CN113213805A - Quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator and preparation method thereof - Google Patents
Quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator and preparation method thereof Download PDFInfo
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- CN113213805A CN113213805A CN202110345674.5A CN202110345674A CN113213805A CN 113213805 A CN113213805 A CN 113213805A CN 202110345674 A CN202110345674 A CN 202110345674A CN 113213805 A CN113213805 A CN 113213805A
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- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 56
- 230000005284 excitation Effects 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 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 abstract description 10
- -1 alcohol amine Chemical class 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 49
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000013008 thixotropic agent Substances 0.000 claims description 7
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims description 6
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021485 fumed silica Inorganic materials 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000378 calcium silicate Substances 0.000 claims description 5
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 5
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-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
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 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
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-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
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 1
- 239000001506 calcium phosphate Substances 0.000 claims 1
- 229910000389 calcium phosphate Inorganic materials 0.000 claims 1
- 235000011010 calcium phosphates Nutrition 0.000 claims 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims 1
- 229910001386 lithium phosphate Inorganic materials 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 abstract description 16
- 239000004570 mortar (masonry) Substances 0.000 abstract description 14
- 229910052943 magnesium sulfate Inorganic materials 0.000 abstract description 8
- 235000019341 magnesium sulphate Nutrition 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004568 cement Substances 0.000 description 62
- 239000011083 cement mortar Substances 0.000 description 45
- 238000003756 stirring Methods 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 31
- 238000000034 method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 12
- 238000003556 assay Methods 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000004567 concrete Substances 0.000 description 6
- 229940043237 diethanolamine Drugs 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011378 shotcrete Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 3
- 229910052912 lithium silicate Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 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
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 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
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
-
- 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
-
- 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
Abstract
The invention discloses a quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator and a preparation method thereof, wherein the accelerator comprises the following raw material components in parts by mass: 40-65 parts of aluminum sulfate; 1-7 parts of magnesium sulfate; 3-15 parts of alcohol amine; 0.5-5 parts of excitation material; 20-60 parts of water. The rapid early-strength alkali-free fluorine-free chlorine-free liquid accelerator disclosed by the invention meets the requirements of high compressive strength of mortar for 6 hours, low mixing amount and good stability; the accelerator has simple preparation method and high safety.
Description
Technical Field
The invention relates to a quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator and a preparation method thereof, belonging to an additive for concrete engineering construction.
Background
The prior alkali-free liquid accelerator product mostly has the following problems: (1) the mixing amount is high, and the standard requirements of the concrete on the setting time and the compressive strength can be met only by high mixing amount; (2) the early strength is low, and the compressive strength of the mortar cannot meet the requirements that the compressive strength of the mortar is more than or equal to 1MPa after 6 hours and more than or equal to 7MPa after 1 day; (3) the stability is poor and the storage time is short. Therefore, the development of the alkali-free accelerator with the characteristics of low doping amount, high speed, early strength, high later strength retention rate, good stability, greenness and harmlessness is a necessary trend for the development of future alkali-free liquid accelerators.
Patent application publication No. CN 110963736A discloses a nano-gel polyaluminium chloride type liquid alkali-free accelerator and a preparation method thereof, rich nucleation sites provided by nano-scale calcium silicate hydrate gel are utilized, under the condition of not introducing other impurity ions, hydration of tricalcium silicate can be rapidly promoted, and the early strength of cement is harmlessly improved, but through experiments, the inventor finds that the compressive strength of mortar in the patent is less than 1MPa for 6h, and the early strength is to be improved.
The accelerator industry in China enters a new development stage, relevant specifications and standards are provided, and research and application of alkali-free liquid accelerators are stimulated and encouraged. Along with the continuous improvement of the attention of people to environmental friendliness and concrete durability at present, the development of the accelerator which is free of alkali, fluorine and chlorine, small in doping amount, short in setting time, rapid in early strength, high in early strength, low in rebound amount, high in later strength retention rate, good in stability, green and harmless is the research direction.
In view of the above, the invention provides a quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator and a preparation method thereof. The accelerator can meet the standard requirements of concrete on setting time and compressive strength under the doping amount of 3-7%; the accelerator has the characteristics of low mixing amount, high speed, early strength, high retention rate of later strength, good stability, greenness and harmlessness.
Disclosure of Invention
The invention aims to solve the technical problems that the prior alkali-free liquid accelerator product generally has the following problems: high mixing amount, low early strength, poor stability and short storage time.
In order to solve one or more technical problems, the invention provides a quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator which comprises the following raw material components in parts by mass:
in the present invention, "fluorine-free" means that F element is not contained; chlorine-free "means free of Cl elements," alkali-free "means free of Na and K elements, or less than 1 wt% (in equivalents of Na)2O content).
In the components of the accelerator, aluminum sulfate is the main component of the accelerator. Preferably, the aluminum sulfate in the raw material of the accelerating agent is 50-60 parts by mass. The magnesium sulfate mainly has the function of improving the early strength of the cement; meanwhile, the magnesium sulfate has the coagulation promoting effect. The alcohol amine has the functions of complexing Al ions on one hand and adsorbing the Al ions on the surface of the aluminum sulfate crystal as a surface active substance to control the stability of a system on the other hand. The alcohol amine is selected from one or more of triethanolamine, diethanolamine and triisopropanolamine.
Preferably, the raw materials of the accelerator also comprise 1-3 parts of a thixotropic agent by mass, and the thixotropic agent has the function of forming a suspension system so that the accelerator does not layer or precipitate; the thixotropic agent is one or more of fumed silica, organic bentonite, hydrogenated castor oil, polyamide wax, attapulgite and nano alumina.
Preferably, the accelerator also comprises 0.1-3 parts of organic acid by mass, wherein the organic acid is used for adjusting the pH of the system and helping to maintain the stability of the system; the organic acid is one or more of polyacrylic acid, maleic acid-acrylic acid copolymer, polymethacrylic acid, formic acid, acetic acid, oxalic acid, salicylic acid and 2-hydroxypropionic acid.
Preferably, when the excitation material is lithium carbonate, the lithium carbonate is 1 to 4 parts by mass, more preferably 2 to 4 parts.
Preferably, when the excitation material contains Na or K element, the excitation material is used in an amount of 0.5 to 1.9 parts by mass, more preferably, 0.7 to 1.5 parts by mass.
Preferably, the accelerator consists of the following components in parts by mass:
other auxiliaries are selected as follows: thixotropic agents, pH adjusting agents; wherein the thixotropic agent can be fumed silica, and is preferably 1.5 parts; the pH regulator is organic acid, such as maleic acid-acrylic acid copolymer 1.0 parts and polyacrylic acid 0.5 parts.
As the same inventive concept, the invention also provides a preparation method of the quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator, which is prepared by mixing the components in the accelerator.
The main innovation point of the invention is that the addition of the exciting material into the accelerating agent can obviously improve the early strength of the concrete, and particularly can meet the requirement that the compressive strength of mortar is more than or equal to 1MPa after 6 hours, unlike the direct addition of the exciting material (exciting agent) into the premixed concrete. In addition, the invention also optimizes the condition that when the lithium carbonate is used as an exciting material and is added into the accelerator, various performance indexes of the cement cementing material can be obviously improved.
The accelerating agent is added with the exciting material, the exciting material has more obvious influence on the cement hydration process, the induction period of the cement hydration can be shortened, the speed of the acceleration period is obviously increased, the occurrence time of a main peak is shortened, and the setting time is further shortened; the generated C-S-H, CH and AFm have compact structures, so that the 6h compressive strength of the mortar is greatly improved.
Compared with the prior art, the invention has the advantages that: the rapid early-strength alkali-free fluorine-free chlorine-free liquid accelerator provided by the invention meets the requirements that the compressive strength of mortar is more than or equal to 1MPa after 6 hours and more than or equal to 7MPa after 1 day; the mixing amount is low, and the standard requirements of compressive strength and setting time can be met when the mixing amount of the quick early-strength alkali-free liquid accelerator is less than or equal to 7 percent; the stability is good; the accelerator has simple preparation method and high safety.
Detailed Description
The present invention is further illustrated by the following examples, comparative examples and application examples.
Example 1
This example provides a fast early strength alkali-free, fluorine-free, chlorine-free liquid accelerator having the following composition (wherein each part is 10g, the same applies below):
wherein the maleic acid-acrylic acid copolymer CasNo:29132-58-9 is obtained from Beijing Yinokay science and technology Co., Ltd., and has a weight average molecular weight of 3000; CasNo of polyacrylic acid 9003-01-4, available from Okay technologies, Beijing; fumed silica is available from Evonik degussa, AEROSIL a 380.
The preparation method comprises the following steps:
(1) uniformly stirring water and diethanol amine, and heating to 60 ℃;
(2) keeping the temperature at 60 ℃, adding aluminum sulfate and stirring until the solution is transparent;
(3) keeping the temperature at 60 ℃, adding magnesium sulfate and stirring for 15 minutes;
(4) keeping the temperature at 60 ℃, adding maleic acid-acrylic acid copolymer, mixing and stirring for 15 minutes;
(5) keeping the temperature at 60 ℃, adding lithium carbonate, mixing and stirring for 20 minutes;
(6) keeping the temperature at 60 ℃, adding fumed silica, mixing and stirring for 15 minutes;
(7) and keeping the temperature at 60 ℃, adding polyacrylic acid, and stirring for 60 minutes to obtain the quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator.
The invention discovers that when the addition amount of the lithium carbonate is 3 parts, the setting time and the strength can both reach the standard requirements, and the action effect of the accelerator is optimal. When the addition amount of the lithium carbonate is too small (less than 0.5 part), the requirement that the compressive strength of the mortar is more than or equal to 1MPa after 6 hours cannot be met, and when the content of the lithium carbonate is too large (more than 5 parts), the setting time can be prolonged.
Comparative example 1
This comparative example also provides a rapid early strength alkali-free fluorine-free chlorine-free liquid accelerator which has substantially the same raw material composition and preparation method as example 1 except that the excitation material lithium carbonate was not added to the raw material composition.
Application example 1
The quick-setting agents obtained in example 1 and comparative example 1 were prepared into neat cement paste and cement mortar respectively for performance measurement, and the measuring method of the setting time of the neat cement paste doped with the quick-setting agent and the measuring method of the compressive strength of the cement mortar doped with the quick-setting agent were measured according to the measuring method in GB/T35159-2017 quick-setting agent for shotcrete.
The accelerating agent prepared in example 1 and comparative example 1 and the excitation material are prepared to obtain the following three groups of cement paste and cement mortar for performance comparison, wherein the reference cement is taken as a basis, the amount of the accelerating agent added into the cement paste or the cement mortar is 7 wt% of the reference cement, and the excitation material is lithium carbonate.
Group (1-1): cement paste and cement mortar containing the accelerator obtained in example 1.
Group (1-2): a cement paste and a cement mortar containing the accelerator obtained in comparative example 1.
Group (1-3): cement paste and cement mortar containing the accelerating agent obtained in comparative example 1 and an activating material.
The three groups of cement paste and cement mortar added with the accelerator are subjected to performance measurement according to the standard requirements of GB/T35159-.
The three groups of pure slurry or mortar are different in that: (1-1) the group is added with an accelerating agent containing an excitation material; (1-2) group is control group, and does not contain excitation material; the (1-3) group is that the exciting material is directly added into cement paste or cement mortar, and after the mixture is mixed, the accelerating agent without exciting material is added. And (3) analysis results: the measurement results of the group (1-1) are significantly better than those of the groups (1-2) and (1-3), wherein the measurement results of the group (1-3) are better than those of the group (1-2). It can be seen that the addition of the lithium carbonate as the excitation material to the accelerator can significantly improve the early strength (especially 6h strength) of the cement-based material.
Example 2
The embodiment provides a quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator which comprises the following components:
the preparation method comprises the following steps:
(1) uniformly stirring water and diethanol amine, and heating to 60 ℃;
(2) keeping the temperature at 60 ℃, adding aluminum sulfate and stirring until the solution is transparent;
(3) keeping the temperature at 60 ℃, adding magnesium sulfate and stirring for 15 minutes;
(4) keeping the temperature at 60 ℃, adding maleic acid-acrylic acid copolymer, mixing and stirring for 15 minutes;
(5) keeping the temperature at 60 ℃, adding lithium silicate, mixing and stirring for 20 minutes;
(6) keeping the temperature at 60 ℃, adding fumed silica, mixing and stirring for 15 minutes;
(7) and keeping the temperature at 60 ℃, adding polyacrylic acid, and stirring for 60 minutes to obtain the quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator.
Comparative example 2
The raw material composition and the preparation method of this comparative example were substantially the same as those of example 2 except that the lithium silicate as the excitation material was not added to the raw material composition.
Application example 2
The quick-setting agents obtained in example 2 and comparative example 2 were prepared into neat cement paste and cement mortar respectively for performance measurement, and the measuring method of the setting time of the neat cement paste doped with the quick-setting agent and the measuring method of the compressive strength of the cement mortar doped with the quick-setting agent were measured according to the measuring method in GB/T35159-2017 quick-setting agent for shotcrete.
The accelerating agent prepared in example 2 and comparative example 2 and the excitation material are prepared into the following three groups of cement paste and cement mortar for performance comparison, wherein the reference cement is taken as a basis, the amount of the accelerating agent added into the cement paste or the cement mortar is 7 wt% of the reference cement, and the excitation material is lithium silicate.
Group (2-1): cement paste and cement mortar containing the accelerator obtained in example 2.
Group (2-2): a cement paste and a cement mortar containing the accelerator obtained in comparative example 2.
Group (2-3): cement paste and cement mortar containing the accelerating agent obtained in comparative example 2 and an activating material.
The three groups of cement paste and cement mortar added with the accelerator are subjected to performance measurement according to the standard requirements of GB/T35159-.
The three groups of pure slurry or mortar are different in that: (2-1) the group is added with an accelerating agent containing an excitation material; (2-2) group is control group, and does not contain excitation material; and the group (2-3) is that the exciting material is directly added into the cement paste or cement mortar, and after the mixture is mixed, the accelerating agent without exciting material is added. Analysis results the assay results of the group (2-1) were significantly better than those of the groups (2-2) and (2-3), with the assay results of the group (2-3) being better than those of the group (2-2).
Example 3
The embodiment provides a quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator which comprises the following components:
the preparation method comprises the following steps:
(1) uniformly stirring water and triethanolamine, and heating to 60 ℃;
(2) keeping the temperature at 60 ℃, adding aluminum sulfate and stirring until the solution is transparent;
(3) keeping the temperature at 60 ℃, adding magnesium sulfate and stirring for 15 minutes;
(4) keeping the temperature at 60 ℃, adding oxalic acid, mixing and stirring for 15 minutes;
(5) keeping the temperature at 60 ℃, adding calcium silicate, mixing and stirring for 20 minutes;
(6) keeping the temperature at 60 ℃, adding attapulgite, mixing and stirring for 15 minutes;
(7) keeping the temperature at 60 ℃, adding acrylic acid and stirring for 60 minutes to obtain the quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator.
Comparative example 3
The raw material composition and the preparation method of this comparative example are substantially the same as those of example 3 except that the calcium silicate exciting material is not added to the raw material composition.
Application example 3
The quick-setting agents obtained in example 3 and comparative example 3 were prepared into neat cement paste and cement mortar respectively for performance measurement, and the measuring method of the setting time of the neat cement paste doped with the quick-setting agent and the measuring method of the compressive strength of the cement mortar doped with the quick-setting agent were measured according to the measuring method in GB/T35159-2017 quick-setting agent for shotcrete.
The accelerating agent prepared in example 3 and comparative example 3 and the excitation material are prepared to obtain the following three groups of cement paste and cement mortar for performance comparison, wherein the reference cement is taken as a basis, the amount of the accelerating agent added into the cement paste or the cement mortar is 7 wt% of the reference cement, and the excitation material is calcium silicate.
Group (3-1): cement paste and cement mortar containing the accelerator obtained in example 3.
Group (3-2): a cement paste and a cement mortar containing the accelerator obtained in comparative example 3.
Group (3-3): cement paste and cement mortar containing the accelerating agent obtained in comparative example 3 and an activating material.
The three groups of cement paste and cement mortar added with the accelerator are subjected to performance measurement according to the standard requirements of GB/T35159-.
The three groups of pure slurry or mortar are different in that: (3-1) the group is added with an accelerating agent containing an excitation material; (3-2) group is control group, and does not contain excitation material; and (3-3) adding exciting material directly into cement paste or cement mortar, mixing and adding accelerating agent containing no exciting material. Analysis results the assay results of the group (3-1) were significantly better than those of the groups (3-2) and (3-3), with the assay results of the group (3-3) being better than those of the group (3-2).
Example 4
The embodiment provides a quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator which comprises the following components:
the preparation method comprises the following steps:
(1) uniformly stirring water and diethanol amine, and heating to 60 ℃;
(2) keeping the temperature at 60 ℃, adding aluminum sulfate and stirring until the solution is transparent;
(3) keeping the temperature at 60 ℃, adding magnesium sulfate and stirring for 15 minutes;
(4) keeping the temperature at 60 ℃, adding acetic acid, mixing and stirring for 15 minutes;
(5) keeping the temperature at 60 ℃, adding lithium sulfate, mixing and stirring for 20 minutes;
(6) keeping the temperature at 60 ℃, adding sepiolite powder, mixing and stirring for 15 minutes;
(7) and keeping the temperature at 60 ℃, adding triethanolamine and stirring for 60 minutes to obtain the quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator.
Comparative example 4
The raw material composition and the production method of this comparative example were substantially the same as those of example 4 except that the excitation material lithium sulfate was not added to the raw material composition.
Application example 4
The quick-setting agents obtained in example 4 and comparative example 4 were prepared into neat cement paste and cement mortar respectively for performance measurement, and the measuring method of the setting time of the neat cement paste doped with the quick-setting agent and the measuring method of the compressive strength of the cement mortar doped with the quick-setting agent were measured according to the measuring method in GB/T35159-2017 quick-setting agent for shotcrete.
The accelerating agent prepared in example 4 and comparative example 4 and the excitation material are prepared into the following three groups of cement paste and cement mortar for performance comparison, wherein the reference cement is taken as a basis, the amount of the accelerating agent added into the cement paste or the cement mortar is 7 wt% of the reference cement, and the excitation material is lithium sulfate.
Group (4-1): cement paste and cement mortar containing the accelerator obtained in example 4.
Group (4-2): a cement paste and a cement mortar containing the accelerator obtained in comparative example 4.
Group (4-3): cement paste and cement mortar containing the accelerator obtained in comparative example 4 and an activating material.
The three groups of cement paste and cement mortar added with the accelerator are subjected to performance measurement according to the standard requirements of GB/T35159-.
The three groups of pure slurry or mortar are different in that: (4-1) the group is added with an accelerating agent containing an excitation material; (4-2) group is control group, and does not contain excitation material; and (4-3) adding the exciting material directly into the cement paste or cement mortar, and adding the accelerating agent without exciting material after mixing. Analysis results the assay results of the group (4-1) were significantly better than those of the groups (4-2) and (4-3), with the assay results of the group (4-3) being better than those of the group (4-2).
Example 5
The embodiment provides a quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator which comprises the following components:
the preparation method comprises the following steps:
(1) uniformly stirring water and diethanol amine, and heating to 60 ℃;
(2) keeping the temperature at 60 ℃, adding aluminum sulfate and stirring until the solution is transparent;
(3) keeping the temperature at 60 ℃, adding magnesium sulfate and stirring for 15 minutes;
(4) keeping the temperature at 60 ℃, adding acetic acid, mixing and stirring for 15 minutes;
(5) keeping the temperature at 60 ℃, adding calcium sulfate, mixing and stirring for 20 minutes;
(6) keeping the temperature at 60 ℃, adding nano alumina, mixing and stirring for 15 minutes;
(7) and keeping the temperature at 60 ℃, adding triethanolamine and stirring for 60 minutes to obtain the quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator.
Comparative example 5
The raw material composition and the preparation method of this comparative example are substantially the same as those of example 5 except that the exciting material calcium sulfate was not added to the raw material composition.
Application example 5
The quick-setting agents obtained in example 5 and comparative example 5 were prepared into neat cement paste and cement mortar respectively for performance measurement, and the measuring method of the setting time of the neat cement paste doped with the quick-setting agent and the measuring method of the compressive strength of the cement mortar doped with the quick-setting agent were measured according to the measuring method in GB/T35159-2017 quick-setting agent for shotcrete.
The accelerating agent prepared in example 5 and the accelerating agent prepared in comparative example 5 and the excitation material are prepared to obtain the following three groups of cement paste and cement mortar for performance comparison, wherein the reference cement is taken as a basis, the amount of the accelerating agent added into the cement paste or the cement mortar is 7 wt% of the reference cement, and the excitation material is calcium sulfate.
Group (5-1): cement paste and cement mortar containing the accelerator obtained in example 4.
Group (5-2): a cement paste and a cement mortar containing the accelerator obtained in comparative example 4.
(5-3) group: cement paste and cement mortar containing the accelerator obtained in comparative example 4 and an activating material.
The three groups of cement paste and cement mortar added with the accelerator are subjected to performance measurement according to the standard requirements of GB/T35159-.
The three groups of pure slurry or mortar are different in that: (5-1) the group is added with an accelerating agent containing an excitation material; (5-2) group is control group, and does not contain excitation material; and (5-3) adding the exciting material directly into the cement paste or cement mortar, and adding the accelerating agent without exciting material after mixing. Analysis results the assay results of the group (5-1) were significantly better than those of the groups (5-2) and (5-3), with the assay results of the group (5-3) being better than those of the group (5-2).
TABLE 1 Performance test results for neat and mortar with addition of accelerator
And (4) analyzing results: analysis of the above five data sets in table 1 shows that the addition of the activating material to the setting accelerator can improve the early strength of the cement-based material as a whole, and particularly, the addition of lithium carbonate to the setting accelerator can significantly improve the early strength (especially 6h strength).
Claims (10)
1. The quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator is characterized by comprising the following raw material components in parts by mass:
2. the accelerator according to claim 1, wherein the accelerator comprises 50 to 60 parts by mass of aluminum sulfate in a raw material.
3. The accelerator according to any one of claims 1 to 2, wherein the accelerator further comprises 1 to 3 parts by mass of a thixotropic agent in the raw materials.
4. The accelerating agent as set forth in any one of claims 1 to 3, wherein the thixotropic agent is one or more of fumed silica, organobentonite, hydrogenated castor oil, polyamide wax, attapulgite and nano alumina.
5. The accelerator according to any one of claims 1 to 4, wherein the accelerator further comprises 0.1 to 3 parts by mass of an organic acid in the raw material.
6. The accelerator according to any one of claims 1 to 5, wherein the organic acid is one or more of polyacrylic acid, maleic acid-acrylic acid copolymer, polymethacrylic acid, formic acid, acetic acid, oxalic acid, salicylic acid and 2-hydroxypropionic acid in parts by mass.
7. Accelerator according to any one of claims 1 to 6, wherein the alcohol amine is selected from one or more of triethanolamine, diethanolamine and triisopropanolamine.
8. The accelerator according to any one of claims 1 to 7, wherein the excitation material is one or more of calcium silicate, lithium carbonate, sodium carbonate, lithium phosphate, sodium phosphate, lithium iron phosphate, calcium phosphate, sodium monohydrogen phosphate, calcium sulfate, calcium carbonate, lithium sulfate, sodium sulfate, and lithium hydroxide.
9. The accelerator according to any one of claims 1 to 8, wherein the excitation material is lithium carbonate, and the lithium carbonate is 1 to 4 parts by mass.
10. A preparation method of a quick early-strength alkali-free fluorine-free chlorine-free liquid accelerator is characterized by mixing the components in the accelerator.
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| CN116462441B (en) * | 2023-05-04 | 2023-10-20 | 湖北腾辰科技股份有限公司 | Early-strength fluorine-free alkali-free liquid accelerator and preparation method thereof |
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