CN106977150A - A kind of preparation method using slag as the cement-base composite material of admixture - Google Patents
A kind of preparation method using slag as the cement-base composite material of admixture Download PDFInfo
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- CN106977150A CN106977150A CN201710313561.0A CN201710313561A CN106977150A CN 106977150 A CN106977150 A CN 106977150A CN 201710313561 A CN201710313561 A CN 201710313561A CN 106977150 A CN106977150 A CN 106977150A
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- parts
- slag
- cement
- mixed
- composite material
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- 239000002893 slag Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 42
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004568 cement Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 15
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims abstract description 15
- 239000011268 mixed slurry Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000010881 fly ash Substances 0.000 claims abstract description 10
- 239000010440 gypsum Substances 0.000 claims abstract description 10
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 230000008961 swelling Effects 0.000 claims abstract description 9
- 239000013530 defoamer Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000004576 sand Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000010456 wollastonite Substances 0.000 claims abstract description 5
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- -1 amine hydrochloride Chemical class 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 11
- 239000012362 glacial acetic acid Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 159000000007 calcium salts Chemical class 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 235000019255 calcium formate Nutrition 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical group CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000004281 calcium formate Substances 0.000 claims description 2
- 229940044172 calcium formate Drugs 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940117957 triethanolamine hydrochloride Drugs 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims 2
- 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 claims 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001879 gelation Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- HHLJUSLZGFYWKW-UHFFFAOYSA-N triethanolamine hydrochloride Chemical class Cl.OCCN(CCO)CCO HHLJUSLZGFYWKW-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000316986 Scutellathous comes Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of using slag as the preparation method of the cement-base composite material of admixture, comprise the following steps：Mix preparation is prepared first, and pretreatment slag micro powder is made in itself and slag mixing and ball milling；Montmorillonite and Cetyltrimethylammonium bromide and hexamethylene are mixed, then the CNT of carboxylated is added, obtain CNT intercalated montmorillonite material, finally cement, pretreatment slag micro powder, CNT intercalated montmorillonite material, flyash, wollastonite in powder, gypsum, natural river sand are mixed evenly, and addition is by the mixture of water reducer, defoamer, swelling agent, dispersant and deionized water, cement base mixed slurry is made after well mixed, add it in mould, jolt ramming is molded, demoulding maintenance, is made cement-base composite material.This method is cheap using slag as raw material, and pretreated slag gelation activity is big, and composite material strength is big, and mechanical property is good.
Description
Technical field：
The present invention relates to building material field, it is specifically related to a kind of using slag as the cement-base composite material of admixture
Preparation method.
Background technology：
Slag is the solid waste produced in steel smelting procedure, based on its mineral composition silicate phase, with potential
Gelling property, its discharge rate is about the 15-20% of crude steel yield.The density of slag is between 3.3-3.6g/cm3Between, from table
From the point of view of on face, steel slag particle connection is more open, and quality is hard.Because Fe content is high, cause steel slag grinding relatively difficult, steel
Being of grindability index 7 of slag, the grindability index 1.0 of grindability indexization 96, normal sand less than blast-furnace cinder.
Developed country, the overall utilization rate Hen Waterloo of slag, almost close to 100%, but developed country is in cement and coagulation
Utilization rate in terms of native product is very low.The slag that Germany produces in steel-making, although its utilization rate is very high, is mostly treated as
Gather materials and use, an only small part slag is used for cement products：And the U.S. comes before nineteen ninety merely with 1% slag raw material
Manufacture cement.In Chinese slag (mainly vessel slag) cumulant more than 30,000,000,000 tons, but these slags whole utilization level not
It is high.Consider from the resource and validity angle of slag, the utilization rate of slag is about 36%, approximate 10% or so slag
It is utilized in building materials field, in terms of about 3% is used for cement.Therefore, the utilization rate for improving slag is to realize steel enterprise of China
The important channel of industry sustainable development.But free oxidation in slag is skilful, the hydration process of magnesia can cause slag cement
The expansion of composite gelled material volume, causes the less stable of system；And the fluctuation of its composition is big, early strength is low, causes
Its application in cement-based material is by limitation.
The content of the invention：
The purpose of the present invention is to disclose a kind of preparation method using slag as the cement-base composite material of admixture, and this is combined
The slag that material is used is cheap, and the slag gelation activity after processing is big, and wearability is good, and the obtained strength of materials is big, mechanics
Performance is good.
To achieve the above object, the present invention uses following technical scheme：
It is a kind of using slag as the preparation method of the cement-base composite material of admixture, comprise the following steps：
(1) calcium salt or sodium salt, polyhydric alcohol amine hydrochloride and water are mixed into solid dissolving, obtains solution A；By binary
After alcoholic compound, organic alcohol amine compound are mixed evenly, glacial acetic acid is added, obtained solution B is mixed；By solution A and
Solution B, which is mixed, is made mixed liquor, and is added to slag in ball mill, ball milling 1-2h, and ball milling is dried after terminating, system
Slag micro powder must be pre-processed；
(2) montmorillonite, Cetyltrimethylammonium bromide and hexamethylene are added in three-necked flask and are mixed evenly,
50-80 DEG C is warming up to, then constant temperature stirring 20-40min adds carboxylic carbon nano-tube, be warming up to 100 DEG C, flow back 2-4h, knot
Room temperature is cooled to after beam, is filtered, dries, obtains CNT intercalated montmorillonite material；
(3) by CNT intercalated montmorillonite made from cement, the obtained pretreatment slag micro powder of step (1), step (2)
Material, flyash, wollastonite in powder, gypsum, natural river sand are mixed evenly, and obtain mixed material；By water reducer, defoamer,
Swelling agent, dispersant and deionized water are mixed evenly, and add it in said mixture material, are made after being well mixed
Cement base mixed slurry,
(4) finally cement base mixed slurry obtained above is added in mould, vacuumizes blebbing, jolt ramming shaping, 24
Fog room is put into after the hour demoulding to conserve 15-30 days, and cement-base composite material is made.
As the preferred of above-mentioned technical proposal, in step (1), calcium salt or sodium salt, polyhydric alcohol amine hydrochloride, binary alcohol compound
Thing, organic alcohol amine compound, glacial acetic acid, water consumption in parts by weight, be specially：Calcium salt or 10-20 parts of sodium salt, polyhydric alcohol amine
2-10 parts of hydrochloride, 5-20 parts of diatomic alcohol compounds, 3-10 parts of organic alcohol amine compound, 0.1-2 parts of glacial acetic acid, 45-60 parts of water.
As the preferred of above-mentioned technical proposal, in step (1), the calcium salt is one kind in calcium acetate, calcium formate；It is described
Sodium salt is one kind in sodium acetate, sodium formate, sodium thiosulfate.
As the preferred of above-mentioned technical proposal, in step (1), the diatomic alcohol compounds are triethylene glycol, Isosorbide-5-Nitrae-fourth two
One or more mixing in alcohol, neopentyl glycol.
As the preferred of above-mentioned technical proposal, in step (1), the polyhydric alcohol amine hydrochloride be triethanolamine hydrochloride and
One or both of triisopropanolamine hydrochloride is mixed.
As the preferred of above-mentioned technical proposal, in step (1), the organic alcohol amine compound is diethylenetriamine, amino
One or more in ehtylethanolamine, N methyldiethanol amine, an ethanol diisopropanolamine.
As the preferred of above-mentioned technical proposal, in step (1), during ball milling, the mass ratio of slag and mixed liquor is 100：
(0.05-0.13)。
As the preferred of above-mentioned technical proposal, in step (2), montmorillonite, Cetyltrimethylammonium bromide, hexamethylene,
The mass ratio of carboxylic carbon nano-tube is 5：(0.3-0.7)：(10-20)：(1-2).
As the preferred of above-mentioned technical proposal, in step (3), the consumption of each component in parts by weight, respectively cement 30-
50 parts, pretreatment 10-20 parts of slag micro powder, 8-12 parts of CNT intercalated montmorillonite material, 28-35 parts of flyash, wollastonite
5-10 parts of powder, 10-20 parts of gypsum, 15-30 parts of natural river sand, 1-5 parts of water reducer, 0.8-1.5 parts of defoamer, 1-3 parts of swelling agent,
0.5-1 parts of dispersant, 5-15 parts of deionized water.
As the preferred of above-mentioned technical proposal, the defoamer is organic silicon defoamer.
As the preferred of above-mentioned technical proposal, the dispersant be lauryl sodium sulfate, neopelex,
One kind in span80, Sodium Polyacrylate, Tween 80.
The invention has the advantages that：
The present invention, as admixture, is not only solved at harm of the industrial residue to environment, and the present invention using slag
Slag gelation activity after reason is big, wearability is good；
The present invention handles montmorillonite, at a certain temperature, octadecyl three using Cetyltrimethylammonium bromide first
Intercalation synthesis between the meeting of methyl bromide ammonium and cheating engaging layer, and the CNT of carboxylated can be with Cetyltrimethylammonium bromide
The group bonding not being bonded so that CNT intercalation and the interlayer of montmorillonite, also effectively prevent the group between CNT
It is poly-；Cement-base composite material intensity produced by the present invention is big, and mechanical property is good, and it is low to prepare cost.
Embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for this
Invention, will not constitute any restriction to the present invention.
Embodiment 1
It is a kind of using slag as the preparation method of the cement-base composite material of admixture, comprise the following steps：
(1) in parts by weight, 10 parts of calcium acetates, 3 parts of diethylenetriamines and water are mixed into solid dissolving, obtains molten
Liquid A；After 5 parts of triethylene glycols, 2 parts of triethanolamine hydrochlorides are mixed evenly, 0.1 part of glacial acetic acid is added, system is mixed
Obtain solution B；Solution A and solution B are mixed mixed liquor are made, and be added to slag in ball mill, ball milling 1-2h,
Ball milling is dried after terminating, and pretreatment slag micro powder is made；Wherein, during ball milling, the mass ratio of slag and mixed liquor is 100：0.05
(2) montmorillonite, Cetyltrimethylammonium bromide and hexamethylene are added in three-necked flask and are mixed evenly,
50 DEG C are warming up to, then constant temperature stirring 20min adds carboxylic carbon nano-tube, be warming up to 100 DEG C, flow back 2h, is cooled down after terminating
To room temperature, filter, dry, obtain CNT intercalated montmorillonite material；Wherein, montmorillonite, Cetyltrimethylammonium bromide,
Hexamethylene, the mass ratio of carboxylic carbon nano-tube are 5：0.3：10：1；
(3) in parts by weight, 30 parts of cement, the obtained pretreatment slag micro powder of 10 parts of steps (1), 8 parts of steps (2) are made
CNT intercalated montmorillonite material, 28 parts of flyash, 5 parts of wollastonites in powder, 10 parts of gypsum, the 15 parts of natural river sands obtained are mixed and stirred
Mix uniform, obtain mixed material；By 1 part of water reducer, 0.8 part of defoamer, 1 part of swelling agent, 0.5 part of dispersant and 5 parts of deionizations
Water is mixed evenly, and adds it in said mixture material, and cement base mixed slurry is made after being well mixed,
(4) finally cement base mixed slurry obtained above is added in mould, vacuumizes blebbing, jolt ramming shaping, 24
Fog room is put into after the hour demoulding to conserve 15-30 days, and cement-base composite material is made.
Embodiment 2
It is a kind of using slag as the preparation method of the cement-base composite material of admixture, comprise the following steps：
(1) in parts by weight, 20 parts of calcium formates, 10 parts of diethylenetriamines and water are mixed into solid dissolving, obtained
Solution A；After 20 parts of BDOs, 10 parts of triisopropanolamine hydrochlorides are mixed evenly, 2 parts of glacial acetic acid, mixing are added
Stir obtained solution B；Solution A and solution B are mixed mixed liquor is made, and be added to slag in ball mill, ball
2h is ground, ball milling is dried after terminating, and pretreatment slag micro powder is made；Wherein, during ball milling, the mass ratio of slag and mixed liquor is 100：
0.13
(2) montmorillonite, Cetyltrimethylammonium bromide and hexamethylene are added in three-necked flask and are mixed evenly,
80 DEG C are warming up to, then constant temperature stirring 40min adds carboxylic carbon nano-tube, be warming up to 100 DEG C, flow back 4h, is cooled down after terminating
To room temperature, filter, dry, obtain CNT intercalated montmorillonite material；Wherein, montmorillonite, Cetyltrimethylammonium bromide,
Hexamethylene, the mass ratio of carboxylic carbon nano-tube are 5：0.7：20：2；
(3) in parts by weight, by 50 parts of cement, the obtained pretreatment slag micro powder of 20 parts of steps (1), 12 parts of steps (2)
Obtained CNT intercalated montmorillonite material, 35 parts of flyash, 10 parts of wollastonites in powder, 20 parts of gypsum, 30 parts of natural river sands are mixed
Conjunction stirs, and obtains mixed material；By 5 parts of water reducers, 1.5 parts of defoamers, 3 parts of swelling agents, 1 part of dispersant and 15 parts go from
Sub- water is mixed evenly, and adds it in said mixture material, and cement base mixed slurry is made after being well mixed,
(4) finally cement base mixed slurry obtained above is added in mould, vacuumizes blebbing, jolt ramming shaping, 24
Fog room is put into after the hour demoulding to conserve 15-30 days, and cement-base composite material is made.
Embodiment 3
It is a kind of using slag as the preparation method of the cement-base composite material of admixture, comprise the following steps：
(1) in parts by weight, 15 parts of sodium acetates, 5 parts of N methyldiethanol amines and water are mixed into solid dissolving, obtained
To solution A；After 10 parts of neopentyl glycols, 3 parts of triethanolamine hydrochlorides are mixed evenly, 0.5 part of glacial acetic acid is added, mixing is stirred
Mixing obtains solution B；Solution A and solution B are mixed mixed liquor is made, and be added to slag in ball mill, ball milling
1.2h, ball milling is dried after terminating, and pretreatment slag micro powder is made；Wherein, during ball milling, the mass ratio of slag and mixed liquor is 100：
0.07
(2) montmorillonite, Cetyltrimethylammonium bromide and hexamethylene are added in three-necked flask and are mixed evenly,
60 DEG C are warming up to, then constant temperature stirring 25min adds carboxylic carbon nano-tube, be warming up to 100 DEG C, flow back 2.5h, terminates rear cold
But to room temperature, filter, dry, obtain CNT intercalated montmorillonite material；Wherein, montmorillonite, octadecyl trimethyl bromination
Ammonium, hexamethylene, the mass ratio of carboxylic carbon nano-tube are 5：0.4：12：1.2；
(3) in parts by weight, 35 parts of cement, the obtained pretreatment slag micro powder of 13 parts of steps (1), 9 parts of steps (2) are made
CNT intercalated montmorillonite material, 30 parts of flyash, 6 parts of wollastonites in powder, 12 parts of gypsum, the 15 parts of natural river sands obtained are mixed and stirred
Mix uniform, obtain mixed material；By 2 parts of water reducers, 1.0 parts of defoamers, 1.5 parts of swelling agents, 0.6 part of dispersant and 7 parts go from
Sub- water is mixed evenly, and adds it in said mixture material, and cement base mixed slurry is made after being well mixed,
(4) finally cement base mixed slurry obtained above is added in mould, vacuumizes blebbing, jolt ramming shaping, 24
Fog room is put into after the hour demoulding to conserve 15-30 days, and cement-base composite material is made.
Embodiment 4
It is a kind of using slag as the preparation method of the cement-base composite material of admixture, comprise the following steps：
(1) in parts by weight, that 14 parts of sodium formates, 7 part of 21 ethanol diisopropanolamine and water are mixed into solid is molten
Solution, obtains solution A；After 11 parts of triethylene glycols, 5 parts of triethanolamine hydrochlorides are mixed evenly, 1 part of glacial acetic acid is added, is mixed
Close stirring obtained solution B；Solution A and solution B are mixed mixed liquor are made, and be added to slag in ball mill,
Ball milling 1.4h, ball milling is dried after terminating, and pretreatment slag micro powder is made；Wherein, during ball milling, the mass ratio of slag and mixed liquor is
100：0.09
(2) montmorillonite, Cetyltrimethylammonium bromide and hexamethylene are added in three-necked flask and are mixed evenly,
70 DEG C are warming up to, then constant temperature stirring 30min adds carboxylic carbon nano-tube, be warming up to 100 DEG C, flow back 3h, is cooled down after terminating
To room temperature, filter, dry, obtain CNT intercalated montmorillonite material；Wherein, montmorillonite, Cetyltrimethylammonium bromide,
Hexamethylene, the mass ratio of carboxylic carbon nano-tube are 5：0.5：14：1.4；
(3) in parts by weight, by 40 parts of cement, the obtained pretreatment slag micro powder of 16 parts of steps (1), 10 parts of steps (2)
Obtained CNT intercalated montmorillonite material, 31 parts of flyash, 7 parts of wollastonites in powder, 14 parts of gypsum, 20 parts of natural river sand mixing
Stir, obtain mixed material；By 3 parts of water reducers, 1.1 parts of defoamers, 2 parts of swelling agents, 0.7 part of dispersant and 9 parts go from
Sub- water is mixed evenly, and adds it in said mixture material, and cement base mixed slurry is made after being well mixed,
(4) finally cement base mixed slurry obtained above is added in mould, vacuumizes blebbing, jolt ramming shaping, 24
Fog room is put into after the hour demoulding to conserve 15-30 days, and cement-base composite material is made.
Embodiment 5
It is a kind of using slag as the preparation method of the cement-base composite material of admixture, comprise the following steps：
(1) in parts by weight, 16 parts of second sodium thiosulfate, 9 parts of diethylenetriamines and water are mixed into solid dissolving,
Obtain solution A；17 parts of triethylene glycols, 1,4- butanediols, neopentyl glycol, 7 parts of triisopropanolamine hydrochlorides are mixed evenly
Afterwards, 1.5 parts of glacial acetic acid are added, obtained solution B is mixed；Solution A and solution B are mixed mixed liquor is made, and with steel
Slag is added in ball mill together, ball milling 1.8h, and ball milling is dried after terminating, and pretreatment slag micro powder is made；Wherein, during ball milling,
The mass ratio of slag and mixed liquor is 100：0.11；
(2) montmorillonite, Cetyltrimethylammonium bromide and hexamethylene are added in three-necked flask and are mixed evenly,
75 DEG C are warming up to, then constant temperature stirring 30min adds carboxylic carbon nano-tube, be warming up to 100 DEG C, flow back 3.5h, terminates rear cold
But to room temperature, filter, dry, obtain CNT intercalated montmorillonite material；Wherein, montmorillonite, octadecyl trimethyl bromination
Ammonium, hexamethylene, the mass ratio of carboxylic carbon nano-tube are 5：0.6：16：1.6；
(3) in parts by weight, by 45 parts of cement, the obtained pretreatment slag micro powder of 18 parts of steps (1), 11 parts of steps (2)
Obtained CNT intercalated montmorillonite material, 33 parts of flyash, 8 parts of wollastonites in powder, 16 parts of gypsum, 25 parts of natural river sand mixing
Stir, obtain mixed material；4 parts of water reducers, 1.3 parts of defoamers, 2.5 parts of swelling agents, 0.8 part of dispersant and 12 parts are gone
Ionized water is mixed evenly, and adds it in said mixture material, and cement base mixed slurry is made after being well mixed,
(4) finally cement base mixed slurry obtained above is added in mould, vacuumizes blebbing, jolt ramming shaping, 24
Fog room is put into after the hour demoulding to conserve 15-30 days, and cement-base composite material is made.
Comparative example 1
Mixed liquor replaces with ethanol in mechanical milling process during pretreatment of slag, and other conditions and embodiment 5 are identical.
Comparative example 2
Using common grinding aid (consisting of 15wt% triethanolamines, 10wt% glycerine, 5wt% during pretreatment of slag
Molasses, 16wt% sodium chloride and 54wt% water), other preparation conditions and embodiment 5 are identical.
After testing, cement-base composite material made from embodiment 1-5, the shrinkage value after 30 days is 100-150 microstrains, and
Shrinkage value of the material of comparative example 1 after 30 days is 1100 microstrains, the shrinkage value of the material of comparative example 2 after 30 days for 700 it is micro- should
Become, illustrate, the low drying shrinkage of cement-based material produced by the present invention is more preferable.
In addition, compression strength of the composite produced by the present invention after 30 days is 65-70MPa, and comparative example 1,2 materials
Compression strength is only 13MPa, 25MPa.
Claims (10)
1. a kind of preparation method using slag as the cement-base composite material of admixture, it is characterised in that comprise the following steps：
(1) calcium salt or sodium salt, polyhydric alcohol amine hydrochloride and water are mixed into solid dissolving, obtains solution A；Binary is refined
After compound, organic alcohol amine compound are mixed evenly, glacial acetic acid is added, obtained solution B is mixed；By solution A and solution B
Mix and mixed liquor is made, and be added to slag in ball mill, ball milling 1-2h, ball milling is dried after terminating, be made pre-
Handle slag micro powder；
(2) montmorillonite, Cetyltrimethylammonium bromide and hexamethylene are added in three-necked flask and are mixed evenly, heated up
To 50-80 DEG C, then constant temperature stirring 20-40min adds carboxylic carbon nano-tube, is warming up to 100 DEG C, flow back 2-4h, after terminating
Room temperature is cooled to, is filtered, dries, obtains CNT intercalated montmorillonite material；
(3) by CNT intercalated montmorillonite material made from cement, the obtained pretreatment slag micro powder of step (1), step (2)
Material, flyash, wollastonite in powder, gypsum, natural river sand are mixed evenly, and obtain mixed material；By water reducer, defoamer, swollen
Swollen dose, dispersant and deionized water are mixed evenly, and add it in said mixture material, and water is made after being well mixed
Mud base mixed slurry,
(4) finally cement base mixed slurry obtained above is added in mould, vacuumizes blebbing, jolt ramming shaping, 24 hours
Fog room is put into after the demoulding to conserve 15-30 days, and cement-base composite material is made.
2. a kind of preparation method using slag as the cement-base composite material of admixture as claimed in claim 1, its feature exists
In：In step (1), calcium salt or sodium salt, polyhydric alcohol amine hydrochloride, diatomic alcohol compounds, organic alcohol amine compound, glacial acetic acid, water
Consumption in parts by weight, be specially：Calcium salt or 10-20 parts of sodium salt, 2-10 parts of polyhydric alcohol amine hydrochloride, diatomic alcohol compounds 5-
20 parts, 3-10 parts of organic alcohol amine compound, 0.1-2 parts of glacial acetic acid, 45-60 parts of water.
3. a kind of preparation method using slag as the cement-base composite material of admixture as claimed in claim 1, its feature exists
In：In step (1), the calcium salt is one kind in calcium acetate, calcium formate；The sodium salt is sodium acetate, sodium formate, thiosulfuric acid
One kind in sodium.
4. a kind of preparation method using slag as the cement-base composite material of admixture as claimed in claim 1, its feature exists
In：In step (1), the diatomic alcohol compounds are that the one or more in triethylene glycol, BDO, neopentyl glycol are mixed
Close.
5. a kind of preparation method using slag as the cement-base composite material of admixture as claimed in claim 1, its feature exists
In：In step (1), the organic alcohol amine compound is diethylene diamine, amino ethyl ethanolamine, N methyldiethanol amine, one
One or more in ethanol diisopropanolamine.
6. a kind of preparation method using slag as the cement-base composite material of admixture as claimed in claim 1, its feature exists
In：In step (1), during ball milling, the mass ratio of slag and mixed liquor is 100：(0.05-0.13).
7. a kind of preparation method using slag as the cement-base composite material of admixture as claimed in claim 1, its feature exists
In：In step (2), montmorillonite, Cetyltrimethylammonium bromide, hexamethylene, the mass ratio of carboxylic carbon nano-tube are 5：
(0.3-0.7)：(10-20)：(1-2).
8. a kind of preparation method using slag as the cement-base composite material of admixture as claimed in claim 1, its feature exists
In：In step (3), the consumption of each component in parts by weight, respectively cement 30-50 parts, pretreatment 10-20 parts of slag micro powder,
8-12 parts of CNT intercalated montmorillonite material, 28-35 parts of flyash, 5-10 parts of wollastonite in powder, 10-20 parts of gypsum, natural river
15-30 parts of sand, 1-5 parts of water reducer, 0.8-1.5 parts of defoamer, 1-3 parts of swelling agent, 0.5-1 parts of dispersant, deionized water 5-15
Part.
9. a kind of preparation method using slag as the cement-base composite material of admixture as claimed in claim 1, its feature exists
In：In step (1), the polyhydric alcohol amine hydrochloride is triethanolamine hydrochloride, one kind in triisopropanolamine hydrochloride or two
Plant mixing.
10. a kind of preparation method using slag as the cement-base composite material of admixture as claimed in claim 8, its feature exists
In：The dispersant is one in lauryl sodium sulfate, neopelex, span80, Sodium Polyacrylate, Tween 80
Kind.
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