CN1286766C - Steel slag-metakaolin compound gel material and preparation method thereof - Google Patents
Steel slag-metakaolin compound gel material and preparation method thereof Download PDFInfo
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- CN1286766C CN1286766C CNB2005100186957A CN200510018695A CN1286766C CN 1286766 C CN1286766 C CN 1286766C CN B2005100186957 A CNB2005100186957 A CN B2005100186957A CN 200510018695 A CN200510018695 A CN 200510018695A CN 1286766 C CN1286766 C CN 1286766C
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- metakaolin
- water glass
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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
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Abstract
The present invention relates to alkali gelled materials without cement clinkers. The gelled materials compounded by steel slag-metakaolin are formed by that steel slag, metakaolin, water glass solution, sodium sulfate and sodium fluoride are mixed. Ingredients have the following quality proportioning: the steel slag: the metakaolin: the water glass liquor: Na2SO4: NaF equals to 1:0.1 to 9:0.66 to 8:0.033 to 0.3:0.022 to 0.2, wherein the fineness of the steel slag is from 400 to 650m<2>/kg, and alkalinity is larger than 1.2; the metakaolin is calcined by coal-series kaolin at the temperature of 650 to 800DEGC, and fineness is from 500 to 700m<2>/kg; the mode number of water glass is from 1.0 to 2.0, and the baume degree of the water glass is from 33 to 44 degrees. The materials of the present invention have the characteristics of gelling properties, and the performance requirements of ordinary portland cement of the same grade can be satisfied.
Description
Technical field
The invention belongs to the ceramic class, be specifically related to gelling material of a kind of non-cement grog and preparation method thereof.
Background technology
Traditional Cement industry industry because it consumes the very big resource and the energy in cement production process, is discharged the material and the defective of product on some performance of a large amount of contaminate environment, makes it face the challenge of Sustainable development; In addition, traditional basic activities such as iron and steel, electric power, coal, metallurgy also produce a large amount of industrial residues on a large amount of natural resource of consumption and energy basis, make land resources, ecotope be faced with huge pressure.Above-mentioned all factors have seriously restricted the construction and the strategy of sustainable development of national economy.Wherein with the quantity discharged maximum of slag, Coaseries kaolin, and never obtain fine utilization.
Summary of the invention
For this reason, the objective of the invention is to utilize the latent hydraulicity characteristics of slag, metakaolin, the use alkali-activator excites the hydration activity of slag and makes the metakaolin polymerization, thereby makes slag and the compound steel slag-metakaolin compound gel material that obtains having gelling property of metakaolin.
Technical scheme of the present invention is: steel slag-metakaolin compound gel material, mix by slag, metakaolin, water glass solution, sodium sulfate, Sodium Fluoride, and its each component quality proportioning is: slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: (0.1-9): (0.66-8): (0.033-0.3): (0.022-0.2); Wherein, the specific surface area of slag is 400-650m
2/ kg, basicity＞1.2; Metakaolin is Coaseries kaolin calcination under 650-800 ℃ of condition, and specific surface area is 500-700m
2/ kg; The modulus of water glass is 1.0-2.0, the degree Beaume 33-44 of water glass °.
Described each component quality proportioning is: slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: (0.1-0.43): (0.66-1.12): (0.033-0.043): (0.022-0.029), wherein the modulus of water glass is 1.0-2.0, the degree Beaume 33-36 of water glass °; With reference to GB GB/T17671-1999 experimental technique, can reach the intensity of the ordinary Portland cement of label 32.5 or 32.5R.
Described each component quality proportioning is: slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: (0.67-1.5): (1.0-2): (0.05-0.075): (0.033-0.05), wherein the modulus of water glass is 1.0-2.0, the degree Beaume 36-40 of water glass °; With reference to GB GB/T17671-1999 experimental technique, can reach the intensity of the ordinary Portland cement of label 42.5 or 42.5R.
Described each component quality proportioning is: slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: (2.3-9): (1.98-8): (0.1-0.3): (0.07-0.2), wherein the modulus of water glass is 1.0-2.0, the degree Beaume 40-44 of water glass °; With reference to GB GB/T17671-1999 experimental technique, can reach the intensity of the ordinary Portland cement of label 52.5 or 52.5R.
The preparation method of steel slag-metakaolin compound gel material comprises the steps: 1). at first the slag of basicity＞1.2 being milled down to specific surface area is 400-650m
2/ kg forms fine steel-making slag powder; Getting Coaseries kaolin calcination under 650-800 ℃ of condition, to become specific surface area be 500-700m
2The metakaolin of/kg; The Sodium Fluoride efflorescence is formed powder; Then in slag: metakaolin: the quality proportioning of Sodium Fluoride is=1: (0.1-9): ratio (0.022-0.2) is carried out mechanically mixing makes it even, seals, adorns bag then, seals up for safekeeping, gets steel slag-metakaolin-Sodium Fluoride powder; 2). the NaOH solid is added in the sodium silicate solution dissolving slowly, and to obtain modulus be that 1.0-2.0, degree Beaume are 33-44 ° water glass solution; Press slag: water glass solution: Na
2SO
4The quality proportioning be=1: (0.66-8): (0.033-0.3) choose water glass solution: Na
2SO
4Sodium sulfate is joined mixed preparing in the water glass solution and get mixing solutions; 3). with step 2) mixing solutions for preparing adds in steel slag-metakaolin-Sodium Fluoride powder slowly, stirs 0.8-1.2min, pours out cast then.
The present invention adopts water glass (modulus 1.0-2.0, degree Beaume 33-44 °), sodium sulfate, the agent of Sodium Fluoride equal excitation excites the non-cement grog gelling material that can obtain different intensity grades such as 32.5,42.5,52.5 to different ratios slag, metakaolin, its water requirement, standard consistency, time of coagulation are under the regulating effect of chemical admixture (ammonium sulfonate, trisodium phosphate, Sodium Fluoride etc.), all can satisfy with label ordinary Portland cement performance requriements, it can prepare the C30-C50 concrete.
Steel slag-metakaolin compound gel material is a kind of with inorganic SiO
4, AlO
4Tetrahedron is main the composition, has the netted keyed jointing structure of space three-dimensional on the structure, and the aquation steel slag particle is not embedded in the novel inorganic silicon-aluminum gelatinized material in the network structure, and hydrated product is a kind of amorphous structure.Its gelling system reaction mechanism can be divided into following two steps:
The first step: metakaolin and amorphous silica are under the effect of water and strong nucleophilic reagent NaOH and KOH, the fracture of Si-O and Al-O covalent linkage takes place, can think in the aqueous solution mixed sols that generates silicic acid and aluminium hydroxide, the partial dehydration condensation generates positive manosil AS between the sol particle.Na
+And K
+Be attracted to around the molecular linkage, balance aluminium (+3 valencys, four-coordination) with negative charge;
Second step: the hydroxyl on the positive manosil AS molecule is extremely unstable in basic solution or under the drying conditions, the formation hydrogen bond that attracts each other, thus further dehydrating condensation forms unique reticulated structure that poly-aluminium silica macromolecular chain constitutes slag and metakaolin compound gel material.
And the action principle of slag breeze in cementitious material system is embodied in the following aspects:
(1) initial network of negatively charged ion formation gelling system in the exciting agent; Alkaline environment is set up and kept to positively charged ion, accelerate metakaolin in alkaline solution depolymerization-polycondensation process; Slag is that to the promoter action of metakaolin the slag aquation discharges Ca on the one hand
2+And OH
-, Ca wherein
2+With the silica reaction of low polymerization degree, OH
-Promote scoriaceous depolymerization; Crystalline inducing action in the slag on the other hand.
(2) slag is mainly made the micro-aggregate of gelling system in early days in aquation, the hydrated product of aquation later stage generating portion, and the miocrystalline material that metakaolin generates under the alkali effect is the main source of this system network skeleton; Slag composite gelled material hydrated product mainly contains Calucium Silicate powder and variant thereof, and its general formula is: CaOAl
2O
3XSiO
2YH
2The O mineral abbreviate C-S-Al-H as.
(3) hydration reaction of steel slag-metakaolin compound gel material is the depolymerization and the reversible equilibrium process of polymeric of silicic acid structure, and when aquation began, the high-polymerization degree vitreum was at OH
-Effect under depolymerization gradually, along with the increase of the silicic acid concentration of low polymerization degree in the solution, reaction is carried out to direction of polymerization, the silicic acid of newly-generated high-polymerization degree and salt thereof are filled and are embedded in the silica back bone network, make structure closely knit gradually.
The present invention utilizes the latent hydraulicity characteristics of slag, metakaolin, use alkali-activator (alkali-activator is water glass solution, sodium sulfate, Sodium Fluoride) excite slag hydration activity and make the metakaolin polymerization, thereby make slag and the compound steel slag-metakaolin compound gel material that obtains having gelling property of metakaolin.
The invention of steel slag-metakaolin compound gel material not only provides a direction for slag, kaolinic application, and can make traditional water mud industry can walk the route of Sustainable development.
Embodiment
One, the preparation method of steel slag-metakaolin compound gel material:
The preparation method of steel slag-metakaolin compound gel material comprises the steps: 1). at first the slag of basicity＞1.2 being milled down to specific surface area is 400-650m
2/ kg forms fine steel-making slag powder; Getting Coaseries kaolin calcination under 650-800 ℃ of condition, to become specific surface area be 500-700m
2The metakaolin of/kg; The Sodium Fluoride efflorescence is formed powder; Then in slag: metakaolin: the quality proportioning of Sodium Fluoride is=1: (0.1-9): ratio (0.022-0.2) is carried out mechanically mixing makes it even, seals, adorns bag then, seals up for safekeeping, gets steel slag-metakaolin-Sodium Fluoride powder; 2). the NaOH solid is added in the sodium silicate solution dissolving slowly, and to obtain modulus be that 1.0-2.0, degree Beaume are 33-44 ° water glass solution; Press slag: water glass solution: Na
2SO
4The quality proportioning be=1: (0.66-8): (0.033-0.3) choose water glass solution: Na
2SO
4Sodium sulfate is joined mixed preparing in the water glass solution and get mixing solutions; 3). with step 2) mixing solutions for preparing adds in steel slag-metakaolin-Sodium Fluoride powder slowly, stirs 0.8-1.2min, pours out cast then.
1,32.5 or the preparation of the steel slag-metakaolin compound gel material of 32.5R strength grade: press slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: (0.1-0.43): (0.66-1.12): (0.033-0.043): (0.022-0.029); Wherein the modulus of water glass is 1.0-2.0, the degree Beaume 33-36 of water glass °; With reference to GB GB/T17671-1999 experimental technique, can reach the intensity of the ordinary Portland cement of label 32.5 or 32.5R.Concrete embodiment such as table 1.
2,42.5 or the preparation of the steel slag-metakaolin compound gel material of 42.5R strength grade: press slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: (0.67-1.5): (1.0-2): (0.05-0.075): (0.033-0.05); Wherein the modulus of water glass is 1.0-2.0, the degree Beaume 36-40 of water glass °; With reference to GB GB/T17671-1999 experimental technique, can reach the intensity of the ordinary Portland cement of label 42.5 or 42.5R.Concrete embodiment such as table 2.
3,52.5 or the preparation of the steel slag-metakaolin compound gel material of 52.5R strength grade: press slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: (2.3-9): (1.98-8): (0.1-0.3): (0.07-0.21); Wherein the modulus of water glass is 1.0-2.0, the degree Beaume 40-44 of water glass °; With reference to GB GB/T17671-1999 experimental technique, can reach the intensity of the ordinary Portland cement of label 52.5 or 52.5R.Concrete embodiment such as table 3.
Slag and metakaolin compound gel material must be under the dry moistureproof condition, otherwise the inefficacy of can luming.
The proportioning of the steel slag-metakaolin compound gel material of table 1 32.5 or 32.5R strength grade
| Strength grade | Glue material proportioning | The water glass solution proportioning | Intensity (MPa) | ||
| Slag: metakaolin: water glass solution: Na 2SO 4∶NaF | Modulus | Solid content (%) | 3d | 28d | |
| 32.5 | 1∶0.1∶0.66∶0.033∶0.022 | 1 | 33 | 26.5 | 37.2 |
| 1∶0.25∶0.75∶0.038∶0.025 | 1.42 | 35 | 26.7 | 38.9 | |
| 1∶0.43∶0.86∶0.043∶0.029 | 1.8 | 36 | 27.3 | 36.2 | |
| 1∶0.1∶0.77∶0.033∶0.022 | 1.1 | 34 | 28.2 | 35.9 | |
| 1∶0.25∶0.88∶0.038∶0.025 | 1.5 | 36 | 26.9 | 37.7 | |
| 1∶0.43∶1.0∶0.043∶0.029 | 2 | 35 | 27.1 | 39.4 | |
| 32.5R | 1∶0.1∶0.88∶0.033∶0.022 | 1 | 36 | 31.2 | 39.1 |
| 1∶0.25∶1.0∶0.038∶0.025 | 1.42 | 33 | 30.5 | 40.5 | |
| 1∶0.43∶1.12∶0.043∶0.029 | 1.8 | 34 | 31.8 | 38.9 | |
The proportioning of the steel slag-metakaolin compound gel material of table 2 42.5 or 42.5R strength grade
| Strength grade | Glue material proportioning | The water glass solution proportioning | Intensity (MPa) | ||
| Slag: metakaolin: water glass solution: Na 2SO 4∶NaF | Modulus | Solid content (%) | 3d | 28d | |
| 42.5 | 1∶0.67∶1.0∶0.05∶0.033 | 1 | 36 | 32.9 | 48.4 |
| 1∶1∶1.2∶0.06∶0.04 | 1.42 | 38 | 33.5 | 49.1 | |
| 1∶1.5∶1.5∶0.075∶0.05 | 1.8 | 40 | 32.3 | 48.1 | |
| 1∶0.67∶1.17∶0.05∶0.033 | 2 | 44 | 31.1 | 47.9 | |
| 1∶1∶1.4∶0.06∶0.04 | 1 | 36 | 27.1 | 49.3 | |
| 1∶1.5∶1.75∶0.075∶0.05 | 1.42 | 38 | 27.3 | 50 | |
| 42.5R | 1∶0.67∶1.34∶0.05∶0.033 | 1 | 36 | 36.6 | 51.2 |
| 1∶1∶1.6∶0.06∶0.04 | 1.42 | 38 | 35.6 | 52.3 | |
| 1∶1.5∶2∶0.075∶0.05 | 1.8 | 40 | 35.4 | 52.4 | |
The proportioning of the steel slag-metakaolin compound gel material of table 3 52.5 or 52.5R strength grade
| Strength grade | Glue material proportioning | The water glass solution proportioning | Intensity (MPa) | ||
| Slag: metakaolin: water glass solution: Na 2SO 4∶NaF | Modulus | Solid content (%) | 3d | 28d | |
| 52.5 | 1∶2.3∶1.98∶0.1∶0.07 | 1 | 41 | 45.5 | 60 |
| 1∶4∶3.0∶0.15∶0.1 | 1.42 | 42 | 48.6 | 62 | |
| 1∶9∶6∶0.3∶0.2 | 1.8 | 41 | 46.4 | 61.5 | |
| 1∶2.3∶2.31∶0.1∶0.07 | 2 | 42 | 47.2 | 63.1 | |
| 1∶4∶3.5∶0.15∶0.1 | 1 | 44 | 46.1 | 60.5 | |
| 1∶9∶7∶0.3∶0.2 | 1.42 | 43 | 49.2 | 62.5 | |
| 52.5R | 1∶2.3∶2.64∶0.1∶0.07 | 1 | 41 | 50.2 | 66 |
| 1∶4∶4.0∶0.15∶0.1 | 1.42 | 42 | 52.6 | 66.5 | |
| 1∶9∶8.0∶0.3∶0.2 | 1.8 | 44 | 53.1 | 64.6 | |
Two, steel slag-metakaolin compound gel material concrete formulating method:
Above-mentioned steel slag-metakaolin compound gel material is carried out the concrete preparation, earlier powder is poured in the stirred vessel, add to gather materials again and carry out dry mixing 1min, then exciting agent is dissolved in and form solution in the water, at last solution is poured into slowly and stirred 2min in the stirred vessel, pour out moulding after guaranteeing to stir, on shaking table, vibrate 30s, mark and support its intensity of test after the length of time, part of test results such as table 4.
Table 4 steel slag-metakaolin compound gel material concrete mix (kg/m
3)
| Numbering | Gelling material | Sand | Stone | Alkali activating agent solution | Intensity (MPa) | ||
| Kind (being aforesaid strength grade) | Consumption | 7d | 28d | ||||
| 1 | 32.5 | 400 | 739 | 1021 | 240 | 30.1 | 40.8 |
| 2 | 32.5R | 400 | 739 | 1021 | 240 | 35.6 | 41.3 |
| 3 | 42.5 | 500 | 672 | 928 | 300 | 40.6 | 50.0 |
| 4 | 42.5R | 500 | 672 | 928 | 300 | 44.2 | 52.0 |
| 5 | 52.5 | 600 | 605 | 835 | 360 | 52.3 | 60.7 |
| 6 | 52.5R | 600 | 605 | 835 | 360 | 57.8 | 62.2 |
Claims (5)
1. steel slag-metakaolin compound gel material is mixed by slag, metakaolin, water glass solution, sodium sulfate, Sodium Fluoride, and its each component quality proportioning is: slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: 0.1-9: 0.66-8: 0.033-0.3: 0.022-0.2; Wherein, the specific surface area of slag is 400-650m
2/ kg, basicity＞1.2; Metakaolin is Coaseries kaolin calcination under 650-800 ℃ of condition, and specific surface area is 500-700m
2/ kg; The modulus of water glass is 1.0-2.0, the degree Beaume 33-44 of water glass °.
2. steel slag-metakaolin compound gel material according to claim 1 is characterized in that: described each component quality proportioning is: slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: 0.1-0.43: 0.66-1.12: 0.033-0.043: 0.022-0.029, wherein the modulus of water glass is 1.0-2.0, the degree Beaume 33-36 of water glass °.
3. steel slag-metakaolin compound gel material according to claim 1 is characterized in that: described each component quality proportioning is: slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: 0.67-1.5: 1.0-2: 0.05-0.075: 0.033-0.05, wherein the modulus of water glass is 1.0-2.0, the degree Beaume 36-40 of water glass °.
4. steel slag-metakaolin compound gel material according to claim 1 is characterized in that: described each component quality proportioning is: slag: metakaolin: water glass solution: Na
2SO
4: NaF=1: 2.3-9: 1.98-8: 0.1-0.3: 0.07-0.2, wherein the modulus of water glass is 1.0-2.0, the degree Beaume 40-44 of water glass °.
5. the preparation method of steel slag-metakaolin compound gel material as claimed in claim 1 is characterized in that comprising the steps: 1). at first the slag of basicity＞1.2 being milled down to specific surface area is 400-650m
2/ kg forms fine steel-making slag powder; Getting Coaseries kaolin calcination under 650-800 ℃ of condition, to become specific surface area be 500-700m
2The metakaolin of/kg; The Sodium Fluoride efflorescence is formed powder; Then in slag: metakaolin: the quality proportioning of Sodium Fluoride is=1: the ratio of 0.1-9: 0.022-0.2 is carried out mechanically mixing makes it even, seals, adorns bag then, seals up for safekeeping, gets steel slag-metakaolin-Sodium Fluoride powder; 2). the NaOH solid is added in the sodium silicate solution dissolving slowly, and to obtain modulus be that 1.0-2.0, degree Beaume are 33-44 ° water glass solution; Press slag: water glass solution: Na
2SO
4The quality proportioning be=1: 0.66-8: 0.033-0.3 chooses water glass solution: Na
2SO
4Sodium sulfate is joined mixed preparing in the water glass solution and get mixing solutions; 3). with step 2) mixing solutions for preparing adds in steel slag-metakaolin-Sodium Fluoride powder slowly, stirs 0.8-1.2min, pours out cast then.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560068B (en) * | 2009-06-03 | 2011-12-28 | 西安建筑科技大学 | Kaolin-slag base geological polymer compound cementing material with enhanced composite organic macromolecule and preparation method thereof |
| CN101698576B (en) * | 2009-10-22 | 2012-11-21 | 厦门市建筑科学研究院集团股份有限公司 | Method for preparing slag-activated metakaolin cementitious materials |
| CN101891448B (en) * | 2010-05-07 | 2012-12-19 | 武汉理工大学 | Cement-base quick repairing material and preparation method thereof |
| CN102093021B (en) * | 2010-12-28 | 2013-05-22 | 济南丞华环保科技发展中心 | Slag micro-powder dry mixed mortar |
| CN103613296B (en) * | 2013-12-04 | 2015-09-09 | 重庆大学 | A kind of low temperature calcination intercalation kaolin soil prepares the method for alkali-activated carbonatite gelling material |
| CN104003632B (en) * | 2014-06-13 | 2016-05-04 | 福州大学 | A kind of method of utilizing Pb-Zn tailings to prepare geopolymer |
| CN106316171A (en) * | 2016-08-05 | 2017-01-11 | 东南大学 | Compound steel slag-based cement used for foundation reinforcement and soil mass improvement |
| CN108503292A (en) * | 2018-05-18 | 2018-09-07 | 武汉工程大学 | The metakaolin base geological polymer and preparation method thereof of slag powder is discarded in a kind of addition |
| CN109399975B (en) * | 2018-11-26 | 2022-03-11 | 武汉理工大学 | Red mud sulfur fixation ash steel slag powder coupling excitation cementing material and application thereof |
| CN109369047A (en) * | 2018-12-03 | 2019-02-22 | 佛山科学技术学院 | A kind of high morning native polywater mud and preparation method thereof by force |
| CN109574564A (en) * | 2018-12-20 | 2019-04-05 | 重庆工程职业技术学院 | A kind of high intensity alkali-activated carbonatite metakaolin sill and preparation method |
| CN115490447B (en) * | 2022-10-09 | 2023-04-25 | 碳达(深圳)新材料技术有限责任公司 | Full solid waste alkali-activated cementing material and preparation method thereof |
| CN116283092A (en) * | 2023-03-08 | 2023-06-23 | 中国矿业大学 | Method for improving crack resistance of alkali slag by using hot-melt modified excitant |
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