CN115215580B - Modified nanofiber stable high-early-strength alkali-free accelerator and preparation method thereof - Google Patents
Modified nanofiber stable high-early-strength alkali-free accelerator and preparation method thereof Download PDFInfo
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- CN115215580B CN115215580B CN202210941553.1A CN202210941553A CN115215580B CN 115215580 B CN115215580 B CN 115215580B CN 202210941553 A CN202210941553 A CN 202210941553A CN 115215580 B CN115215580 B CN 115215580B
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- nanofiber
- alkali
- modified
- free accelerator
- stirring
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 238000000034 method Methods 0.000 claims abstract description 13
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- 238000003756 stirring Methods 0.000 claims description 82
- 238000006243 chemical reaction Methods 0.000 claims description 44
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 39
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- -1 alcohol amine Chemical class 0.000 claims description 13
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 9
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
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- 108010064470 polyaspartate Proteins 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
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- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
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- 239000000665 guar gum Substances 0.000 claims description 4
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- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- VWQXLMJSFGLQIT-UHFFFAOYSA-N prop-2-enoyl bromide Chemical compound BrC(=O)C=C VWQXLMJSFGLQIT-UHFFFAOYSA-N 0.000 claims description 4
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- CYMRPDYINXWJFU-UHFFFAOYSA-N 2-carbamoylbenzoic acid Chemical compound NC(=O)C1=CC=CC=C1C(O)=O CYMRPDYINXWJFU-UHFFFAOYSA-N 0.000 claims description 3
- SHDZTIZBSYDZSH-UHFFFAOYSA-N 2-methylprop-2-enoyl bromide Chemical compound CC(=C)C(Br)=O SHDZTIZBSYDZSH-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
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- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
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- 238000010041 electrostatic spinning Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 6
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- 238000006703 hydration reaction Methods 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
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- 238000010276 construction Methods 0.000 description 7
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- 239000004113 Sepiolite Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 229910052624 sepiolite Inorganic materials 0.000 description 5
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
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- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
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- 238000005507 spraying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XPULYJRIWWWQFM-UHFFFAOYSA-N CCO.NCCNCCN Chemical compound CCO.NCCNCCN XPULYJRIWWWQFM-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- HUFUZBQNAVESGX-UHFFFAOYSA-N prop-2-enoyl chloride;pyridine Chemical compound ClC(=O)C=C.C1=CC=NC=C1 HUFUZBQNAVESGX-UHFFFAOYSA-N 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
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- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 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 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
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- 210000002345 respiratory system Anatomy 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
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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
- 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
- C04B20/0048—Fibrous materials
- C04B20/006—Microfibres; Nanofibres
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
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Abstract
The invention discloses a modified nanofiber stable high-early-strength alkali-free accelerator and a preparation method thereof. The modified nanofiber stable high early strength alkali-free accelerator is prepared by the following steps: (1) preparation of modified nanofiber. And (2) preparing the alkali-free accelerator. According to the invention, the high-performance alkali-free accelerator with a high-stability high-early-strength structure is obtained by preparing the amino modified nanofiber as a suspension stabilizer, on one hand, the amino modified nanofiber can form a three-dimensional network structure to stabilize the whole suspension system through space lap joint, and on the other hand, aluminum phase complex ions can be adsorbed and fixed in the three-dimensional network structure through amine groups on the surface, so that the stability time of the suspension system is further improved. In addition, the nanofiber network structure can be rapidly oriented to reduce the viscosity of the system when stressed, can be rapidly overlapped to help the system to be stable when static, and simultaneously has good stability and working performance under the condition of higher concentration solid phase. In addition, the nanofiber can be distributed in a hardened body in the hydration process, so that the coagulation and hardening effects are effectively improved, the effects of high early strength development and later strength maintenance are achieved, the durability improvement of sprayed concrete is achieved, and the alkali-free accelerator has good use value for preparing high-performance sprayed concrete.
Description
Technical Field
The invention belongs to the field of concrete additive materials, and in particular relates to a modified nanofiber stable high-early-strength alkali-free accelerator and a preparation method thereof, and the product can be used for construction of high-performance sprayed concrete and sprayed mortar.
Background
Along with the development of engineering construction, the strength, durability, construction quality and the like of sprayed concrete are continuously improved, and the wet spraying process is gradually developed into a main stream spraying construction process adopted by tunnel engineering due to the advantages of quality and construction safety. The liquid accelerator is also used as an important raw material for the wet spraying process, and has been developed. The traditional alkali accelerator using sodium silicate and sodium aluminate as main accelerator components has strong stimulation to the skin and respiratory tract of constructors, and causes later strength loss and hidden durability hazards such as alkali aggregate reaction to sprayed concrete, etc., so the traditional alkali accelerator is gradually replaced by alkali-free liquid accelerator.
The main coagulation accelerating component in the existing alkali-free accelerator is an aluminum phase material, wherein aluminum sulfate is used as the main component, but the solubility of the aluminum sulfate is only 36.5g at 20 ℃, so that the use requirement of liquid alkali-free accelerator is difficult to meet, and fluorine-containing molecules such as hydrofluoric acid or magnesium fluosilicate and the like are commonly used at present to complex aluminum ions to form soluble components such as hexafluoroaluminate and the like so as to increase the aluminum phase content in the alkali-free accelerator, so that the alkali-free accelerator meets the field use requirement. However, the use of fluorine-containing raw materials, especially hydrofluoric acid, brings greater personnel health risks to alkali-free accelerators during synthesis and use, and because of the formation of polyfluoro complexes, although accelerating the setting process of cement, the early hydration process of cement is greatly affected, so that the early strength development of sprayed concrete is slow, and risks are brought to the early structural safety of tunnel lining support structures and the like. Therefore, the fluorine ion content of the alkali-free accelerator is strictly limited in the technical standard of the iron group of the China, namely, the tunnel shotcrete liquid alkali-free accelerator. Therefore, how to prepare the fluorine-free chlorine-free alkali-free liquid accelerator with high-concentration aluminum phase so as to comprehensively improve the mechanical and durability properties of sprayed concrete is a development hot spot of the existing alkali-free accelerator products.
Because of the insufficient solubility of aluminum sulfate, the suspension type high aluminum phase fluorine-free alkali-free accelerator is developed gradually, and the alkali-free accelerator is safe, environment-friendly and corrosion-free, can ensure that the sprayed concrete has good durability, high mechanical strength and reduced spraying resilience, and is a main development direction in the future. Patent CN110963736a discloses a nano gel polymeric aluminum liquid alkali-free accelerator, which utilizes the double hydrolysis effect of aluminum carbonate to realize the formation of polymeric aluminum sulfate, maintains high aluminum ion concentration in the system, and utilizes nano hydrated calcium silicate gel to rapidly promote the hydration of tricalcium silicate, thereby harmlessly improving the early strength of cement. Patent CN111018392B discloses a method for synthesizing a fluorine-free alkali-free accelerator at normal temperature, which is characterized in that 3-aminopropyl triethoxysilane and disodium sulfosuccinate are mixed to be used as a dispersing agent, and an acrylic polymer is used as a stable coagulant to prepare the fluorine-free alkali-free accelerator, so that the fluorine-free alkali-free accelerator has a good effect.
Patent CN109761532a discloses a low-rebound high-early-strength alkali-free accelerator, which is prepared stably by using talcum powder or montmorillonite powder as a suspending agent, and has higher early strength. Patent CN114409306a discloses a fluorine-free high early strength liquid alkali-free accelerator using sepiolite, magnesium aluminum silicate by using anionic polymer as complexation activator. Bentonite and the like are used as a stable suspending agent to prepare the alkali-free accelerator, and the alkali-free accelerator has the characteristics of low mixing amount and high strength.
Because the suspension system is a thermodynamically unstable system, the stability of the suspension type fluorine-free alkali-free accelerator prepared by the prior art is generally difficult to maintain for a long time, the problems of layering, crystallization or gelation are relatively easy to occur, and the suspension type fluorine-free alkali-free accelerator is generally accompanied with the problems of increased cost, overlarge viscosity and unstable effect, so that the suspension type fluorine-free alkali-free accelerator has difficulty in large-scale application. Therefore, the fluorine-free alkali-free liquid accelerator with better stability and rheological property is researched, and meanwhile, the high early strength of sprayed concrete and the high later strength and the high durability can be kept, so that the fluorine-free alkali-free liquid accelerator has important significance for the whole industry.
Disclosure of Invention
The invention aims to solve the problems and provide a modified nanofiber stable high early strength alkali-free accelerator and a preparation method thereof.
The invention relates to a modified nanofiber stable high early strength alkali-free accelerator which is prepared from the following components in parts by mass:
50 to 65 percent of aluminum sulfate,
5-15% of pseudo-boehmite,
alcohol amine 3-8%,
0.5 to 2.5 percent of modified nano fiber,
0.5 to 1 percent of organic acid,
0.1 to 0.5 percent of stabilizer,
0.05 to 0.1 percent of rheology modifier,
the rest is water;
the sum of the mass percentages of the components is 100 percent.
The modified nanofiber is obtained by modifying the surface of the nanofiber by using a polyamine reagent; the diameter of the modified nanofiber is in the range of 30nm-150nm, and the length-diameter ratio is in the range of 3-30.
The nanofiber in the alkali-free accelerator is at least one of cellulose nanocrystals, cellulose nanofibrils, bacterial cellulose, electrostatic spinning cellulose nanofibrils, polyamide nanofibers, polylactic acid nanofibers, polyvinylpyrrolidone nanofibers, polyethylene terephthalate nanofibers and nanoglass fibers; the polyamine reagent is at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethylene polyamine.
The alcohol amine in the alkali-free accelerator is at least one of diethanolamine, triethanolamine and triisopropanolamine; the organic acid is at least one of oxalic acid, tartaric acid, malic acid, citric acid, ascorbic acid, salicylic acid, lactic acid, polyaspartic acid and ethylenediamine tetraacetic acid.
The stabilizer in the alkali-free accelerator is at least one of polyacrylamide, cinnamamide, polycarboxylic acid, di (hydrogenated tallow) phthalic acid amide and modified acrylic acid polymer; the rheology modifier is at least one of xanthan gum, guar gum, temperature roller gum, polyethylene glycol and cellulose ether.
The preparation method of the modified nanofiber stable high early strength alkali-free accelerator specifically comprises the following steps:
(1) Preparation of modified nanofibers: and (3) washing and drying the nanofiber, oxidizing the nanofiber in an ozone oxidation machine for 15min, putting the oxidized nanofiber into a solution dissolved with an acrylation reagent for reaction, putting the acrylation nanofiber into the solution dissolved with a polyamine reagent for reaction, and filtering and washing after the reaction to obtain the modified nanofiber.
(2) Preparing an alkali-free accelerator: adding the modified nanofiber, the organic acid and the rheology modifier into water, and stirring at a high speed for 5min to form a uniform suspension; slowly adding 50% of aluminum sulfate and pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 50% of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding alcohol amine and a stabilizer into the system, keeping stirring at a high speed for 1h, and further stirring the reaction solution at a low speed for 1.5-3h to obtain the modified nanofiber stable high early strength alkali-free accelerator.
The method comprises the steps that (1) in the preparation of the modified fiber, an acrylating reagent is at least one of acryloyl chloride, acryloyl bromide, acrylic anhydride, methacryloyl chloride, methacryloyl bromide and methacrylic anhydride, and the concentration of the acrylating reagent is 5-30%; the reaction solvent is at least one of pyridine, N-dimethylformamide and dimethyl sulfoxide; the concentration of polyamine reagent is 10-20%, and the reaction solvent is at least one of ethanol, acetone, isopropanol, acetonitrile and tetrahydrofuran.
The high-speed stirring linear speed in the preparation of the alkali-free accelerator in the step (2) of the preparation method is more than 10m/s, and the low-speed stirring linear speed is between 0.5 and 2 m/s.
The modified nanofiber stable high-early-strength alkali-free accelerator and the preparation method thereof have the positive effects that:
compared with the existing alkali-free accelerator, the fluorine-free alkali-free liquid accelerator prepared by the method has better stability and lower viscosity, can ensure that sprayed concrete has higher early strength and higher later strength retention rate, and can effectively ensure the durability of the sprayed concrete. Firstly, organic acid with complexing capability is used as a complexing solubilizer to perform compatibilization on aluminum phase ions, and nano fibers with the surfaces modified by polyamine groups are used as a suspension stabilizer, so that on one hand, a three-dimensional nano network structure is formed through mutual lap joint among the nano fibers, compared with a suspension system of layered clay, the suspension system is more stable, and meanwhile, amine groups on the surfaces of the fibers can react with the aluminum phase ions formed by complexing to fix the aluminum phase ions in grids formed by the nano fibers, so that sedimentation and crystallization caused by excessive dissolution and suspension can be effectively prevented, and the alkali-free accelerator has stronger stability.
Meanwhile, the orientation convergence conversion of the nanofibers can be realized when the nanofibers are stressed, the shearing viscosity of the accelerator can be effectively reduced, and the nanofibers can be quickly overlapped with each other to form a network stable structure when the nanofibers are not stressed, so that the static stability of the accelerator is ensured, and the alkali-free accelerator has better working and use performances. Meanwhile, for sprayed concrete using the alkali-free accelerator, the amino modified nano fibers can effectively promote hydration of cement particles to play a role in accelerating early strength, and the nano fibers distributed in the concrete can play a role in toughening and cracking resistance, so that the toughness and durability of the sprayed concrete are effectively improved.
The modified nanofiber stable high-early-strength alkali-free accelerator provided by the invention has clear action mechanism, simple production process and excellent performance, is suitable for large-scale production, and has important significance for preparing high-performance sprayed concrete.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1: a modified nanofiber stable high early strength alkali-free accelerator is prepared by the following steps of
(1) Preparing modified nano fiber A: washing and drying 25g of cellulose nanocrystals, oxidizing in an ozone oxidation machine for 15min, putting the oxidized cellulose nanocrystals into 20% concentration acryloyl chloride pyridine solution for reaction for 3h, putting the intermediate product into 15% diethylenetriamine ethanol solution for reaction for 2h, and filtering and washing after the reaction to obtain modified nanofiber A;
(2) Preparing an alkali-free accelerator: 12g of modified nanofiber A, 6g of oxalic acid and 0.6g of xanthan gum are added into 319.4g of water, and the mixture is stirred at a high speed for 5min to form a uniform suspension; slowly adding 260g of aluminum sulfate and 100g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 260g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 40g of diethanolamine and 2g of polyacrylamide into the system, keeping stirring at a high speed for 1h, and stirring at a low speed for 1.5-3h, thereby obtaining the modified nanofiber stable high early strength alkali-free accelerator.
Example 2: a modified nanofiber stable high early strength alkali-free accelerator is prepared by the following steps of
(1) Preparing modified nano fiber B: washing and drying 25g of bacterial cellulose, oxidizing in an ozone oxidation machine for 15min, putting the oxidized bacterial cellulose into an N, N-dimethylformamide solution of 20% concentration of acryloyl bromide for reaction for 3h, putting an intermediate product into an acetone solution of 15% triethylene tetramine for reaction for 2h, and filtering and cleaning after the reaction to obtain modified nanofiber B;
(2) Preparing an alkali-free accelerator: adding 6g of modified nanofiber B, 6g of malic acid and 0.8g of temperature-sensitive glue into 325.7g of water, and stirring at a high speed for 5min to form a uniform suspension; slowly adding 250g of aluminum sulfate and 130g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 250g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 30g of triethanolamine and 1.5g of polycarboxylic acid into the system, keeping stirring at a high speed for 1h, and stirring the reaction solution after high-speed stirring at a low speed for 1.5-3h, thus obtaining the modified nanofiber stable high-early-strength alkali-free accelerator.
Example 3: a modified nanofiber stable high early strength alkali-free accelerator is prepared by the following steps of
(1) Preparing modified nanofiber C: washing and drying 25g of polylactic acid nanofiber, oxidizing in an ozone oxidation machine for 15min, putting the oxidized polylactic acid nanofiber into a dimethyl sulfoxide solution of methacrylic anhydride with the concentration of 20% for reaction for 3h, putting an intermediate product into an acetonitrile solution of tetraethylenepentamine for reaction for 2h, and filtering and cleaning after the reaction to obtain a modified nanofiber C:
(2) Preparing an alkali-free accelerator: 15g of modified nanofiber C, 8g of tartaric acid and 0.6g of guar gum are added into 259.4g of water, and the mixture is stirred at a high speed for 5min to form a uniform suspension; slowly adding 275g of aluminum sulfate and 120g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 275g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 45g of triisopropanolamine and 2g of cinnamamide into the system, keeping stirring at a high speed for 1h, and stirring at a low speed for 1.5-3h again to obtain the modified nanofiber stable high early strength alkali-free accelerator.
Example 4: a modified nanofiber stable high early strength alkali-free accelerator is prepared by the following steps of
(1) Preparing modified nano fiber D: washing and drying 25g of polyvinylpyrrolidone nanofiber, oxidizing in an ozone oxidation machine for 15min, putting the oxidized polyvinylpyrrolidone nanofiber into a dimethyl sulfoxide solution of 20% concentration acrylic anhydride for reaction for 3h, putting an intermediate product into a tetrahydrofuran solution of 15% ethylenediamine for reaction for 2h, and filtering and washing after the reaction to obtain a modified nanofiber D;
(2) Preparing an alkali-free accelerator: 20g of modified nanofiber D, 9g of lactic acid and 0.7g of cellulose ether are added into 287.3g of water, and the mixture is stirred at a high speed for 5min to form a uniform suspension; slowly adding 275g of aluminum sulfate and 80g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 275g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 50g of triisopropanolamine and 3g of di (hydrogenated tallow) phthalic acid amide into the system, keeping stirring at a high speed for 1h, and stirring the reaction solution after high-speed stirring at a low speed for 1.5-3h, thereby obtaining the modified nanofiber stable high-early-strength alkali-free accelerator.
Example 5: a modified nanofiber stable high early strength alkali-free accelerator is prepared by the following steps of
(1) Preparing modified nano fiber E: washing and drying 25g of nano glass fiber, oxidizing in an ozone oxidation machine for 15min, putting the oxidized nano glass fiber into an N, N-dimethylformamide solution of 20% concentration of acryloyl chloride for reaction for 3h, putting an intermediate product into a 15% polyethylene polyamine acetone solution for reaction for 2h, and filtering and cleaning after the reaction to obtain modified nano fiber E;
(2) Preparing an alkali-free accelerator: 23g of modified nanofiber E, 10g of polyaspartic acid and 0.9g of xanthan gum are added into 242.6g of water, and the mixture is stirred at a high speed for 5min to form a uniform suspension; slowly adding 300g of aluminum sulfate and 50g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 300g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 70g of diethanolamine and 3.5g of modified acrylic polymer into the system, keeping stirring at a high speed for 1h, and stirring at a low speed for 1.5-3h to obtain the modified nanofiber stable high-early-strength alkali-free accelerator.
Example 6: a modified nanofiber stable high early strength alkali-free accelerator is prepared by the following steps of
(1) Preparing modified nanofiber F: washing and drying 25g of cellulose nanofibrils, oxidizing the cellulose nanofibrils in an ozone oxidation machine for 15min, putting the oxidized cellulose nanofibrils in a pyridine solution of 20% concentration of methacryloyl bromide for reaction for 3h, putting an intermediate product in an ethanol solution of 15% diethylenetriamine for reaction for 2h, and filtering and cleaning after the reaction to obtain modified nanofibrils F;
(2) Preparing an alkali-free accelerator: 18g of modified nanofiber F, 7g of oxalic acid and 1g of polyethylene glycol 2000 are added into 286.5g of water, and the mixture is stirred at a high speed for 5min to form a uniform suspension; slowly adding 290g of aluminum sulfate and 50g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 290g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 55g of triethanolamine and 2.5g of cinnamamide into the system, keeping stirring at a high speed for 1h, and stirring at a low speed for 1.5-3h again to obtain the modified nanofiber stable high early strength alkali-free accelerator.
Example 7: a modified nanofiber stable high early strength alkali-free accelerator is prepared by the following steps of
(1) Preparation of modified nanofibers G: washing and drying 25G of polyamide nanofiber, oxidizing in an ozone oxidation machine for 15min, putting the oxidized polyamide nanofiber into a dimethyl sulfoxide solution of 20% of acryloyl bromide for reaction for 3h, putting an intermediate product into a tetrahydrofuran solution of 15% of tetraethylenepentamine for reaction for 2h, and filtering and cleaning after the reaction to obtain modified nanofiber G;
(2) Preparing an alkali-free accelerator: 10G of modified nanofiber G, 8G of citric acid and 0.5G of temperature roller glue are added into 319.4G of water, and the mixture is stirred at a high speed for 5min to form a uniform suspension; slowly adding 260g of aluminum sulfate and 100g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 260g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 65g of triethanolamine and 4.5g of polycarboxylic acid into the system, keeping stirring at a high speed for 1h, and stirring at a low speed for 1.5-3h again to obtain the modified nanofiber stable high early strength alkali-free accelerator.
Example 8: a modified nanofiber stable high early strength alkali-free accelerator is prepared by the following steps of
(1) Preparing modified nanofiber H: washing and drying 25g of polyethylene glycol terephthalate nanofiber, oxidizing in an ozone oxidation machine for 15min, putting the oxidized polyethylene glycol terephthalate nanofiber into an N, N-dimethylformamide solution of 20% concentration acrylic anhydride for reaction for 3H, putting an intermediate product into an isopropanol solution of 15% triethylene tetramine for reaction for 2H, and filtering and cleaning after the reaction to obtain a modified nanofiber H;
(2) Preparing an alkali-free accelerator: 15g of modified nanofiber H, 7g of oxalic acid and 0.7g of guar gum are added into 289.3g of water, and the mixture is stirred at a high speed for 5min to form a uniform suspension; slowly adding 240g of aluminum sulfate and 150g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 240g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 55g of diethanolamine and 3g of polyacrylamide into the system, keeping stirring at a high speed for 1h, and stirring at a low speed for 1.5-3h again to obtain the modified nanofiber stable high early strength alkali-free accelerator.
Comparative example 1: conventional stabilizer alkali-free accelerator
18g of sepiolite, 7g of oxalic acid and 1g of polyethylene glycol 2000 are added into 286.5g of water and stirred at a high speed for 5min to form a uniform suspension; 290g of aluminum sulfate and 50g of pseudo-boehmite are slowly added into the suspension to be stirred at a high speed for 0.5h, the rest 290g of aluminum sulfate is slowly added into the suspension while being stirred, the high speed is kept for 1.5h, and finally 55g of triethanolamine and 2.5g of cinnamamide are added into the system to be stirred at a high speed for 1h, and the reaction solution after high speed stirring is stirred at a low speed for 1.5-3h, so that the conventional stabilizer alkali-free accelerator can be obtained.
Comparative example 2: unmodified nanofiber stable alkali-free accelerator
18g of unmodified cellulose nanofibrils, 7g of oxalic acid and 1g of polyethylene glycol 2000 are added into 286.5g of water, and the mixture is stirred at a high speed for 5min to form a uniform suspension; slowly adding 290g of aluminum sulfate and 50g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 290g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 55g of triethanolamine and 2.5g of cinnamamide into the system, keeping stirring at a high speed for 1h, and stirring the reaction solution after high-speed stirring at a low speed for 1.5-3h, thus obtaining the unmodified nanofiber stable alkali-free accelerator.
Comparative example 3: modified nanofiber stable alkali-free accelerator
(1) Preparing modified nano fiber E: as above;
(2) Preparing an alkali-free accelerator: adding 40g of modified nanofiber E, 10g of polyaspartic acid and 0.9g of xanthan gum into 225.6g of water, and stirring at a high speed for 5min to form a uniform suspension; slowly adding 300g of aluminum sulfate and 50g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 300g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 70g of diethanolamine and 3.5g of modified acrylic polymer into the system, keeping stirring at a high speed for 1h, and stirring at a low speed for 1.5-3h to obtain the modified nanofiber stable alkali-free accelerator.
Comparative example 4: modified nanofiber stable alkali-free accelerator
(1) Preparing modified nano fiber E: as above;
(2) Preparing an alkali-free accelerator: adding 2g of modified nanofiber E, 10g of polyaspartic acid and 0.9g of xanthan gum into 263.6g of water, and stirring at a high speed for 5min to form a uniform suspension; slowly adding 300g of aluminum sulfate and 50g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 300g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 70g of diethanolamine and 3.5g of modified acrylic polymer into the system, keeping stirring at a high speed for 1h, and stirring at a low speed for 1.5-3h to obtain the modified nanofiber stable alkali-free accelerator.
Comparative example 5: modified nanofiber stable alkali-free accelerator
(1) Preparation of modified nanofibers I: washing and drying 25g of cellulose nanocrystals with the diameter of 400-600nm and the length-diameter ratio of 50-80, oxidizing in an ozone oxidation machine for 15min, putting the oxidized cellulose nanocrystals into 20% concentration acryloyl chloride pyridine solution for reaction for 3h, putting an intermediate product into 15% diethylenetriamine ethanol solution for reaction for 2h, and filtering and washing after the reaction to obtain modified nanofiber I;
(2) Preparing an alkali-free accelerator: 12g of modified nanofiber I, 6g of oxalic acid and 0.6g of xanthan gum are added into 319.4g of water, and the mixture is stirred at a high speed for 5min to form a uniform suspension; slowly adding 260g of aluminum sulfate and 100g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 260g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 40g of diethanolamine and 2g of polyacrylamide into the system, keeping stirring at a high speed for 1h, and stirring at a low speed for 1.5-3h to obtain the modified nanofiber stable alkali-free accelerator.
Comparative example 6: modified nanofiber stable alkali-free accelerator
(1) Preparing modified nanofiber J: washing and drying 25g of cellulose nanocrystals with the diameter of 10-20nm and the length-diameter ratio of 20-60, oxidizing in an ozone oxidation machine for 15min, putting the oxidized cellulose nanocrystals into 20% concentration acryloyl chloride pyridine solution for reaction for 3h, putting an intermediate product into 15% diethylenetriamine ethanol solution for reaction for 2h, and filtering and washing after the reaction to obtain modified nanofiber I;
(2) Preparing an alkali-free accelerator: 12g of modified nanofiber J, 6g of oxalic acid and 0.6g of xanthan gum are added into 319.4g of water, and the mixture is stirred at a high speed for 5min to form a uniform suspension; slowly adding 260g of aluminum sulfate and 100g of pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 260g of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, finally adding 40g of diethanolamine and 2g of polyacrylamide into the system, keeping stirring at a high speed for 1h, and stirring at a low speed for 1.5-3h to obtain the modified nanofiber stable alkali-free accelerator.
Description of effects:
the modified nanofiber stable high early strength alkali-free accelerator prepared in examples 1 to 8 of the invention and the alkali-free accelerator prepared in comparative examples 1 to 6 were used for performance test according to GB/T35159-2017 accelerator for shotcrete and QCR 807-2020 liquid alkali-free accelerator for tunnel shotcrete.
Wherein the viscosity and yield stress of the accelerator are obtained by testing through a rheometer
First, the physical and chemical properties of the alkali-free accelerator are set forth in table 1:
table 1 results of physical and chemical properties test of alkali-free accelerator.
As can be seen from the data in Table 1, the prepared accelerator meets the requirements of no fluorine and no alkali, has uniform pH value and presents certain acidity due to hydrolysis of high content of aluminum sulfate in water. From the results of the yield stress and the plastic viscosity, the yield stress of examples 1-8 is kept within a certain range, the plastic viscosity is also in the range of 300-450cps, and although the alkali accelerator and the fluorine-containing alkali-free accelerator are larger, the construction operation requirements of sprayed concrete can be met, while the use of sepiolite in comparative example 1 can lead to the excessively high yield stress and viscosity under the condition of high solid content, and the use of sepiolite is difficult, and the use of unmodified nanofibers in comparative example 2 can lead to the reduction of the yield stress, and the use of modified nanofibers with the quality and the size outside the range of comparative examples 3-4 and comparative examples 5-6 respectively can also have corresponding effects on the yield stress and the viscosity.
From the stability data, the alkali-free accelerator prepared in examples 1-8 can maintain stability for more than 90d at normal temperature, and the phenomena of layering, crystallization, gelation and the like can not occur during the process, so that the stable quality of the alkali-free accelerator during the process is ensured. Whereas stabilization with sepiolite in comparative example 1 resulted in about 5ml of supernatant at 14d on the one hand and gel formation of the lower suspension during standing due to the higher viscosity on the other hand. Comparative example 2 because unmodified nanofibers were used, it was difficult to lock the aluminum phase material in the three-dimensional network structure formed by the fibers, and thus a significant delamination phenomenon occurred in 10 d. In contrast, comparative examples 3-4, because too much and too little modified nanofibers, respectively, resulted in the presence of gels and delaminates in the accelerator during storage, respectively, resulting in a decrease in the stability of the accelerator system. Comparative examples 5-6 too loose or tight a three-dimensional network structure and reduced the stability of the system due to the use of oversized or undersized modified nanofibers as stabilizers, respectively. Therefore, the modified nano fiber with proper size and dosage is the key point of stabilizing the alkali-free accelerator in the invention.
The setting time and strength of the alkali-free accelerator of examples and comparative examples using the cement paste and mortar are shown in table 2, and the cement used in the test is the reference cement, and the amount of the alkali-free accelerator is 7% of the amount of cement used.
Table 2 results of alkali-free accelerator clean mortar testing.
As can be seen from the data in Table 2, the synthesized alkali-free accelerator meets the related standard requirements in the setting time, and can ensure the rapid setting construction of sprayed concrete. From the mortar strength, the advantages of the early strength of the examples 1-8 are larger, the strength of the 6h can reach more than 1.2MPa, the strength of the 1d can reach more than 18MPa, the later strength is kept better, the 28d compressive strength ratio can reach more than 100%, and the 90d compressive strength retention rate can reach more than 105%, which is due to the fact that the modified nano fibers are contained in the modified nano fibers, and on the other hand, the high aluminum phase ion concentration and the good service performance are simultaneously maintained, so that the cement gel material has good early strength formation and strength development performance in the hydration process, and has important significance for preparing high-performance sprayed concrete.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any simple modification, equivalent variation and variation of the above embodiment according to the technical matter of the present invention still fall within the scope of the technical scheme of the present invention.
Claims (6)
1. The modified nanofiber stable high early strength alkali-free accelerator is characterized by being prepared from the following components in parts by mass:
50 to 65 percent of aluminum sulfate,
5-15% of pseudo-boehmite,
alcohol amine 3-8%,
0.5 to 2.5 percent of modified nano fiber,
0.5 to 1 percent of organic acid,
0.1 to 0.5 percent of stabilizer,
0.05 to 0.1 percent of rheology modifier,
the rest is water;
the sum of the mass percentages of the components is 100 percent;
the modified nanofiber is polyamine surface modified nanofiber, and the specific preparation steps comprise the steps of washing and drying the nanofiber, oxidizing the nanofiber in an ozone oxidation machine for 15min, putting the oxidized nanofiber into a solution dissolved with an acrylation reagent for reaction for 3h, putting the acrylation nanofiber into the solution dissolved with a polyamine reagent for reaction for 2h, and filtering and washing the nanofiber after reaction to obtain the modified nanofiber; the nanofiber is at least one of cellulose nanocrystals, cellulose nanofibrils, bacterial cellulose, electrostatic spinning cellulose nanofibrils, polyamide nanofibres, polylactic acid nanofibres, polyvinylpyrrolidone nanofibres, polyethylene terephthalate nanofibres and nano glass fibers, the diameter of the modified nanofiber is in the range of 30-150 nm, and the length-diameter ratio is in the range of 3-30; the polyamine reagent is at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethylene polyamine, the concentration is 10-20%, and the solvent is at least one of ethanol, acetone, isopropanol, acetonitrile and tetrahydrofuran; the acrylating reagent is at least one of acryloyl chloride, acryloyl bromide, acrylic anhydride, methacryloyl chloride, methacryloyl bromide and methacrylic anhydride, the concentration is 5-30%, and the solvent is at least one of pyridine, N-dimethylformamide and dimethyl sulfoxide.
2. The modified nanofiber stable high-early-strength alkali-free accelerator according to claim 1, wherein the alcohol amine is at least one of diethanolamine, triethanolamine and triisopropanolamine; the organic acid is at least one of oxalic acid, tartaric acid, malic acid, citric acid, ascorbic acid, salicylic acid, lactic acid, polyaspartic acid and ethylenediamine tetraacetic acid.
3. The modified nanofiber stable high early strength alkali-free accelerator according to claim 1, wherein the stabilizer is at least one of polyacrylamide, cinnamamide, polycarboxylic acid, di (hydrogenated tallow) phthalic acid amide and modified acrylic acid polymer; the rheology modifier is at least one of xanthan gum, guar gum, temperature roller gum, polyethylene glycol 2000 and cellulose ether.
4. The method for preparing the modified nanofiber stable high-early-strength alkali-free accelerator according to claim 1, which is characterized by comprising the following steps:
adding the modified nanofiber, the organic acid and the rheology modifier into water, and stirring at a high speed for 5min to form a uniform suspension; slowly adding 50% of aluminum sulfate and pseudo-boehmite into the suspension, stirring at a high speed for 0.5h, slowly adding the rest 50% of aluminum sulfate into the suspension while stirring, keeping stirring at a high speed for 1.5h, adding alcohol amine and a stabilizer into the system, keeping stirring at a high speed for 1h, and stirring the reaction solution at a low speed for 1.5-3h to obtain the modified nanofiber stable high early strength alkali-free accelerator.
5. The method of manufacturing according to claim 4, wherein: the high-speed stirring linear speed is more than 10m/s, and the low-speed stirring linear speed is between 0.5 and 2 m/s.
6. The use of a modified nanofiber stabilized high early strength alkali-free accelerator as a shotcrete and shotcrete accelerator according to claim 1.
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| DE4223494A1 (en) * | 1992-07-17 | 1994-01-20 | Heidelberger Zement Ag | Fast curing hydraulic binder |
| CN110835377A (en) * | 2019-11-05 | 2020-02-25 | 浙江科技学院 | Novel hydrophobically modified nano-cellulose and preparation method and application thereof |
| CN112794674A (en) * | 2019-11-14 | 2021-05-14 | 江苏博思通新材料有限公司 | Low-resilience alkali-free liquid accelerator for concrete and preparation method thereof |
| CN113123159A (en) * | 2021-04-09 | 2021-07-16 | 陕西科技大学 | Cellulose nano fibril suspension and preparation method thereof |
| CN113603384A (en) * | 2021-08-11 | 2021-11-05 | 石家庄市长安育才建材有限公司 | Super-early-strength fluoride-free alkali-free liquid accelerator and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE4223494A1 (en) * | 1992-07-17 | 1994-01-20 | Heidelberger Zement Ag | Fast curing hydraulic binder |
| CN110835377A (en) * | 2019-11-05 | 2020-02-25 | 浙江科技学院 | Novel hydrophobically modified nano-cellulose and preparation method and application thereof |
| CN112794674A (en) * | 2019-11-14 | 2021-05-14 | 江苏博思通新材料有限公司 | Low-resilience alkali-free liquid accelerator for concrete and preparation method thereof |
| CN113123159A (en) * | 2021-04-09 | 2021-07-16 | 陕西科技大学 | Cellulose nano fibril suspension and preparation method thereof |
| CN113603384A (en) * | 2021-08-11 | 2021-11-05 | 石家庄市长安育才建材有限公司 | Super-early-strength fluoride-free alkali-free liquid accelerator and preparation method thereof |
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