CN116462439A - Carbide slag-based low-shrinkage excitant and preparation method and application thereof - Google Patents
Carbide slag-based low-shrinkage excitant and preparation method and application thereof Download PDFInfo
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- CN116462439A CN116462439A CN202310727674.0A CN202310727674A CN116462439A CN 116462439 A CN116462439 A CN 116462439A CN 202310727674 A CN202310727674 A CN 202310727674A CN 116462439 A CN116462439 A CN 116462439A
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- steel slag
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- 239000002893 slag Substances 0.000 title claims abstract description 247
- 238000002360 preparation method Methods 0.000 title description 13
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 147
- 239000010959 steel Substances 0.000 claims abstract description 147
- 239000000463 material Substances 0.000 claims abstract description 80
- 239000011347 resin Substances 0.000 claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 239000012190 activator Substances 0.000 claims abstract description 57
- 239000004568 cement Substances 0.000 claims abstract description 48
- 239000010440 gypsum Substances 0.000 claims abstract description 35
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 35
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 29
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 29
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 24
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims description 58
- 230000036571 hydration Effects 0.000 abstract description 17
- 238000006703 hydration reaction Methods 0.000 abstract description 17
- 230000008859 change Effects 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 89
- 239000002250 absorbent Substances 0.000 description 36
- 230000002745 absorbent Effects 0.000 description 36
- 239000000203 mixture Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 31
- 239000004576 sand Substances 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 239000000292 calcium oxide Substances 0.000 description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 11
- 239000000395 magnesium oxide Substances 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000005284 excitation Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 229910001653 ettringite Inorganic materials 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 206010053567 Coagulopathies Diseases 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 102000018779 Replication Protein C Human genes 0.000 description 1
- 108010027647 Replication Protein C Proteins 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000035602 clotting Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a carbide slag-based low-shrinkage excitant, which is prepared from the following components in percentage by mass: 65-75% of carbide slag, 15-20% of desulfurized gypsum, 4-10% of sodium silicate and 5% of lithium sulfate. When the steel slag powder is excited, a certain amount of micron-level high water-absorbing resin is externally doped, so that the hydration speed can be increased, and the shrinkage of the material can be inhibited. Experimental results prove that when the mass of carbide slag is 71%, the mass of desulfurized gypsum is 18%, the mass of sodium silicate is 6%, the mass of lithium sulfate is 5%, and the mass of micron-sized high-water-absorbing resin is 0.3% of the total mass of the low-shrinkage high-early-strength activator, steel slag and cement, the shrinkage change of the material is minimum, the compressive strength is highest, wherein the mass ratio of the steel slag to the activator is 1:1, the shrinkage change is (2.5 to 2.6). Times.10 ‑6 The compressive strengths of 14d, 28d and 60d reach 18.3MPa, 34.5MPa and 41.2MPa.
Description
Technical Field
The invention relates to the technical field of excitants, in particular to a carbide slag-based low-shrinkage excitant, and a preparation method and application thereof.
Background
The steel slag is an industrial waste produced in the steelmaking process, a large amount of stored steel slag occupies land resources, resource waste is caused, water pollution around a slag yard can be caused, a large amount of dust can be produced when the steel slag is piled in the open air, and haze weather is caused. At present, the steel slag is mainly used as a cementing material or a mineral admixture, and although the steel slag has similar mineral components as cement cementing material, the steel slag is calcined at a high temperature of more than 1400 ℃ in the forming process, a layer of compact glass body taking Si-O, A-O as a main body is formed on the surface of the steel slag, and the layer of glass body is formed by f-CaO and C 3 S、C 2 S and other components are wrapped, so that the fine particles are coarse in crystal form and low in activity. Therefore, although the steel slag has potential gelling activity, certain excitation measures are needed to be fully utilized. The steel slag powder is simply excited by industrial chemical reagents, so that the cost is high, and the excited slurry is large in shrinkage deformation and easy to crack after hardening. Accordingly, it is an urgent need in the art to provide an activator capable of reducing the post-shrinkage of a hardened slurry and suppressing the occurrence of cracking.
Disclosure of Invention
The invention aims to provide a carbide slag-based low-shrinkage excitant, and a preparation method and application thereof. The exciting agent provided by the invention can reduce the later shrinkage of the hardened slurry and inhibit cracking after exciting the steel slag.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a carbide slag-based low-shrinkage excitant, which is prepared from the following components in percentage by mass: 65-75% of carbide slag, 15-20% of desulfurized gypsum, 4-10% of sodium silicate and 5% of lithium sulfate.
Preferably, the composition is prepared from the following components in percentage by mass: 66% -74% of carbide slag, 16% -19% of desulfurized gypsum, 6% -9% of sodium silicate and 5% of lithium sulfate.
Preferably, the composition is prepared from the following components in percentage by mass: 67-72% of carbide slag, 17-18% of desulfurized gypsum, 6-8% of sodium silicate and 5% of lithium sulfate.
Preferably, the grain size of the carbide slag is less than or equal to 200 meshes.
Preferably, the carbide slag comprises the following chemical components in percentage by mass: caCl (CaCl) 2 1.03%~1.45%，CaO 88.12~91.93%，Na 2 O 0.48%~0.62%，SiO 2 1.94%~5.92%，MgO 0.42%~1.54%，Fe 2 O 3 0.21%~0.37%，SO 3 0.52% -0.77% of Al 2 O 3 2.56%~3.12%。
Preferably, the CaSO in the desulfurized gypsum 4 ·2H 2 The mass of O is 90%; the modulus of the sodium silicate is 1.3-1.6.
The invention also provides a preparation method of the carbide slag-based low-shrinkage excitant, which comprises the following steps:
mixing carbide slag, desulfurized gypsum, sodium silicate and lithium sulfate to obtain the carbide slag-based low-shrinkage activator.
The invention also provides the application of the carbide slag-based low-shrinkage activator prepared by the technical scheme or the preparation method of the technical scheme in the steel slag-based composite cementing material.
Preferably, the mass ratio of the carbide slag-based low shrinkage activator to the steel slag is 1:1 or 7:3.
preferably, the steel slag-based composite cementing material further comprises micron-sized high water-absorbing resin and cement, wherein the mass of the micron-sized high water-absorbing resin is 0.1% -0.3% of the total mass of the carbide slag-based low shrinkage activator and the steel slag.
The invention provides a carbide slag-based low-shrinkage excitant, which is prepared from the following components in percentage by massThe preparation method comprises the following steps: 65-75% of carbide slag, 15-20% of desulfurized gypsum, 4-10% of sodium silicate and 5% of lithium sulfate. In the invention, strong alkali environment and enough active Ca are provided in slurry solution by adding carbide slag, desulfurized gypsum and sodium silicate 2+ At the same time, sodium silicate reacts with cement to generate calcium hydroxide to obtain sodium hydroxide, na + Is introduced to lead the glass body with low activity to generate fracture depolymerization, and Li in lithium sulfate + And SO 4 2- Is favorable for exciting C in steel slag powder 3 S and C 2 S, hydration; improves the hydration activity of the steel slag under the combined action of sodium, calcium and sulfur; besides the added sodium silicate can accelerate the hydration speed, the hydrated calcium silicate and calcium aluminate gel formed after the steel slag is excited can also play a role in filling in a network structure, so that the strength of the cementing material is further improved, and expansion cracking and shrinkage are inhibited. Experimental results show that when the mass of carbide slag is 71%, the mass of desulfurized gypsum is 18%, the mass of sodium silicate is 6%, the mass of lithium sulfate is 5%, the mass of the micron-sized high-water-absorbing resin is 0.3% of the total mass of the low-shrinkage high-early-strength activator, steel slag and cement, the shrinkage change of the material is minimum, the compressive strength is highest, wherein the mass ratio of the steel slag to the activator is 1:1, the shrinkage change is (2.5 to 2.6). Times.10 -6 Compressive strengths of 14d, 28d and 60d reach 18.3MPa, 34.5MPa and 41.2MPa; the mass ratio of the exciting agent to the steel slag is 7: at 3, the shrinkage is changed to (2.2 to 2.3). Times.10 -6 The compressive strengths of 14d, 28d and 60d reach 18.8MPa, 33.0MPa and 41.7MPa.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a steel slag-based composite cementitious material prepared in application example 11;
FIG. 2 is a 14-day SEM scan of the steel slag-based composite cementitious material prepared in application example 25;
FIG. 3 is a 28-day SEM scan of the steel slag-based composite cementitious material prepared in application example 25;
FIG. 4 is a 60-day SEM scan of the steel slag-based composite cementitious material prepared in application example 25;
fig. 5 is an XRD analysis result of the steel slag-based composite cementitious material prepared in application example 18.
Detailed Description
The invention provides a carbide slag-based low-shrinkage excitant, which is prepared from the following components in percentage by mass: 65-75% of carbide slag, 15-20% of desulfurized gypsum, 4-10% of sodium silicate and 5% of lithium sulfate.
The carbide slag-based low-shrinkage activator provided by the invention comprises 65% -75%, preferably 66% -74%, and more preferably 67% -72% of carbide slag by taking the mass of the carbide slag-based low-shrinkage activator as 100%. In the invention, the grain size of the carbide slag is preferably less than or equal to 200 meshes; the carbide slag preferably comprises the following chemical components in percentage by mass: caCl (CaCl) 2 1.03%~1.45%，CaO 88.12~91.93%，Na 2 O 0.48%~0.62%，SiO 2 1.94%~5.92%，MgO 0.42%~1.54%，Fe 2 O 3 0.21%~0.37%，SO 3 0.52% -0.77% of Al 2 O 3 2.56% -3.12%, more preferably CaCl 2 1.13%~1.45%，CaO 89.12~91.93%，Na 2 O 0.52%~0.62%，SiO 2 4.98%~5.90%，MgO 0.45%~1.52%，Fe 2 O 3 0.26%~0.37%，SO 3 0.55 to 0.77 percent of Al 2 O 3 2.76% -3.12%; the carbide slag is preferably produced by the water purification material factory of the Yuan Heng in the consolidated city. In the invention, the carbide slag has an excitation effect on the steel slag, and can improve the activity of the steel slag.
The carbide slag-based low-shrinkage activator provided by the invention further comprises 15% -20%, preferably 16% -19%, more preferably 17% -18% of desulfurized gypsum based on 100% of the mass of the carbide slag-based low-shrinkage activator. In the present invention, caSO in the desulfurized gypsum 4 ·2H 2 The mass of O is preferably 90%; the desulfurized gypsum preferably comprises the following chemical components in percentage by mass: 48.06% -50.02% of CaO and SO 3 43.57%~44.86%，SiO 2 2.95%~3.48%，MgO 1.48%~2.04%、Al 2 O 3 1.18-1.85% and less than or equal to 3% of impurities, more preferably 48.06% of CaO and SO 3 43.57%，SiO 2 2.95%，MgO 1.48%，Al 2 O 3 1.18% and 2.76% of impurities; the particle size of the desulfurized gypsum is preferably less than or equal to 200 meshes; the desulfurized gypsum is preferably produced by a water purification material factory of the consolidated Yuan Heng. In the present invention, the desulfurized gypsum can be addedThe formation of ettringite increases the strength of the cement.
The carbide slag-based low-shrinkage activator provided by the invention further comprises 4% -10%, preferably 6% -9%, and more preferably 6% -8% of sodium silicate by taking the mass of the carbide slag-based low-shrinkage activator as 100%. In the invention, the modulus of the sodium silicate is preferably 1.3-1.6. The source of the sodium silicate is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the invention, the sodium silicate can accelerate the hydration speed, can play the best skeleton network structure and excitation effect, and the hydrated calcium silicate and calcium aluminate gel formed after the steel slag is excited can play a role in filling in the network structure, thereby further improving the strength of the cementing material.
The carbide slag-based low-shrinkage activator provided by the invention also comprises 5% of lithium sulfate by taking the mass of the carbide slag-based low-shrinkage activator as 100%. In the invention, the purity of the lithium sulfate is preferably more than or equal to 95wt%; the lithium sulfate is preferably manufactured by Shandong Ruifer lithium company, inc. In the present invention, li+ and SO in lithium sulfate 4 2- Is favorable for exciting C in steel slag 2 S and C 3 Hydration of S.
In the invention, the carbide slag and sodium silicate provide strong alkali environment and enough active Ca in slurry solution 2+ At the same time, sodium silicate reacts with cement to generate calcium hydroxide to obtain sodium hydroxide, na + The introduction of the method ensures that the glass body with low structural activity of the steel slag is broken and depolymerized, and improves the hydration activity of the steel slag under the combined action of sodium, calcium and sulfur; li in the added lithium sulfate + And SO 4 2- Is favorable for exciting C in steel slag 2 S and C 3 Hydration of S.
Based on the theory of the formation of a cementing material structure, the pH value of an excitation solution is optimized by mixing carbide slag, desulfurized gypsum, sodium silicate and lithium sulfate, so that the purposes of reducing the later shrinkage of hardened slurry and inhibiting the generation of cracking are achieved by exciting solid waste steel slag powder; the method can also realize the recycling utilization of the full solid waste, satisfies engineering application, and solves the problems of expansion cracking, large shrinkage, low utilization rate and the like of the industrial solid waste steel slag caused by unstable structure in the practical application process.
The invention also provides a preparation method of the carbide slag-based low-shrinkage excitant, which comprises the following steps:
mixing carbide slag, desulfurized gypsum, sodium silicate and lithium sulfate to obtain the carbide slag-based low-shrinkage activator.
In the invention, the carbide slag preferably further comprises pretreatment before use; the pretreatment is preferably carried out by putting carbide slag into a heating furnace at 300 ℃ and heating for 3 hours. In the invention, the pretreatment can remove harmful gases in carbide slag and improve excitation activity.
In the present invention, the mixing is preferably performed under stirring. The stirring operation is not particularly limited, so long as the uniform mixing of the raw materials is ensured.
The preparation method provided by the invention has simple process and is suitable for industrial production.
The invention also provides the application of the carbide slag-based low-shrinkage activator prepared by the technical scheme or the preparation method of the technical scheme in the steel slag-based composite cementing material.
In the invention, the mass ratio of the carbide slag-based low-shrinkage activator to the steel slag is preferably 1:1 or 7:3,
in the invention, the chemical components of the steel slag preferably comprise 32.0% -37.2% of CaO and SiO by mass percent 2 19.1%~28.9%，Fe 2 O 3 24.0%~30.5%，Al 2 O 3 6.3% -8.2% of MgO and 3.9% -5.5%, more preferably 34.2% of CaO and SiO 2 27.1%，Fe 2 O 3 26.7%，Al 2 O 3 7.8% and 4.2% MgO; the steel slag is preferably converter steel slag produced by He Steel group; the grain diameter of the steel slag is preferably less than or equal to 120 meshes; the density of the steel slag is preferably 3.2g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The steel slag is preferably steel slag powder.
In the present invention, the steel slag is preferably pretreated before use: the pretreatment is preferably performed by ball milling, sieving with a 120-mesh sieve, immersing in an acidic solution, filtering and drying in sequence. In the invention, the pretreatment can lead the free calcium oxide and the free magnesium oxide in the steel slag to expand first, thereby avoiding cracking expansion during later use and further inhibiting the expansion cracking phenomenon of the cementing material.
The operation of the ball milling is not particularly limited, and the ball milling operation well known to those skilled in the art may be employed.
In the present invention, the acidic solution is preferably a hydrochloric acid solution; the pH of the acidic solution is preferably 5; the soaking temperature is preferably 25 ℃; the soaking time is preferably 3 days. The source of the hydrochloric acid solution is not particularly limited, and may be prepared by commercially available products known to those skilled in the art or by a known preparation method. In the invention, the steel slag is treated in the acid solution, so that the swelling and cracking phenomena of the cementing material can be further inhibited compared with the neutral and alkaline solutions.
The filtering operation is not particularly limited in the present invention, and filtering operations well known to those skilled in the art may be employed.
The drying operation is not particularly limited, and the drying operation can be carried out until the weight is constant.
The application operation of the carbide slag-based low-shrinkage activator in the steel slag-based composite cementing material is not particularly limited, and the carbide slag-based low-shrinkage activator can be obtained by adopting operations well known to those skilled in the art.
In the invention, the steel slag-based composite cementing material preferably further comprises a micron-sized high water absorption resin and cement; the mass of the micron-sized high-water-absorbing resin is preferably 0.1% -0.3% of the total mass of the carbide slag-based low-shrinkage exciting agent, the steel slag and the cement, and more preferably 0.15% -0.20% of the total mass of the carbide slag-based low-shrinkage exciting agent, the steel slag and the cement; the particle size of the micro-sized high water absorbent resin is preferably < 0.1mm. In the present invention, the micro-sized high water absorbent resin preferably comprises the following chemical components in mass percent: 88% of low-crosslinking sodium polyacrylate, 8% -10% of water and 0.5% -1.0% of crosslinking agent; the mass percentage of sodium in the low-crosslinking sodium polyacrylate is preferably 24.5%; the micron-sized high water absorbent resin is preferably victory oilAnd (3) the field-length safety and control stock group limited company. In the invention, the micron-sized high water absorbent resin has good hydrophilicity, can provide an adhesion platform for hydration products, has a cavity inside, can continuously release water from the cavity, and can promote soluble Ca 2＋ The material is released continuously, the hydration speed is increased, the hydration product is increased continuously, the strength is improved continuously, the pores can be filled, the material is more compact, and the compressive strength is improved.
In the invention, when the steel slag-based composite cementing material comprises the micron-sized high water absorption resin, the steel slag-based composite cementing material is preferably mixed by uniformly mixing the raw materials except the micron-sized high water absorption resin, and then adding the micron-sized high water absorption resin and mixing for 3min. In the present invention, the mixing operation can avoid agglomeration of the micro-scale water absorbent resin.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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 raw materials used in the examples are as follows:
the grain diameter of carbide slag is less than or equal to 200 meshes;
the carbide slag comprises the following chemical components in percentage by mass: caCl (CaCl) 2 1.25%，CaO 89.02%，Na 2 O 0.59%，SiO 2 4.94%，MgO 0.51%，SO 3 0.68%，Al 2 O 3 2.69% and Fe 2 O 3 0.32%；
The carbide slag is produced by a water purification material factory of the strengthening Yuan Heng;
CaSO in desulfurized gypsum 4 ·2H 2 The mass of O is 90%;
the particle size of the desulfurized gypsum is less than or equal to 200 meshes;
the desulfurization gypsum comprises the following chemical components in percentage by mass: caO 48.06%, SO 3 43.57%，SiO 2 2.95%，MgO 1.48%，Al 2 O 3 1.18% and 2.76% of impurities;
the desulfurized gypsum is produced by a water purification material factory of consolidated Yuan Heng;
sodium silicate is white powder produced by national pharmaceutical group chemical reagent Co., ltd, the modulus is 1.3, and the water insoluble matter is less than or equal to 0.50%;
the lithium sulfate is produced by Shandong Ruifer lithium industry Co., ltd, and the purity is more than or equal to 95wt%;
the micron-sized high water absorbent resin is produced by the Ministry of long security group of victory oil fields, and the grain diameter is less than 0.1mm.
Examples 1 to 14
The amounts of the components of the carbide slag-based low shrinkage activator in examples 1 to 14 are shown in Table 1, and the unit is g.
Table 1 amounts of the components of the carbide slag-based Low shrinkage excitant in examples 1 to 14
The preparation method of the carbide slag-based low-shrinkage activator in examples 1-14 comprises the following steps: and (3) uniformly stirring and mixing the carbide slag, the desulfurized gypsum, the sodium silicate and the lithium sulfate to obtain the carbide slag-based low-shrinkage activator.
Raw materials of application example:
the chemical composition of the steel slag is CaO 34.2 percent and SiO is calculated by mass percent 2 27.1%，Fe 2 O 3 26.7% and Al 2 O 3 7.8% and 4.2% MgO;
the steel slag powder is converter steel slag produced by He Steel group Handa Steel company, the grain size is less than or equal to 120 meshes, and the density is 3.2g/cm 3 ；
The steel slag pretreatment comprises the steps of sequentially performing ball milling, sieving by a 120-mesh sieve, soaking in hydrochloric acid solution with the pH value of 5 at 25 ℃ for 3 days, filtering and drying;
standard sand is produced by Xiamen Aisi European standard sand limited company, has fineness modulus of 2.6, belongs to middle sand and accords with national standard GB/T17671-1999;
cement produced by China Association Cement group Co., ltd., P.II 42.5 Portland Cement having a density value of 3.16g/cm 3 The Bo specific surface area is 3570cm 2 /g。
Application example 1
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 189g of water, 202.5g of the carbide slag-based low shrinkage activator of example 1 and 0.9g of the micron-sized high water absorbent resin.
Application example 2
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 189g of water, 202.5g of carbide slag-based low shrinkage activator of example 2 and 0.9g of micron-sized high water absorbent resin.
Application example 3
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 189g of water, 202.5g of the carbide slag-based low shrinkage activator of example 3 and 0.9g of the micron-sized high water absorbent resin.
Application example 4
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 189g of water, 202.5g of the carbide slag-based low shrinkage activator of example 4 and 1.35g of the micron-sized high water absorbent resin.
Application example 5
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 189g of water, 202.5g of carbide slag-based low shrinkage activator of example 5 and 1.125g of micron-sized high water absorbent resin.
Application example 6
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 189g of water, 202.5g of the carbide slag-based low shrinkage activator of example 6 and 0.875g of the micron-sized high water absorbent resin.
Application example 7
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 189g of water, 202.5g of the carbide slag-based low shrinkage activator of example 7 and 0.45g of the micron-sized high water absorbent resin.
Application example 8
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 189g of water, 283.5g of the carbide slag-based low shrinkage activator of example 8 and 0.9g of the micron-sized high water absorbent resin.
Application example 9
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 189g of water, 283.5g of the carbide slag-based low shrinkage activator of example 9 and 0.9g of the micron-sized high water absorbent resin.
Application example 10
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 189g of water, 283.5g of the carbide slag-based low shrinkage activator of example 10 and 0.9g of the micron-sized high water absorbent resin.
Application example 11
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 189g of water, 283.5g of the carbide slag-based low shrinkage activator of example 11 and 1.35g of the micron-sized high water absorbent resin.
Application example 12
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 189g of water, 283.5g of the carbide slag-based low shrinkage activator of example 12 and 1.125g of the micron-sized high water absorbent resin.
Application example 13
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 189g of water, 283.5g of the carbide slag-based low shrinkage activator of example 13 and 0.875g of the micron-sized high water absorbent resin.
Application example 14
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 189g of water, 283.5g of the carbide slag-based low shrinkage activator of example 14 and 0.45g of the micron-sized high water absorbent resin.
Application example 15
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, and 202.5g and 0.9g of the carbide slag-based low shrinkage activator of example 1 of the high water absorption resin with a micrometer.
Application example 16
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, and 202.5g and 0.9g of the carbide slag-based low shrinkage activator of example 2 of the high water absorption resin with a micrometer.
Application example 17
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, and 202.5g and 0.9g of the carbide slag-based low shrinkage activator of example 3 of the high water absorption resin with a micrometer.
Application example 18
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, and 202.5g and 1.35g of the carbide slag-based low shrinkage activator of example 4 of the high water absorption resin with a micrometer.
Application example 19
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, 202.5g of carbide slag-based low shrinkage activator of example 5 and 1.125g of micron-sized high water absorbing resin.
Application example 20
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, and 202.5g and 0.875g of the carbide slag-based low shrinkage activator of example 6 of the high water absorption resin with a micrometer.
Application example 21
The composition of the steel slag-based composite cementing material is 202.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, and 202.5g and 0.45g of the carbide slag-based low shrinkage activator of example 7 of the high water absorption resin with a micrometer.
Application example 22
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, 283.5g of the carbide slag-based low shrinkage activator of example 8 and 0.9g of the micron-sized high water absorbent resin.
Application example 23
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, 283.5g of the carbide slag-based low shrinkage activator of example 9 and 0.9g of the micron-sized high water absorbent resin.
Application example 24
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, 283.5g of the carbide slag-based low shrinkage activator of example 10 and 0.9g of the micron-sized high water absorbent resin.
Application example 25
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, 283.5g of the carbide slag-based low shrinkage activator of example 11 and 1.35g of the micron-sized high water absorbent resin.
Application example 26
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, 283.5g of the carbide slag-based low shrinkage activator of example 12 and 1.125g of the high-water-absorption resin with a micrometer.
Application example 27
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, 283.5g of the carbide slag-based low shrinkage activator of example 13 and 0.875g of the micron-sized high water absorbent resin.
Application example 28
The composition of the steel slag-based composite cementing material is 121.5g of steel slag, 45g of cement, 225g of water, 1350g of standard sand, 283.5g of the carbide slag-based low shrinkage activator of example 14 and 0.45g of the micron-sized high water absorbent resin.
Comparative application example 1
The steel slag-based composite cementing material comprises 150g of steel slag, 33g of cement and 77g of water.
Comparative application example 2
The steel slag-based composite cementing material comprises 90g of steel slag, 33g of cement and 54g of water.
Comparative application example 3
The steel slag-based composite cementing material comprises 405g of steel slag, 45g of cement, 225g of water and 1350g of standard sand.
The preparation method of the steel slag-based composite cementing material in application examples 1-28 and comparative application examples 1-3 comprises the following steps:
the raw materials are mixed and molded by reference to GB/T1346-2001 method for checking water consumption, setting time and stability of cement standard consistency, a molding test mold is a six-way mold with the thickness of 40mm multiplied by 40mm, the molded test mold is put into a standard curing box for curing after pouring, the temperature is 45+/-2 ℃, the relative humidity is more than or equal to 90%, the mold is removed after curing for 48 hours, and then standard curing is carried out until the specified age.
The alkali-activated steel slag has certain requirements on the pH of an activation environment, and the pH of the environment is about 13 according to an alkali activation mechanism, so that the pH of the slurry prepared in application examples 1-14 is tested, and the results are shown in tables 2 and 3.
TABLE 2 pH of slurries prepared by application examples 1 to 7
| Application example 1 | Application example 2 | Application example 3 | Application example 4 | Application example 5 | Application example 6 | Application example 7 | |
| pH | 13.2 | 13.2 | 13.0 | 12.9 | 13.1 | 13.0 | 13.1 |
TABLE 3 pH of slurries prepared by application examples 8 to 14
| Application example 8 | Application example 9 | Application example 10 | Application example 11 | Application example 12 | Application example 13 | Application example 14 | |
| pH | 13.3 | 13.1 | 12.9 | 12.7 | 13.2 | 13.1 | 13.2 |
As can be seen from tables 2 and 3, the environment of the cementing materials prepared in application examples 1-14 basically meets the requirements.
The setting time of the steel slag-based composite cementitious materials prepared in application examples 1 to 14 and comparative application examples 1 to 2 was measured using a "cement paste standard consistency and setting time tester" (JC/T727), and the results are shown in tables 4 and 5.
TABLE 4 setting time of steel slag based composite cementitious materials prepared in application examples 1 to 7 and comparative application example 1
| Comparative application example 1 | Application example 1 | Application example 2 | Application example 3 | Application example 4 | Application example 5 | Application example 6 | Application example 7 | |
| Initial setting/min | 300 | 240 | 228 | 204 | 246 | 212 | 240 | 220 |
| Final setting/min | 486 | 426 | 414 | 384 | 432 | 404 | 430 | 408 |
TABLE 5 setting time of steel slag based composite cementitious materials prepared in application examples 8 to 14 and comparative application example 2
| Comparative application example 2 | Application example 8 | Application example 9 | Application example 10 | Application example 11 | Application example 12 | Application example 13 | Application example 14 | |
| Initial setting/min | 336 | 276 | 252 | 232 | 302 | 242 | 278 | 244 |
| Final setting/min | 504 | 456 | 432 | 450 | 440 | 428 | 454 | 426 |
As can be seen from tables 4 and 5, increasing the amount of the activator increases the setting time by about 15%; along with the increase of the mixing amount of the carbide slag, the initial setting time and the final setting time are reduced, the initial setting time is the shortest in application example 3, the final setting time is the longest in application example 8, the initial setting time is 204 min and 276min respectively, and the final setting time is 426 min and 456min respectively, because the combined action of the carbide slag, the desulfurized gypsum and the lithium sulfate can influence the cement hydration process, so that the setting time is reduced; comparing application examples 2, 4, 5, 6, 7 with comparative application example 1, it can be seen that the initial setting time of application example 4 is significantly higher than other application examples, the initial setting time is 246min, the final setting time is 432min, but still lower than comparative application example 1, application examples 9, 11, 12, 13, 14 and comparative application example 2 are compared, the initial setting time of application example 11 is significantly higher than other application examples, the initial setting time is 302min, the final setting time is 440min, but still lower than comparative application example 2, it is illustrated that when the content of desulfurized gypsum and lithium sulfate is fixed, the setting time is reduced along with the increase of sodium silicate content, because the amount of sodium silicate affects the environmental pH, si-O tetrahedron and Al-O tetrahedron depolymerization phenomenon already occur in the steel slag under the high alkaline environment, the existence form of a silicon tetrahedron structure exists mainly in the form of Q0, Q1 and Q2 (as shown in FIG. 1, the steel slag-based composite cementitious material prepared in FIG. 1 is shortened), the hydration speed is accelerated under the high pH environment, and the coagulation time map is accumulated; the quick setting phenomenon is not found in the setting time test process of the alkali-excited steel slag paste, and the initial setting time and the final setting time of the cementing material system are longer because the activity excitation of carbide slag and desulfurized gypsum is slower.
The shrinkage deformation measurements were carried out on application examples 1 to 14 and comparative application examples 1 to 2 by using a new revised "test method Standard for Long-term Properties and durability of ordinary concrete" GB/T50082, and the results are shown in FIGS. 6 and 7.
TABLE 6 shrinkage deformation change Rate of steel slag based composite cementitious Material prepared in application examples 1 to 7 and comparative application example 1
TABLE 7 shrinkage deformation change rate of steel slag based composite cementitious materials prepared in application examples 8 to 14 and comparative application example 2
As can be seen from tables 6 and 7, the shrinkage changes of the materials of comparative application examples 1 and 2 at 14d, 28d and 60d are more obvious, and the overall shrinkage deformation of application examples 1 to 14 is reduced, because the steel slag particles are continuously depolymerized and dispersed under the high-pH environment, hydration products are continuously accumulated, and the overall structure becomes compact; the shrinkage deformation of the materials of application examples 2, 4 and 5 and application examples 9, 11 and 12 at 14d is significantly reduced compared with the other application examples, wherein steel slag and activator 1: application example 4 was changed by 50% in the case of 1 blend amount as compared with comparative application example 1; steel slag and activator 3: application example 11 was 53% changed compared to comparative application example 2 in the case of the 7-doped amount; the high-content high-shrinkage of the micro-scale high-water-absorbing resin of application examples 4 to 7 and application examples 11 to 14 is increased from the shrinkage change, because the micro-scale high-water-absorbing resin has cavities inside, and the shrinkage is indirectly increased by increasing the whole pores. The mixing amount of the carbide slag is 71% as a whole, the desulfurized gypsum is 18%, the shrinkage changes of sodium silicate 6%, lithium sulfate 5% and the micron-sized high water absorbent resin are the smallest, and the shrinkage changes of 14d, 28d and 60d are also smoother.
FIG. 2 is a 14-day SEM scan of the steel slag-based composite cementitious material prepared in application example 25; FIG. 3 is a 28-day SEM scan of the steel slag-based composite cementitious material prepared in application example 25; FIG. 4 is a 60-day SEM scan of the steel slag-based composite cementitious material prepared in application example 25; fig. 5 is an XRD analysis result of the steel slag-based composite cementitious material prepared in application example 18.
Compressive strength tests were conducted on application examples 15 to 28 and comparative application example 3 according to the cement mortar strength test method (ISO method) GB/T17671-2021, as shown in tables 8 and 9.
TABLE 8 compressive Strength of slag based composite cementitious Material prepared in application examples 15-21 and comparative application example 3
| 14d compressive Strength/MPa | 28d compressive Strength/MPa | 60d compressive strength/MPa | |
| Comparative application example 3 | 11.4 | 26.2 | 33.9 |
| Application example 15 | 14.7 | 29.1 | 37.7 |
| Application example 16 | 17.7 | 31.7 | 39.9 |
| Application example 17 | 13.9 | 28.2 | 35.7 |
| Application example 18 | 18.3 | 34.5 | 41.2 |
| Application example 19 | 17.2 | 32.9 | 40.5 |
| Application example 20 | 15.5 | 30.3 | 38.3 |
| Application example 21 | 15.1 | 29.9 | 36.5 |
Table 9 compressive Strength of slag-based composite cementitious Material prepared in application examples 22 to 28 and comparative application example 3
| 14d compressive Strength/MPa | 28d compressive Strength/MPa | 60d compressive strength/MPa | |
| Comparative application example 3 | 11.4 | 26.2 | 33.9 |
| Application example 22 | 17.2 | 30.2 | 40.4 |
| Application example 23 | 15.6 | 28.4 | 37.0 |
| Application example 24 | 14.4 | 26.7 | 36.2 |
| Application example 25 | 18.8 | 33.0 | 41.7 |
| Application example 26 | 17.7 | 31.4 | 41.0 |
| Application example 27 | 16.0 | 28.8 | 38.8 |
| Application example 28 | 15.2 | 27.6 | 38.2 |
As can be seen from tables 8 and 9 and fig. 2 to 5, the compressive strength of the application examples 15 to 28 was significantly improved in 14d, 28d and 60d as compared with the comparative application example 3; in application examples 15-17 (or application examples 22-24), the content of the desulfurized gypsum is sequentially decreased, the strength is increased and then decreased, which means that the content of the desulfurized gypsum accelerates the formation of ettringite in application examples 15 and 16 (or application examples 22 and 23) to increase the strength, the content of the desulfurized gypsum is excessively saturated in application example 17 (or application example 24) to influence the later strength, the influence of the micron-sized high water absorbent resin is remarkable, the strength is continuously decreased along with the continuous decrease of the content of the micron-sized high water absorbent resin, and when the doping amount of the micron-sized high water absorbent resin is 0.3%, the compressive strength of application example 18 is respectively increased by 60.5%, 31.6% and 21.5% in 14d, 28d and 60d compared with comparative application example 3, and the compressive strength of application example 25 is increased by 64.9%, 25.9% and 23.0% compared with comparative application example 3; application example 21 when the amount of the micro-scale high water absorbent resin is 0.1%Compressive strength at 14d, 28d and 60d increased by 32.4%, 14.1% and 7.6%, respectively, as compared to comparative application example 3, and application example 28 increased by 33.3%, 5.3% and 12.7%, respectively, as compared to comparative application example 3. The reason why the micron-sized high water absorbent resin has increased strength is that the micron-sized high water absorbent resin has good hydrophilicity, can provide an adhesion platform for hydration products, has cavities inside the micron-sized high water absorbent resin, can continuously release water from the cavities, and can promote soluble Ca 2＋ The product is released continuously, the hydration speed is increased, the hydration products of C-S-H gel, C-A-S-H, ettringite and hydrated calcium aluminate are increased continuously, and the strength is improved continuously (as shown in figure 5). In addition, the micron-sized high water absorbent resin is uniformly dispersed in the slurry, so that the pores can be filled, the material is more compact, and the compressive strength is directly improved.
From the above data, the following conclusions can be drawn:
(1) The pH value of the slurry is about 13.0, which indicates that the mixing ratio meets the alkali environment requirement of alkali excitation.
(2) The mass ratio of the steel slag to the exciting agent is 1:1 to 3: the 7 clotting time became longer, about 15% increase in total. With the increase of the mixing amount of the exciting agent, the initial setting time and the final setting time are reduced, and with the increase of the sodium silicate content, the initial setting time and the final setting time are reduced.
(3) The shrinkage variations of 14d, 28d and 60d are more pronounced and the overall shrinkage deformation of the application example is reduced compared to the comparative application example. In the exciting agent, the shrinkage variation of the material is minimal when the mass of carbide slag is 71wt%, the mass of desulfurized gypsum is 18wt%, the mass of sodium silicate is 6wt%, the mass of lithium sulfate is 5% and the mass of the micron-sized high water absorbent resin is 0.3wt%, and the shrinkage variation of application example 4 is (2.5-2.6) multiplied by 10 -6 Shrinkage variation of application example 11 was (2.2 to 2.3). Times.10 -6 And was stable during the experimental age.
(4) Compared with the comparative examples, the compressive strength of the examples 14d, 28d and 60d is obviously improved; the content of the desulfurized gypsum is gradually decreased, and the strength is increased and then decreased; when carbide slag and desulfurized gypsum are fixed, the influence of the micron-sized high water absorption resin is remarkable, and the strength is increased along with the increasing of the content of the micron-sized high water absorption resin; the mass ratio of the steel slag to the exciting agent is 1: in the case of 1, the best effect of application example 18 is that the compressive strengths of 14d, 28d and 60d reach 18.3MPa, 34.5MPa and 41.2MPa; the mass ratio of the steel slag to the exciting agent is 3: in 7 cases, the best effect of application example 25 is that the compressive strength of 14d, 28d and 60d reaches 18.8MPa, 33.0MPa and 41.7MPa, and the engineering requirements are met.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (2)
1. The application of the carbide slag-based low-shrinkage activator in the steel slag-based composite cementing material;
the carbide slag-based low-shrinkage excitant is prepared from the following components in percentage by mass: 65% -75% of carbide slag, 15% -20% of desulfurized gypsum, 4% -10% of sodium silicate and 5% of lithium sulfate;
the steel slag-based composite cementing material also comprises micron-sized high water-absorbing resin and cement, wherein the mass of the micron-sized high water-absorbing resin is 0.1% -0.3% of the total mass of the carbide slag-based low shrinkage excitant, the steel slag and the cement.
2. The use according to claim 1, characterized in that the mass ratio of carbide slag-based low shrinkage activator to steel slag is 1:1 or 7:3.
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| CN103058566A (en) * | 2013-01-15 | 2013-04-24 | 逄鲁锋 | Autogenous curing agent for cement-based material and preparation method thereof |
| CN105884316A (en) * | 2016-04-19 | 2016-08-24 | 北京建筑材料科学研究总院有限公司 | Baking-free brick prepared from iron tailings and preparation method of baking-free brick |
| CN114751662A (en) * | 2022-03-31 | 2022-07-15 | 抚顺大伙房水泥有限责任公司 | Alkaline steel slag activity excitant and preparation method of steel slag cementing material |
| CN114940600A (en) * | 2022-06-16 | 2022-08-26 | 山东理工大学 | Full-solid waste filling material and preparation method thereof |
| CN115073116A (en) * | 2022-06-20 | 2022-09-20 | 涉县清漳水泥制造有限公司 | Grouting material containing steel slag solid waste base cementing material |
| CN115784651A (en) * | 2022-12-29 | 2023-03-14 | 河北高速集团工程咨询有限公司 | Steel slag-based anti-freezing geopolymer and preparation method thereof |
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2023
- 2023-06-20 CN CN202310727674.0A patent/CN116462439B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058566A (en) * | 2013-01-15 | 2013-04-24 | 逄鲁锋 | Autogenous curing agent for cement-based material and preparation method thereof |
| CN105884316A (en) * | 2016-04-19 | 2016-08-24 | 北京建筑材料科学研究总院有限公司 | Baking-free brick prepared from iron tailings and preparation method of baking-free brick |
| CN114751662A (en) * | 2022-03-31 | 2022-07-15 | 抚顺大伙房水泥有限责任公司 | Alkaline steel slag activity excitant and preparation method of steel slag cementing material |
| CN114940600A (en) * | 2022-06-16 | 2022-08-26 | 山东理工大学 | Full-solid waste filling material and preparation method thereof |
| CN115073116A (en) * | 2022-06-20 | 2022-09-20 | 涉县清漳水泥制造有限公司 | Grouting material containing steel slag solid waste base cementing material |
| CN115784651A (en) * | 2022-12-29 | 2023-03-14 | 河北高速集团工程咨询有限公司 | Steel slag-based anti-freezing geopolymer and preparation method thereof |
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