obtain steel slag slurry A;
(3) Weighing 10 parts of zero water sodium metasilicate according to the weight ratio of 2:8, and dividing the zero water sodium metasilicate into a silicon source A and a silicon source B;
(4) Adding the silicon source A obtained in the step (3) into the steel slag slurry A obtained in the step (2) to obtain steel slag slurry B;
(5) Stirring the steel slag slurry B obtained in the step (4) at a rotation speed of 400rpm, and introducing carbon dioxide gas into the steel slag slurry B at a flow speed of 150ml/min until the pH value of the steel slag slurry B is less than 8, so as to obtain steel slag slurry C;
(6) Adding the silicon source B obtained in the step (3) into the steel slag slurry C obtained in the step (5) to obtain steel slag slurry D;
(7) Stirring the steel slag slurry D obtained in the step (6) at a rotating speed of 400rpm, and introducing carbon dioxide gas into the steel slag slurry D at a flow speed of 150ml/min until the pH value of the steel slag slurry D is less than 8, so as to obtain steel slag slurry E;
(8) And (3) centrifugally washing the steel slag slurry E obtained in the step (7), and drying the steel slag slurry E to constant weight in vacuum at 60 ℃ to obtain steel slag-based in-situ growth hybrid nano-particles, namely steel slag-based in-situ growth hybrid nano-calcium carbonate and nano-silica.
Example 8
The carbonization method for preparing the steel slag-based in-situ growth hybrid nano calcium carbonate and nano silicon dioxide comprises the following steps:
(1) Weighing 150 parts of water, 100 parts of absolute ethyl alcohol and 10 parts of cetyl trimethyl ammonium bromide according to parts by weight, and preparing a solution A, so that the solution A is kept at a constant temperature of 80 ℃;
(2) Weighing 25 parts of steel slag according to parts by weight, adding the steel slag into the solution A obtained in the step (1) while stirring the solution A at a rotation speed of 400rpm, and stirring the solution A for 5min to obtain steel slag slurry A;
(3) Weighing 25 parts of zero water sodium metasilicate according to the weight ratio of 1:9, and dividing the zero water sodium metasilicate into a silicon source A and a silicon source B;
(4) Adding the silicon source A obtained in the step (3) into the steel slag slurry A obtained in the step (2) to obtain steel slag slurry B;
(5) Stirring the steel slag slurry B obtained in the step (4) at a rotating speed of 400rpm, and introducing carbon dioxide gas into the steel slag slurry B at a flow speed of 350ml/min until the pH value of the steel slag slurry B is less than 8, so as to obtain steel slag slurry C;
(6) Adding the silicon source B obtained in the step (3) into the steel slag slurry C obtained in the step (5) to obtain steel slag slurry D;
(7) Stirring the steel slag slurry D obtained in the step (6) at a rotation speed of 400rpm, and introducing carbon dioxide gas into the steel slag slurry D at a flow speed of 350ml/min until the pH value of the steel slag slurry D is less than 8, so as to obtain steel slag slurry E;
(8) And (3) centrifugally washing the steel slag slurry E obtained in the step (7), and drying the steel slag slurry E to constant weight in vacuum at 60 ℃ to obtain steel slag-based in-situ growth hybrid nano-particles, namely steel slag-based in-situ growth hybrid nano-calcium carbonate and nano-silica.
Characterization tests are carried out on the steel slag-based in-situ growth hybrid nano-particles obtained in examples 1 to 8, and the steel slag-based in-situ growth hybrid nano-particles are used for modifying cement-based materials, and specifically comprise the following steps:
(1) Characterization tests are carried out on the steel slag-based in-situ growth hybrid nano-particles obtained in the examples 1-4, namely, the steel slag-based in-situ growth hybrid nano-calcium silicate hydrate and nano-silica are characterized and tested, and the concrete steps are as follows:
fig. 1 is an SEM image of the raw steel slag used in example 1, and it can be seen that: the surface of the steel slag is rough.
Fig. 2 is an SEM image of the steel slag slurry a obtained in step (2) of example 1 after drying, and it can be seen that: the steel slag generates hydration reaction to a certain extent when meeting water, and hydration products are formed on the surface of the steel slag, namely, hydrated calcium silicate is generated.
Fig. 3 is an SEM image of the steel slag slurry B obtained in step (4) of example 1 after drying, and it can be seen that: hemispherical nanoparticles exist on the surface of the steel slag, and the hemispherical nanoparticles are tightly combined with the steel slag matrix.
Further, elemental composition of hemispherical nanoparticles was analyzed. Fig. 4 is EDS spectrum of the steel slag slurry B obtained in step (4) of example 1 after drying, and it can be seen that: the hemispherical particles on the surface of the steel slag are nano hydrated calcium silicate with low calcium-silicon ratio, wherein the molar ratio of calcium to silicon is 0.2;
fig. 5 is an SEM image of the steel slag-based in-situ grown hybrid nanoparticles obtained in example 1, as follows: spherical nano particles with the particle size of about 40nm are grown on the surface of the steel slag in situ.
FIG. 6 is an FT-IR diagram of steel slag-based in-situ grown hybrid nanoparticles obtained in example 1. For the undisturbed steel slag, the temperature is 516cm -1 There is an in-plane bending vibration peak of si—o. However, in the FT-IR spectrum of the obtained steel slag-based in-situ grown hybrid nano particles, the peak is obviously weakened, and the peak is replaced by 461cm -1 There appears a distinct peak of the flexural vibration characteristic of Si-O-Si. Further, the original steel slag is 985cm -1 An antisymmetric telescopic vibration absorption peak of Si-O-Si appears at the position, and in the obtained steel slag-based in-situ growth hybrid nano-particle, the peak is obviously shifted to the left, namely, the peak is shifted to 1080cm -1 Where it is located. This indicates that the polymerization degree of Si-O-Si is significantly improved, and the reason for the increase in the polymerization degree is hydrolysis polycondensation of tetraethyl orthosilicate. Thus, it can be considered that: by utilizing a sol-gel method and through hydrolysis polycondensation reaction of tetraethoxysilane, the in-situ growth of hybrid nano particles, namely nano calcium silicate hydrate and nano silicon dioxide on the surface of steel slag can be realized.
Fig. 7 to 9 are SEM images of steel slag-based in-situ grown hybrid nanoparticles obtained in examples 2 to 4, and it can be seen that: the surface of the steel slag is in-situ grown with mixed nano particles.
(2) Characterization tests are carried out on the steel slag-based in-situ growth hybrid nano-particles obtained in examples 5 to 8, namely steel slag-based in-situ growth hybrid nano-calcium carbonate and nano-silica, and the specific steps are as follows:
fig. 10 is an SEM image of the steel slag slurry C obtained in step (5) of example 5 after drying, and it can be seen that: the nano calcium carbonate and the nano silicon dioxide are grown on the surface of the steel slag in situ, wherein the nano silicon dioxide is tightly combined with the steel slag matrix.
Fig. 11 is an SEM image of the steel slag-based in-situ grown hybrid nanoparticles obtained in example 5, as follows: the nano silicon dioxide with the grain diameter of 30-50 nm grows on the surface of the steel slag in situ.
Fig. 12 is an XRD pattern of the steel slag-based in-situ grown hybrid nanoparticle obtained in example 5, which shows that: in the XRD pattern of the obtained steel slag-based in-situ grown nano hybrid particles, obvious characteristic diffraction peaks of calcium carbonate appear. In summary, it can be considered that: by the carbonization method, the in-situ growth of hybrid nano particles, namely nano calcium carbonate and nano silicon dioxide on the surface of the steel slag can be realized.
Fig. 13 to 15 are SEM images of steel slag-based in-situ grown hybrid nanoparticles obtained in examples 6 to 8, and it can be seen that: the surface of the steel slag is in-situ grown with mixed nano particles.
(3) Effect of the steel slag-based in-situ grown hybrid nanoparticles obtained in example 1 and example 5 as nanoadditives on cement-based material properties
The steel slag-based in-situ grown hybrid nanoparticle obtained in example 1 and the steel slag-based in-situ grown hybrid nanoparticle obtained in example 5 were used as nano additives, which were respectively incorporated into cement paste. By thermogravimetric analysis, it can be calculated: the content of the steel slag based in-situ grown hybrid nanoparticle obtained in example 1 was 11.64%, and the content of the steel slag based in-situ grown hybrid nanoparticle obtained in example 5 was 19.76%. On this basis, comparative example 1, comparative example 2 and example 9, and comparative example 3, comparative example 4 and example 10 were designed according to the controlled variable method. The method comprises the following steps:
comparative example 1
According to the weight portions, 469.64 portions of P.II 52.5 cement, 30.36 portions of steel slag and 200 portions of water are weighed and mixed into a cement slurry. The fluidity of the freshly mixed cement paste was measured by reference to GB/T8077-2012 "concrete admixture homogeneity test method", and the compressive strength of the hardened cement paste was measured by reference to GB/T17671-2021 "cement mortar strength test method (ISO method).
Comparative example 2
According to the weight portions, 469.64 portions of P.II 52.5 cement, 30.36 portions of steel slag, 4 portions of commercial nano silicon dioxide with the grain size of about 40nm and 200 portions of water are weighed and mixed into cement slurry. The fluidity of the freshly mixed cement paste was measured by reference to GB/T8077-2012 "concrete admixture homogeneity test method", and the compressive strength of the hardened cement paste was measured by reference to GB/T17671-2021 "cement mortar strength test method (ISO method).
Example 9
According to the weight portions, 469.64 portions of P.II 52.5 cement, 34.36 portions of the steel slag based in-situ growth hybrid nano particles obtained in the example 1 and 200 portions of water are weighed and mixed into a cement slurry. The fluidity of the freshly mixed cement paste was measured by reference to GB/T8077-2012 "concrete admixture homogeneity test method", and the compressive strength of the hardened cement paste was measured by reference to GB/T17671-2021 "cement mortar strength test method (ISO method).
As shown in table 1, the performance index of the cement paste is shown. Obviously, the incorporation of the ordinary nanosilica in comparative example 2 significantly reduced the fluidity of the freshly mixed cement slurry compared to comparative example 1 without the nanosilica, but in example 9, the incorporation of the steel slag-based in-situ grown nano hybrid particles obtained in example 1 had less negative effect on the fluidity of the freshly mixed cement slurry. In addition, although the 3d compressive strength and the 28d compressive strength of the hardened cement paste are obviously improved by the common nano silicon dioxide and the steel slag-based in-situ grown nano particles, the 3d compressive strength and the 28d compressive strength of the hardened cement paste are greatly improved by the steel slag-based in-situ grown hybrid nano particles. The above results all show that compared with the common nano silicon dioxide, the steel slag-based in-situ growth hybrid nano particles have better dispersibility in a cement matrix and can be used for modifying the cement-based material better.
TABLE 1 Performance index of cement slurries
| Group of | Fluidity/mm | 3d compressive Strength/MPa | 28d compressive Strength/MPa |
| Comparative example 1 | 120 | 42.5 | 62.3 |
| Comparative example 2 | 91 | 48.3 | 67.6 |
| Example 9 | 103 | 53.2 | 72.7 |
Comparative example 3
According to the weight portions, 483.76 portions of P.II 52.5 cement, 16.24 portions of steel slag and 200 portions of water are weighed and mixed into a cement slurry. The fluidity of the freshly mixed cement paste was measured by reference to GB/T8077-2012 "concrete admixture homogeneity test method", and the compressive strength of the hardened cement paste was measured by reference to GB/T17671-2021 "cement mortar strength test method (ISO method).
Comparative example 4
According to the weight portions, 483.76 portions of P.II 52.5 cement, 16.24 portions of steel slag, 4 portions of commercial nano silicon dioxide with the grain size of about 40nm and 200 portions of water are weighed and mixed into cement slurry. The fluidity of the freshly mixed cement paste was measured by reference to GB/T8077-2012 "concrete admixture homogeneity test method", and the compressive strength of the hardened cement paste was measured by reference to GB/T17671-2021 "cement mortar strength test method (ISO method).
Example 10
According to the weight portions, 483.76 portions of P.II 52.5 cement, 20.24 portions of steel slag based in-situ growth hybrid nano particles obtained in example 5 and 200 portions of water are weighed and mixed into a cement slurry. The fluidity of the freshly mixed cement paste was measured by reference to GB/T8077-2012 "concrete admixture homogeneity test method", and the compressive strength of the hardened cement paste was measured by reference to GB/T17671-2021 "cement mortar strength test method (ISO method).
As shown in table 2, the performance index of the cement paste is shown. Obviously, the incorporation of the ordinary nanosilica in comparative example 4 significantly reduced the fluidity of the freshly mixed cement slurry compared to comparative example 3 without the nanosilica, but in example 10, the incorporation of the steel slag-based in-situ grown nano-hybrid particles obtained in example 1 had less negative impact on the fluidity of the freshly mixed cement slurry. In addition, although the 3d compressive strength and the 28d compressive strength of the hardened cement paste are obviously improved by the common nano silicon dioxide and the steel slag-based in-situ grown nano particles, the 3d compressive strength and the 28d compressive strength of the hardened cement paste are greatly improved by the steel slag-based in-situ grown hybrid nano particles. The above results all show that compared with the common nano silicon dioxide, the steel slag-based in-situ growth hybrid nano particles have better dispersibility in a cement matrix and can be used for modifying the cement-based material better.
TABLE 2 Performance index of cement slurries
| Group of | Fluidity/mm | 3d compressive Strength/MPa | 28d compressive Strength/MPa |
| Comparative example 3 | 118 | 42.8 | 62.2 |
| Comparative example 4 | 87 | 51.2 | 68.7 |
| Example 10 | 105 | 56.6 | 76.2 |
(4) Effect of the steel slag-based in-situ grown hybrid nanoparticles obtained in example 2 and example 6 as mineral admixture on cement-based material properties
The steel slag-based in-situ grown hybrid nanoparticle obtained in example 2 and the steel slag-based in-situ grown hybrid nanoparticle obtained in example 6 were used as mineral admixtures, and the gelation activity and volume stability thereof were analyzed as follows:
comparative example 5
According to the weight portions, 315 portions of P.II 52.5 cement, 135 portions of steel slag, 1350 portions of sand and 225 portions of water are weighed and mixed into cement mortar, and the compressive strength of the hardened cement mortar is measured by referring to GB/T17671-2021 method for testing cement mortar strength (ISO method).
Example 11
According to the parts by weight, 315 parts of P.II 52.5 cement, 135 parts of steel slag based in-situ growth mixed nano particles obtained in example 2, 1350 parts of sand and 225 parts of water are weighed and mixed into cement mortar, and the compressive strength of the hardened cement mortar is determined by referring to GB/T17671-2021 cement mortar strength test method (ISO method).
Example 12
According to the parts by weight, 315 parts of P.II 52.5 cement, 135 parts of steel slag based in-situ growth mixed nano particles obtained in example 6, 1350 parts of sand and 225 parts of water are weighed and mixed into cement mortar, and the compressive strength of the hardened cement mortar is determined by referring to GB/T17671-2021 cement mortar strength test method (ISO method).
As shown in table 3, the 28d compressive strength of the cement mortar is given. Obviously, the steel slag with the mixed nano particles grown in situ can effectively improve the 28d compressive strength of cement mortar, namely, the steel slag-based in-situ grown mixed nano particles can improve the gelation activity of the steel slag. Clearly, the improvement of the gelation activity of the steel slag is beneficial to the application of the steel slag in a large amount in cement-based materials.
Table 3 compressive strength of cement mortar
| Group of | 28d compressive Strength/MPa |
| Comparative example 5 | 42.8 |
| Example 11 | 47.9 |
| Example 12 | 49.6 |
Comparative example 6
The volume stability of the undisturbed steel slag is measured by referring to GB/T1346-2011 method for testing the water consumption, setting time and stability of cement standard consistence. Wherein the mass ratio of the undisturbed steel slag to the cement is 3:7.
Example 13
The volume stability of the steel slag-based in-situ growth hybrid nanoparticle obtained in example 2 was determined with reference to GB/T1346-2011 method for testing water consumption, setting time and stability of Cement standard consistencies. Wherein the mass ratio of the steel slag-based in-situ grown hybrid nano particles to cement obtained in the example 2 is 3:7.
Example 14
The volume stability of the steel slag-based in-situ growth hybrid nanoparticle obtained in example 6 was determined with reference to GB/T1346-2011 method for testing water consumption, setting time and stability of Cement standard consistencies. Wherein the mass ratio of the steel slag-based in-situ grown hybrid nano particles to cement obtained in the example 6 is 3:7.
Comparative example 7
The volume stability of the undisturbed steel slag is measured by referring to GB/T1346-2011 method for testing the water consumption, setting time and stability of cement standard consistence. Wherein the mass ratio of the undisturbed steel slag to the cement is 6:4.
Example 15
The volume stability of the steel slag-based in-situ growth hybrid nanoparticle obtained in example 2 was determined with reference to GB/T1346-2011 method for testing water consumption, setting time and stability of Cement standard consistencies. Wherein, the mass ratio of the steel slag-based in-situ growth hybrid nano particles to the cement obtained in the example 2 is 6:4.
Example 16
The volume stability of the steel slag-based in-situ growth hybrid nanoparticle obtained in example 6 was determined with reference to GB/T1346-2011 method for testing water consumption, setting time and stability of Cement standard consistencies. Wherein the mass ratio of the steel slag-based in-situ grown hybrid nano particles to cement obtained in the example 6 is 6:4.
As shown in table 4, the rayleigh clamp expansion values of the cement slurries are given. Obviously, when the blending amount of the steel slag is 30wt% of the total amount of the cementing material, the steel slag (example 13 and example 14) in which the hybrid nano particles are grown in situ can significantly reduce the expansion value of the Lei clamp of the cement paste compared with the original steel slag of comparative example 6. Further, when the blending amount of the steel slag is 50wt% of the total amount of the cementing material, the Lei clamp expansion value of comparative example 7 blended with the as-is steel slag is more than 5mm, and the volume stability is not qualified. However, when the steel slag with hybrid nano particles grown in situ is doped at 50w%, see example 15 and example 16, the expansion value of the Lei clamp is still less than 5mm. This shows that the steel slag-based in-situ growth of hybrid nano particles is beneficial to improving the volume stability of steel slag.
TABLE 4 stability of cement slurries
| Group of | Lei's clamp expansion value/mm |
| Comparative example 6 | 3.5 |
| Example 13 | 1.0 |
| Example 14 | 1.5 |
| Comparative example 7 | 5.5 |
| Example 15 | 1.0 |
| Example 16 | 2.0 |
Claims (10)
1. The steel slag-based in-situ growth hybrid nano-particles comprise a steel slag matrix, and are characterized in that calcium-containing nano-particles are grown on the surface of the steel slag matrix in situ, and nano-silicon dioxide is grown on the surface of the steel slag matrix in situ by taking the calcium-containing nano-particles as nucleation sites.
2. The steel slag based in-situ grown hybrid nanoparticle of claim 1, wherein the calcium-containing nanoparticle is a nano-calcium silicate hydrate or a nano-calcium carbonate.
3. A method for preparing the steel slag-based in-situ growth hybrid nanoparticle according to claim 1, wherein the calcium-containing nanoparticle is nano calcium silicate hydrate, the method is a sol-gel method, and the method comprises the following steps:
(1) Mixing water, absolute ethyl alcohol, ammonia water and a surfactant to prepare a solution A, and keeping the solution A at a constant temperature; adding steel slag into the solution A, and stirring to obtain steel slag slurry A;
(2) Mixing a silicon source with absolute ethyl alcohol and separating into a solution B and a solution C;
(3) Dropwise adding the solution B into the steel slag slurry A, and stirring to obtain steel slag slurry B;
(4) Dropwise adding the solution C into the steel slag slurry B, and stirring to obtain steel slag slurry C; and washing and drying to obtain the steel slag-based in-situ growth hybrid nano particles.
4. The method for preparing steel slag based in-situ growth hybrid nano particles according to claim 3, wherein in the step (1), the water, the absolute ethyl alcohol and the ammonia water are respectively in parts by volume: 45-5 parts, 5-45 parts and 0-2 parts of surfactant, wherein the mass part of the surfactant is 0-2 parts; the mass portion of the steel slag is 1-4 portions.
5. The method for preparing steel slag based in-situ growth hybrid nano-particles according to claim 3, wherein in the step (2), the silicon source and the absolute ethyl alcohol are respectively 0.5-2 parts by volume and 5-10 parts by volume.
6. The method for preparing steel slag based in-situ growth hybrid nano-particles according to claim 3, wherein in the step (1), the constant temperature of the solution is 30-60 ℃.
7. A method for preparing the steel slag-based in-situ growth hybrid nano-particles according to claim 1, wherein the calcium-containing nano-particles are nano-calcium carbonate, the method is a carbonization method, and the method comprises the following steps:
(1) Mixing water, absolute ethyl alcohol and a surfactant to prepare a solution A, and keeping the solution at a constant temperature; adding steel slag into the solution A, and stirring to obtain steel slag slurry A;
(2) Weighing a silicon source A and a silicon source B, and adding the silicon source A into the steel slag slurry A to obtain steel slag slurry B;
(3) Introducing carbon dioxide gas into the steel slag slurry B until the pH value of the steel slag slurry B is less than 8, so as to obtain steel slag slurry C;
(4) Adding a silicon source B into the steel slag slurry C to obtain steel slag slurry D; and introducing carbon dioxide gas into the steel slag slurry D until the pH value of the steel slag slurry D is less than 8, obtaining steel slag slurry E, washing and then truly drying to obtain the steel slag-based in-situ growth hybrid nano particles.
8. The method for preparing steel slag based in-situ grown hybrid nanoparticles according to claim 7, wherein in step (1), the constant temperature of the solution is: 30-80 ℃.
9. The method for preparing steel slag based in-situ growth hybrid nano-particles according to claim 7, wherein in the step (3), the carbon dioxide gas is introduced at a rate of: 150-350 ml/min; the stirring speed is as follows: 200-400 rpm.
10. The method for preparing steel slag based in-situ growth hybrid nano-particles according to claim 7, wherein in the step (1), the steel slag, water, absolute ethyl alcohol and surfactant are respectively in parts by weight: 10 to 50 parts, 100 to 200 parts, 50 to 150 parts and 0 to 10 parts.
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