CN115368051A - Antifreeze accelerator, preparation method thereof and sprayed concrete - Google Patents
Antifreeze accelerator, preparation method thereof and sprayed concrete Download PDFInfo
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- CN115368051A CN115368051A CN202211307702.5A CN202211307702A CN115368051A CN 115368051 A CN115368051 A CN 115368051A CN 202211307702 A CN202211307702 A CN 202211307702A CN 115368051 A CN115368051 A CN 115368051A
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- 239000011378 shotcrete Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000002528 anti-freeze Effects 0.000 title claims abstract description 9
- 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 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000000536 complexating effect Effects 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 13
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000004480 active ingredient Substances 0.000 claims abstract 2
- 238000007710 freezing Methods 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910021389 graphene Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000004113 Sepiolite Substances 0.000 claims description 6
- 229910052624 sepiolite Inorganic materials 0.000 claims description 6
- 235000019355 sepiolite Nutrition 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000004471 Glycine Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004567 concrete Substances 0.000 abstract description 19
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000005507 spraying Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000004568 cement Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 16
- 238000010276 construction Methods 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000009775 high-speed stirring Methods 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001653 ettringite Inorganic materials 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- -1 magnesium fluorosilicate Chemical compound 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241001374849 Liparis atlanticus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/601—Agents for increasing frost resistance
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
- C04B2111/00155—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
-
- 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 provides an antifreeze type accelerator, a preparation method thereof and sprayed concrete, wherein the antifreeze type accelerator comprises the following active ingredients in preparation raw materials in percentage by weight: 50-60% of aluminum sulfate, 2-5% of inorganic salt, 0.5-1.0% of stabilizing component, 1-3% of antifreezing component, 2-5% of organic complexing component, 0.005-0.02% of inorganic nano component and the balance of water. The antifreezing accelerator has the advantages that the antifreezing accelerator is stable in state under low-temperature environment due to synergistic effect of various preparation raw materials, and when concrete is added in the mixing process, the setting time of the concrete can be shortened, the early and later strength of the concrete can be improved, and the antifreezing accelerator is used for spraying the concrete and can reduce the rebound rate.
Description
Technical Field
The invention relates to the field of concrete building materials, in particular to an anti-freezing accelerator and a preparation method thereof, and also relates to sprayed concrete prepared from the anti-freezing accelerator.
Background
The continuous development of science, technology and social economy promotes the rapid development of railways and highways in China, and the development of high-speed railways is particularly rapid. The construction of the tunnel in China will enter a high-speed propulsion stage in the future large-scale construction of highway main lines, intercity high-speed rails and city subways and the future construction of submarine tunnels. At present, the demand of sprayed concrete in projects such as tunnel construction, coal mine reinforcement, urban road and waterproof facility repair in China is increasing, and the demand of high-quality accelerating agents is also increasing.
The western region of China is in plateau, the breadth of the population is wide, the population is in cold winter in about 3 months every year, the temperature difference between day and night is large, and the temperature is low for a long time. In the construction process of sprayed concrete, when the temperature is lower than 0 ℃, the free water begins to freeze, the cement setting and hardening are slowed down, and the temperature is reduced to about-15 ℃, the free water almost completely freezes, so that the hydration and hardening of the cement are completely stopped, the rebound quantity of the sprayed concrete is greatly increased, and the performance and the using effect of the accelerator are seriously influenced. On the other hand, the alkali-free setting accelerators developed at the present stage all use aluminum sulfate as a main raw material, and under a negative temperature environment, along with the formation of liquid water ice crystals and the reduction of the solubility of the aluminum sulfate, the alkali-free setting accelerators are in a destabilization state, so that the phenomena of crystallization and precipitation and the like are generated, so that the alkali-free setting accelerators are difficult to pump, the effect is reduced or even lost, the construction resilience is further increased, and crystal particles in the setting accelerators can cause the pipe blockage at the discharge port of the wet spraying machine to influence the construction progress. In addition, the existing alkali-free accelerator has the problems of low early and later strength and slow strength development in low-temperature construction.
Therefore, how to improve the frost resistance of the accelerator and ensure the smooth construction of the sprayed concrete in a low-temperature environment is an important link for shortening the construction period and improving the social benefit and the economic benefit. At present, the research on alkali-free setting accelerators has achieved more results, but the research on improving the freezing resistance under low temperature conditions is less.
Disclosure of Invention
In view of the above, the invention provides an anti-freezing accelerator which is stable in a low-temperature environment.
An anti-freezing accelerator comprises the following effective components in preparation raw materials in percentage by weight: 50-60% of aluminum sulfate, 2-5% of inorganic salt, 0.5-1.0% of stabilizing component, 1-3% of antifreezing component, 2-5% of organic complexing component, 0.005-0.02% of inorganic nano component and the balance of water.
Further, the inorganic salt includes at least one of sodium aluminate, magnesium fluorosilicate, and sodium fluoride.
Further, the stabilizing component includes at least one of pseudoboehmite and sepiolite.
Further, the antifreeze component comprises at least one of dimethyl sulfoxide and ethylene glycol.
Further, the inorganic nano-component includes graphene oxide.
Further, the sheet diameter of the graphene oxide is 20-200nm.
Further, the organic complexing component comprises at least one of ethylenediamine tetraacetic acid, glycine and diethylenetriamine.
The antifreezing accelerator provided by the invention is prepared from raw materials including aluminum sulfate, inorganic salt, a stabilizing component, an antifreezing component, an organic complexing component and an inorganic nano component, wherein the raw materials are synergistic, the antifreezing accelerator is stable in state in a low-temperature environment, when the antifreezing accelerator is mixed and added into concrete, the setting time of the concrete can be shortened, the early and later strength of the concrete can be improved, and the antifreezing accelerator can be used for spraying the concrete and can reduce the rebound rate.
The invention also provides a preparation method of the anti-freezing accelerator, which comprises the following steps:
and (2) uniformly mixing the stable component with water, adding inorganic salt and aluminum sulfate, heating to 60-70 ℃, adding the organic complex component, the inorganic nanometer component and the antifreezing component after the aluminum sulfate is dissolved, uniformly stirring, and cooling to obtain the antifreezing accelerator.
The invention also provides sprayed concrete, and the raw materials for preparing the sprayed concrete comprise the anti-freezing accelerator.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified. In addition, unless otherwise specified, all terms and processes related to the present embodiment should be understood according to the conventional knowledge and conventional methods in the art.
An anti-freezing accelerator comprises the following effective components in preparation raw materials in percentage by weight: 50-60% of aluminum sulfate, 2-5% of inorganic salt, 0.5-1.0% of stabilizing component, 1-3% of antifreezing component, 2-5% of organic complexing component, 0.005-0.02% of inorganic nano component and the balance of water.
The antifreezing accelerator provided by the invention is prepared from raw materials including aluminum sulfate, inorganic salt, a stabilizing component, an antifreezing component, an organic complexing component and an inorganic nano component, wherein the raw materials are synergistic, the antifreezing accelerator is stable in state in a low-temperature environment, when the antifreezing accelerator is mixed and added into concrete, the setting time of the concrete can be shortened, the early and later strength of the concrete can be improved, and the antifreezing accelerator can be used for spraying the concrete and can reduce the rebound rate.
The aluminum sulfate is dissociated in water, SO42- (sulfate ion) generated by hydrolysis of the aluminum sulfate reacts with Ca < 2+ > (calcium ion) generated by hydration of cement to generate fine secondary gypsum, the activity of the secondary gypsum is higher than that of the original gypsum in the cement, the reaction process with C3A (tricalcium aluminate) in the cement is accelerated, needle-shaped ettringite crystals are easier to generate, the aluminum sulfate and Ca (OH) 2 in a liquid phase can directly and quickly react to generate ettringite, the ettringite expands in volume and forms a compact net-shaped structure in a mutually staggered mode to fill pores, SO that slurry is compact, the strength development is facilitated, and the cement concrete is quickly coagulated; on the other hand, since the concentration of Ca2+ in the liquid phase is reduced, dissolution of C3A is promoted; al3+ (aluminum ions) can also accelerate the generation of C-S-H gel, shorten the induction period of C3S, accelerate the further hydration of C3S and further accelerate the setting of cement. Along with the reduction of the temperature, the solubility of aluminum sulfate in the accelerating agent is reduced, and a supersaturated solution is easily formed to be crystallized and separated out, so that the stability of the system is influenced. Therefore, other additives are added into the antifreezing accelerator disclosed by the invention, so that the raw materials have synergistic effect, and the antifreezing accelerator is stable in state in a low-temperature environment.
The inorganic salt has the same ion effect and salt effect, can change the solubility of cement colloid, quickens the hydration process of cement, and has chemical action with cement colloid minerals to generate double salt, complex or indissolvable compound with the solubility product smaller than that of corresponding single salt, thereby quickening the hydration of cement, and forming a crystallization center to quicken the setting and hardening of cement. The inorganic salt can preferably be a salt having a mineral structure similar to that of cement, including sodium aluminate; optionally, fluoride, such as magnesium fluosilicate and sodium fluoride; and combinations of the foregoing.
The stable component is in a three-dimensional network structure after absorbing water, so that aluminum in a supersaturated state can be absorbed, the suspension efficiency of supersaturated aluminum phase substances in the setting accelerator is greatly improved, partial suspended aluminum phase substances are prevented from crystallizing in a normal temperature storage mode or at a low temperature, and the stability and the freezing resistance are greatly improved. The stabilizing component preferably comprises at least one of pseudoboehmite and sepiolite.
The antifreezing component can reduce the freezing point of water in the accelerator, relieve the aluminum sulfate from forming supersaturated solution at low temperature to a certain extent, inhibit the aluminum sulfate from crystallizing, change the liquid phase concentration of the concrete, reduce the freezing point, ensure that the concrete has liquid phase at negative temperature, and ensure that the cement can still be continuously hydrated. The antifreeze component of the present invention may preferably comprise at least one of dimethyl sulfoxide and ethylene glycol.
The inorganic nano-component is a metastable intermediate substance between a macroscopic solid and molecules, and when the particle size enters a nano-order (1-100 nm), the ratio of surface atoms to the total atomic number of a bulk phase of the nano-particle is sharply increased along with the reduction of the particle size, so that the nano-particle shows strong volume effect, quantum effect, surface effect and macroscopic quantum tunneling effect. The inorganic nanometer component has large specific surface area, more surface atoms, high surface energy and insufficient atom coordination, so that the surface atoms have high activity, are unstable and easy to combine, and can be complexed with Al & lt 3+ & gt to improve the system stability.
The inorganic nano-component adopted by the anti-freezing accelerator disclosed by the invention preferably comprises graphene oxide. The graphene oxide is a carbon-based nano material obtained by oxidizing graphene, has a high specific surface area, and has a large number of randomly distributed epoxy functional groups on the surface, such as hydroxyl groups and epoxy groups on a two-dimensional plane, and a small number of carboxyl groups and carbonyl groups on the edge, so that multifunctional binding sites are provided, and can form intermolecular hydrogen bonds with water molecules while complexing with Al < 3+ > to increase the stability of the system, thereby inhibiting the crystallization of the water molecules to a certain extent and being beneficial to further lowering the freezing point. Meanwhile, the graphene oxide serving as a novel high-performance nano material has unique mechanical properties and nano size effect, can be effectively filled into the pores of concrete, increases the compactness of the system, is favorable for improving the early strength of the sprayed concrete under the low-temperature condition, and correspondingly improves the durability. More preferably, the sheet diameter of the graphene oxide is 20-200nm, and the graphene oxide in the sheet diameter range has the advantages of good nano size effect, large specific surface area, more epoxy groups and good Al3+ complexing effect.
The organic complexing component can complex Al < 3+ > and prevent Al < 3+ > from being separated out in cooperation with the inorganic nano component. After the anti-freezing accelerator is mixed with cement, the organic complexing component can also be complexed with calcium ions in the cement to promote the hydration of the cement. The organic complexing component preferably adopts a complexing agent with carboxyl and/or amino, and comprises at least one of ethylenediamine tetraacetic acid, glycine and diethylenetriamine, the complexing agent contains polydentate ligands, more ligands are contained under the same mass, each ligand contains a plurality of coordination atoms, more lone-pair electrons can be provided, and a chelate with a ring structure can be formed by complexing with Al3+, so that the crystallization precipitation of Al3+ is effectively inhibited, and the low-temperature stability of the anti-freezing accelerator is improved.
The antifreeze accelerator provided by the invention has almost no corrosion effect on steel bars, is safe and environment-friendly, has excellent antifreeze performance, has no phenomena of crystallization, precipitation and the like at a temperature of-5 ℃ to-30 ℃, has a stable period of more than 60 days, is low in mixing amount, can promote the concrete to be quickly condensed, can be used for construction in a low-temperature environment, reduces the rebound rate of sprayed concrete, and enables the sprayed concrete to have higher early and later strength.
The invention also provides a preparation method of the anti-freezing accelerator, which comprises the following steps:
adding the stabilizer into a vessel containing water under the state of high-speed stirring (500 r/min), stirring for 30min, reducing the rotating speed to the state of ordinary stirring (250 r/min) after the stabilizer is completely dispersed and dissolved, adding inorganic salt and aluminum sulfate into the vessel, heating to 60-70 ℃, preserving the temperature for 1-2h, sequentially adding an organic complexing component, an inorganic nano-component and an antifreezing component after the aluminum sulfate is completely dissolved, continuing stirring for 1h, then cooling, and naturally cooling to obtain the antifreezing accelerator.
The invention also provides sprayed concrete, and the raw materials for preparing the sprayed concrete comprise the anti-freezing accelerator. The anti-freezing accelerator can effectively enable the sprayed concrete to be used for construction in a low-temperature environment, reduces the rebound rate of the sprayed concrete, and enables the sprayed concrete to have higher early and later strength.
The following describes in detail specific embodiments of the present invention.
Example 1
Adding 1g of pseudo-boehmite into a vessel containing 41.5g of water under the state of high-speed stirring (500 r/min), stirring for 30min, reducing the rotating speed to the state of ordinary stirring (250 r/min) after complete dispersion and dissolution, adding 1g of magnesium fluosilicate, 2g of sodium aluminate and 50g of aluminum sulfate into the vessel, heating to 60-70 ℃, preserving the temperature for 1-2h, sequentially adding 2g of ethylenediamine tetraacetic acid, 0.5g of graphene oxide dispersion liquid (with the concentration of 10 mg/ml) and 2g of dimethyl sulfoxide after complete dissolution of the aluminum sulfate, continuously stirring for 1h, then cooling, naturally cooling, and finally preparing a finished product, namely the freeze-resistant alkali-free liquid accelerator. The graphene oxide dispersion liquid is the graphene oxide dispersion liquid with the model XF224, which is produced by Nanjing Xiapong nano material science and technology Limited company.
Example 2
Adding 0.5g of sepiolite into a vessel containing 30.5g of water under the state of high-speed stirring (500 r/min), stirring for 30min, reducing the rotating speed to the state of ordinary stirring (250 r/min) after complete dispersion and dissolution, adding 2g of magnesium fluosilicate, 3g of sodium fluoride and 55g of aluminum sulfate into the vessel, heating to 60-70 ℃, preserving the temperature for 1-2h, sequentially adding 5g of diethylenetriamine, 1g of graphene oxide dispersion liquid (with the concentration of 10 mg/ml) and 3g of ethylene glycol after complete dissolution of the aluminum sulfate, continuing stirring for 1h, then cooling, naturally cooling, and finally preparing a finished product, namely the freeze-resistant alkali-free liquid accelerator. The graphene oxide dispersion liquid is the graphene oxide dispersion liquid with the model XF224, which is produced by Nanjing Xifeng nano material science and technology Limited company.
Example 3
Adding 0.8g of sepiolite into a vessel containing 28.2g of water under the condition of high-speed stirring (500 r/min), stirring for 30min, reducing the rotating speed to the ordinary stirring (250 r/min) state after complete dispersion and dissolution, adding 5g of sodium fluoride and 60g of aluminum sulfate into the vessel, heating to 60-70 ℃, preserving the temperature for 1-2h, sequentially adding 3g of glycine, 2g of graphene oxide dispersion liquid (with the concentration of 10 mg/ml) and 1g of dimethyl sulfoxide after complete dissolution of the aluminum sulfate, continuously stirring for 1h, then cooling, naturally cooling, and finally preparing a finished product, namely the freeze-resistant alkali-free liquid accelerator. The graphene oxide dispersion liquid is the graphene oxide dispersion liquid with the model XF224, which is produced by Nanjing Xifeng nano material science and technology Limited company.
Comparative example 1
Adding 0.7g of sepiolite into a vessel containing 31.3g of water under the state of high-speed stirring (500 r/min), stirring for 30min, reducing the rotating speed to the state of ordinary stirring (250 r/min) after complete dispersion and dissolution, adding 5g of sodium fluoride and 58g of aluminum sulfate into the vessel, heating to 60-70 ℃, preserving the temperature for 1-2h, adding 5g of diethanol amine after complete dissolution of the aluminum sulfate, continuing stirring for 1h, then cooling and naturally cooling.
Comparative example 2
Samples were taken from a commercially available conventional suspension accelerator meeting GB/T35159-2017 and Q/CR 807-2020 standards.
In order to further illustrate the beneficial effect of the anti-freezing accelerator, the cement paste setting time test is carried out according to GB/T35159-2017 accelerator for sprayed concrete, and the test adopts the following mixture ratio:
conch p.o42.5 cement: 400g, water: 140g.
In addition, the cement mortar strength test is carried out, and the test adopts the following mixture ratio:
conch p.o42.5 cement: 900g, standard sand: 1350g, water: 450g.
All the raw materials used in the tests are placed in an environment with the temperature of minus 10 ℃ for 30min in advance, then the tests are carried out, the accelerator is doped according to 6 percent of the weight of the cement, and the water consumption subtracts the water in the liquid accelerator. And placing the mortar test mold in a freezer at the temperature of-10 ℃ for storage after the mortar strength is formed. The stability test of the alkali-free accelerator is to examine each sample in-10 ℃ and-30 ℃ environments. The test results are shown in the following table:
from the above test results, it can be seen that the samples of comparative example 1 and comparative example 2 were stably stored at-10 ℃ for less than 5 days, and the samples were crystallized and solidified to lose fluidity when they were left to stand. The anti-freezing accelerator disclosed by the invention has good low-temperature storage performance, and a sample state is stable at-30 ℃, so that the anti-freezing accelerator can be stored for a long time, and the stability time is as long as more than 60 days.
The anti-freezing alkali-free liquid accelerator prepared by the three embodiments of the invention can ensure that the initial setting time of the sea snail cement is less than 3min and the final setting time is less than 6min by 6 percent of doping amount under the condition of low temperature of-10 ℃, meets the standard requirement of GB/T35159-2017 accelerator for sprayed concrete, the strength of the mortar in 1 day is up to more than 12Mpa, the compression strength ratio in 28 days is more than 100 percent, and the anti-freezing alkali-free liquid accelerator has higher early strength and later strength.
The antifreezing alkali-free accelerator prepared by the invention can greatly improve the low-temperature stability of the accelerator, and the product has no phenomena of crystallization, precipitation and the like at the temperature of-5 ℃ to-30 ℃, and the stabilization period is more than 60 days. The concrete has good condensation effect under low temperature, obviously improves the early and later compressive strength, has low rebound rate of the sprayed concrete, and has good application effect when being applied to low-temperature sprayed concrete construction.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (9)
1. An anti-freezing accelerator is characterized in that: the anti-freezing accelerator comprises the following active ingredients in preparation raw materials in percentage by weight: 50-60% of aluminum sulfate, 2-5% of inorganic salt, 0.5-1.0% of stabilizing component, 1-3% of antifreezing component, 2-5% of organic complexing component, 0.005-0.02% of inorganic nano component and the balance of water.
2. The freeze resistant accelerator according to claim 1, characterized in that: the inorganic salt comprises at least one of sodium aluminate, magnesium fluosilicate and sodium fluoride.
3. The freeze resistant accelerator according to claim 1, characterized in that: the stabilizing component includes at least one of pseudoboehmite and sepiolite.
4. The freeze resistant accelerator according to claim 1, characterized in that: the antifreeze component comprises at least one of dimethyl sulfoxide and ethylene glycol.
5. The freeze resistant accelerator according to claim 1, characterized in that: the inorganic nano-component comprises graphene oxide.
6. The freeze resistant accelerator according to claim 5, characterized in that: the sheet diameter of the graphene oxide is 20-200nm.
7. The freeze resistant accelerator according to any one of claims 1 to 6, characterized in that: the organic complexing component comprises at least one of ethylenediamine tetraacetic acid, glycine and diethylenetriamine.
8. A preparation method of an anti-freezing accelerator is characterized by comprising the following steps: the method comprises the following steps:
and (3) uniformly mixing the stable component with water, adding inorganic salt and aluminum sulfate, heating to 60-70 ℃, adding the organic complex component, the inorganic nanometer component and the antifreezing component after the aluminum sulfate is dissolved, uniformly stirring, and cooling to obtain the antifreezing accelerator.
9. A shotcrete, comprising: the anti-freezing accelerator as claimed in any one of claims 1 to 7 is included in the raw materials for preparing the shotcrete.
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Application publication date: 20221122 |