CN110218019A - Early high-strength compound alkali-free liquid accelerator, preparation method and gunite concrete - Google Patents
Early high-strength compound alkali-free liquid accelerator, preparation method and gunite concrete Download PDFInfo
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- CN110218019A CN110218019A CN201910659832.7A CN201910659832A CN110218019A CN 110218019 A CN110218019 A CN 110218019A CN 201910659832 A CN201910659832 A CN 201910659832A CN 110218019 A CN110218019 A CN 110218019A
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- free liquid
- accelerator
- liquid accelerator
- strength composite
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- 239000007788 liquid Substances 0.000 title claims abstract description 96
- 239000011378 shotcrete Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000004567 concrete Substances 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 title abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 37
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 239000003381 stabilizer Substances 0.000 claims abstract description 25
- 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 24
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 21
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 14
- 239000004568 cement Substances 0.000 claims description 71
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 66
- 239000002131 composite material Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 40
- 239000011775 sodium fluoride Substances 0.000 claims description 33
- 235000013024 sodium fluoride Nutrition 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 26
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 24
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 23
- 239000012452 mother liquor Substances 0.000 claims description 20
- -1 alcohol amine Chemical class 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000003044 adaptive effect Effects 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 4
- 235000019792 magnesium silicate Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 230000006978 adaptation Effects 0.000 claims description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 18
- 230000001976 improved effect Effects 0.000 description 15
- 230000001276 controlling effect Effects 0.000 description 14
- 238000010276 construction Methods 0.000 description 10
- 239000011083 cement mortar Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 241000282320 Panthera leo Species 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 241001374849 Liparis atlanticus Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000008093 supporting effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000007328 Hericium erinaceus Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 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
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- 206010003549 asthenia Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 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
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- C04B2103/12—Set accelerators
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
This application discloses a kind of early high-strength compound alkali-free liquid accelerator, preparation method and gunite concretes, and the alkali-free liquid accelerator includes following components by weight: aluminum sulfate: 45%~55%；Active aluminium hydroxide: 5%~10%；Fluoride salt: 5%~10%；Hydramine: 1.5%~4%；Polyacrylamide: 0.5%~1%；Organic water-reducing agent: 1%~3%；Stabilizer: 0.8%~1%；Water: 25%~35%.
Description
Technical Field
The disclosure relates to the technical field of building materials, in particular to an early high-strength composite alkali-free liquid accelerator, a preparation method and sprayed concrete, which are mainly applied to the sprayed concrete of geotechnical engineering such as tunnels, mines, side slopes and the like.
Background
The accelerator is an additive capable of quickly setting and hardening concrete, is an indispensable material in sprayed concrete, has the functions of accelerating the quick setting and hardening of the sprayed concrete, increasing the once spraying thickness, reducing the rebound loss, preventing the concrete from falling off due to gravity, and effectively wrapping reinforcing steel bars and an arch frame to form a reinforced concrete supporting structure. The accelerator is mainly used in anchor-shotcrete support, tunnels, mines, deep foundation pits, water conservancy, side slopes and other geotechnical engineering, and is very widely applied.
The quick-setting admixture is divided into a powdery quick-setting admixture and a liquid quick-setting admixture, wherein the powdery quick-setting admixture is mainly applied to dry-sprayed concrete, and the problems of large resilience, large dust amount, large concrete later strength loss and low construction efficiency exist in the dry-sprayed concrete. The liquid accelerator is mainly applied to wet-sprayed concrete, and the wet-sprayed concrete has the advantages of small dust, high construction efficiency and high concrete strength, and is being popularized and applied in a large area. The development of wet spraying is necessarily accompanied by the development of liquid accelerators.
At present, liquid accelerators are mainly divided into an alkali type and an alkali-free type, and the alkali liquid accelerators are mainly sodium aluminate type and sodium silicate type, so that alkali aggregate reaction is easy to occur due to strong alkalinity, the later strength loss of concrete is serious, and the alkalinity has great harm to human bodies. The alkali-free liquid accelerator has the advantages of high long-term strength retention rate, no alkali or chlorine, safety, environmental protection, high durability and the like, and is gradually replacing the alkali-free liquid accelerator, so that the alkali-free liquid accelerator becomes the development trend of the liquid accelerator.
The existing alkali-free liquid accelerator has the problems of large doping amount (7-12% of the mass of cement), single material performance, poor adaptability to different cements, low accelerating effect, few active effective components, poor stability, low early strength of concrete, high price and the like, so that the popularization of the alkali-free liquid accelerator is very difficult. Therefore, further development of alkali-free liquid accelerators is required.
Disclosure of Invention
In view of the above-mentioned drawbacks and deficiencies of the prior art, it would be desirable to provide an early high strength composite alkali-free liquid accelerator and a method for preparing the same. The accelerator can effectively improve the concentration of a solution, greatly reduce the doping amount of the accelerator, shorten the initial and final setting time, improve the construction efficiency, improve the early strength and the later strength of sprayed concrete, and has good adaptability to different cements. During site construction, the method can effectively reduce resilience and dust and improve the support effect of the sprayed concrete.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
The invention provides an early high-strength composite alkali-free liquid accelerator, which comprises the following components in parts by weight:
45 to 55 percent of aluminum sulfate;
5 to 10 percent of active aluminum hydroxide;
5 to 10 percent of fluoride salt;
1.5 to 4 percent of alcohol amine;
0.5 to 1 percent of polyacrylamide;
1-3% of organic water reducing agent;
0.8 to 1 percent of stabilizer;
25 to 35 percent of water.
In some embodiments of the examples herein, the fluoride salt is selected from one or more of sodium fluoride, potassium fluoride, magnesium fluoride.
In some embodiments of the examples herein, the alcohol amine is selected from the group consisting of one or more of diethanolamine, triethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, and ethyldiethanolamine.
Further, the triethanolamine comprises 0.5-1% of triethanolamine by weight.
Further, the alcohol amine comprises diethanolamine, and the weight part of the diethanolamine is 1-3%.
In some embodiments of the examples herein, the organic water reducing agent is a polyethylene glycol based condensation polymer.
In some embodiments of the examples herein, the stabilizing agent is hydrous magnesium silicate.
On the other hand, the invention provides a preparation method of the early high-strength composite alkali-free liquid accelerator, which comprises the following steps:
step 1: mixing fluoride salt, diethanolamine and water to obtain fluoride salt solution;
step 2: heating the fluoride solution to 60-70 ℃, adding aluminum sulfate, active aluminum hydroxide and a stabilizer, and stirring at a high speed to obtain an alkali-free accelerator mother liquor;
and step 3: and adding alcohol amine, polyacrylamide and an organic water reducing agent into the alkali-free accelerator mother liquor, controlling the temperature to be 40-60 ℃, and filtering to obtain the early high-strength composite alkali-free liquid accelerator.
In some embodiments of the invention, one or more of the following technical features are also included:
A1) in the step 1, sodium fluoride is added into water at normal temperature, the mixture is rapidly stirred for 10-30 min, then diethanolamine is added, and the stirring is continued for 10-20 min, so that a sodium fluoride solution is obtained;
A2) in the step 2, when the sodium fluoride solution is heated to 60-70 ℃, aluminum sulfate and active aluminum hydroxide are added for multiple times, high-speed shearing stirring is carried out at 500-800 rpm/min, then a stabilizer is added, the temperature is controlled to be about 70 ℃, the stirring time is 90-150 min, and an alkali-free accelerator mother liquor is obtained preliminarily;
A3) and 3, compounding the alkali-free accelerator mother liquor, adding triethanolamine, polyacrylamide and an organic water reducing agent, controlling the temperature at 40-60 ℃, stirring at 300-500 rpm/min, and reacting for 60-90 min, and filtering to obtain the early high-strength composite alkali-free liquid accelerator.
In a third aspect, the invention provides sprayed concrete, which comprises the early high-strength composite alkali-free liquid accelerator, wherein the doping amount of the alkali-free liquid accelerator is 3-5% of the mass of cement in the sprayed concrete;
cement variety adaptation coefficient c of alkali-free liquid acceleratoraLess than 0.8 of the total weight of the composition,
the method for testing the cement variety adaptive coefficient comprises the following steps:
applying the alkali-free liquid accelerator to five test cement varieties in a mixing amount of 4%, and acquiring the dispersion coefficient of each subentry index aiming at different cement varieties, wherein the subentry indexes comprise an initial setting time index, a final setting time index, a 1d strength index and a 28d strength ratio index, and the adaptive coefficient caIs the sum of the discrete coefficients of each of the fractional indicators.
The specific method comprises the following steps:
applying the alkali-free liquid accelerator to five tested cement varieties in a mixing amount of 4% to perform a cement paste setting time test to obtain a setting time index of each group of cement paste, wherein the time index comprises an initial setting time index and a final setting time index, and the setting time dispersion coefficient is cνt(ratio of standard deviation sigma of cement paste setting time to average value u) as initial setting time dispersion coefficient(ratio of standard deviation of initial setting time to average value of initial setting time of cement paste) and coefficient of variation of final setting time(ratio of standard deviation of cement paste final set time to average final set time);
the alkali-free liquid accelerator is applied to five cement varieties to be tested for cement mortar strength tests at the mixing amount of 4 percent, and the strength index of each group of cement mortar is obtained, wherein the strength index comprises a 1d (one day) strength index and a 28d (28 days) strength ratio index. 1d coefficient of variation of intensity index cνsThe discrete coefficient is the ratio of the standard deviation of the 1d strength of the mortar to the average value u of the 1d strength of the mortar and the index of the 28d strength ratioIs the ratio of the standard deviation of the strength ratio of the mortar 28d to the average value of the strength ratio of the mortar 28 d.
Adaptation coefficient of cement varietyIs composed ofThe coefficient is a dimensionless index, and the standard value of the adaptive coefficient is 0.8 through a large amount of test data under the condition of meeting the standard requirement. When the value is less than the value, the liquid setting accelerator has good adaptability to different cements, and can meet the adaptability to different cement varieties; when the value is larger than the value, the adaptability of the liquid accelerator to different cement is poor, the adaptability to certain brand of cement varieties can be only met, and the liquid accelerator cannot meet related requirements when being applied to other brand of cement varieties.
The test cement is selected from the group consisting of commercially available standard cement, landscape cement, conch cement, lion cement and three gorges cement. Wherein,
and (3) reference cement: produced by the national institute of building materials science, ltd;
and (3) landscape cement: manufactured by Shandong Shanshui Cement group, Inc.;
sea snail cement: produced by Anhui conch Cement Ltd;
lion head cement: manufactured by taiyuan lion cement corporation;
three gorges cement: manufactured by gezhou dam group cement limited.
The early high-strength composite alkali-free liquid accelerator provided by the embodiment of the application can improve the accelerating effect of the accelerator to a certain extent by adding the active aluminum hydroxide, and the active aluminum hydroxide is easy to release aluminum ions in the solution. And the active aluminum hydroxide is nontoxic and harmless, relatively stable, difficult to deliquesce and free of corrosion to the steel bar.
Detailed Description
The early high-strength composite alkali-free liquid accelerator, the preparation method and the application in the construction of sprayed concrete are described in detail below.
As mentioned in the background, aluminum hydroxide is used as a common liquid accelerator in the prior art. The aluminum sulfate type liquid accelerator is added with an aluminum hydroxide component, and because the aluminum hydroxide is an amphoteric compound and has low solubility in a solution, sufficient aluminum ions (the aluminum ions are effective ions for accelerating the setting of the accelerator) cannot be provided in the hydrolysis process. Therefore, the accelerating effect of the accelerator is improved little or hardly by adding aluminum hydroxide. And certain aluminum hydroxide doping amount is reached, when saturated solubility is reached, the coagulation accelerating effect cannot be improved no matter how much aluminum hydroxide is doped, so that the initial setting time is too long, the construction of sprayed concrete is not facilitated, the slump is easy to occur, the thickness of a sprayed layer is reduced once, and the construction efficiency is influenced.
In view of the above-mentioned drawbacks of the prior art, a first aspect of embodiments of the present application provides an early high-strength composite alkali-free liquid accelerator.
The alkali-free liquid accelerator comprises the following components in parts by weight:
45 to 55 percent of aluminum sulfate;
5 to 10 percent of active aluminum hydroxide;
5 to 10 percent of fluoride salt;
1.5 to 4 percent of alcohol amine;
0.5 to 1 percent of polyacrylamide;
1-3% of organic water reducing agent;
0.8 to 1 percent of stabilizer;
25 to 35 percent of water.
In the alkali-free liquid accelerator provided by the embodiment of the application, the fluoride salt is selected from one or more of sodium fluoride, potassium fluoride and magnesium fluoride. Fluoride and sulfate ions in fluoride salts react with calcium ions, consuming a large amount of calcium ions, C3The silicon-rich layer formed by hydrolyzing the surface of S (tricalcium silicate) is difficult to form an electric double layer, the C/S (calcium-silicon ratio Ca/Si) value of the generated C-S-H (hydrated calcium silicate) is small, and moisture can continuously permeate C-S-H to C3S diffuses to C3The induction period of S disappears, thereby promoting C3And (4) hydrating the S. Meanwhile, due to a large amount of hydration heat released by the reaction, the hydration reaction of each component in the cement is promoted, a large amount of calcium silicate gel is formed, and the coagulation accelerating effect of the accelerator is improved.
In addition, active aluminum hydroxide is doped into the alkali-free liquid accelerator provided by the embodiment of the application, the accelerating effect of the accelerator can be improved to a certain degree, and the active aluminum hydroxide is easy to release aluminum ions in the solution. But after the mixing amount of the active aluminum hydroxide exceeds a certain mixing amount, the accelerating effect is not obviously improved, and the accelerating effect on the accelerating agent is weakened.
If the activated aluminum hydroxide is simply replaced, the accelerating effect on the accelerating agent is weakened after the adding amount reaches a certain amount. Therefore, fluoride salt components are added, fluoride ions in the solution can further promote the dissolution of active aluminum hydroxide and aluminum sulfate, the synergistic effect of the fluoride salt components and the aluminum sulfate and the active aluminum hydroxide can effectively improve the quick-setting effect of the quick-setting agent, the mixing amount of the quick-setting agent is reduced by 3-5%, the setting time is shortened (the initial setting time can be controlled to be about 2min, and the final setting time is less than 6 min), the construction of sprayed concrete is facilitated, the slump is not easy to occur, the thickness of a primary sprayed layer can be improved, the construction efficiency is improved, and the effect of the quick-setting agent is obviously enhanced.
In the alkali-free liquid accelerator provided by the embodiment of the application, the alcohol amine comprises 0.5-1% of triethanolamine and 1-3% of diethanolamine. Wherein the early strength of triethanolamine is promoting C3A(3CaO·Al2O3) The hydration of the calcium carbonate accelerates the formation of ettringite. The triethanolamine has a pair of unshared electrons in the molecule, is easy to form covalent bonds with metal ions to form stable complexes, and the complexes form a plurality of soluble regions in solutionThe diffusion rate of hydration products is improved, the incubation period in the cement hydration process is shortened, and the early strength is improved.
In the alkali-free liquid accelerator provided by the embodiment of the application, the organic water reducing agent is a polyethylene glycol type condensation polymer. The polyethylene glycol type condensation polymer is an organic water-reducing component and can stably exist, the content of aluminum ions in the accelerator can be improved by adding the active aluminum hydroxide and the polyethylene glycol type condensation polymer, the early strength and the later strength of concrete can be effectively improved, the later strength is almost not lost, and even is improved to a certain extent, so that the strength performance of the liquid accelerator on sprayed concrete is obviously improved. Several other water reducing agents, such as melamine type water reducing agents, polycarboxylic acid type water reducing agents, naphthalene type high efficiency water reducing agents, etc., have been tested, and have no corresponding effect after being doped or can not exist stably in a solution.
In the alkali-free liquid accelerator provided by the embodiment of the application, the stabilizing agent is hydrous magnesium silicate. Aiming at the liquid water reducing agent added with the active aluminum hydroxide and the polyethylene glycol type polycondensate, if other stabilizing agents are used for replacing hydrated magnesium silicate, the liquid accelerating agent can not achieve ideal effect.
The second aspect of the embodiments of the present application provides a preparation method of an early high-strength composite alkali-free liquid accelerator, comprising the following steps:
① firstly weighing a certain amount of water, adding sodium fluoride into the water at normal temperature, rapidly stirring for 10-30 min, then adding diethanolamine, and continuing stirring for 10-20 min to obtain a sodium fluoride solution;
② heating the sodium fluoride solution to 60-70 ℃, adding aluminum sulfate and active aluminum hydroxide for multiple times, shearing and stirring at a high speed of 500-800 rpm/min, then adding a stabilizer, controlling the temperature to be about 70 ℃, and stirring for 90-150 min to obtain an alkali-free accelerator mother liquor preliminarily;
③, compounding the alkali-free accelerator mother liquor, adding triethanolamine, polyacrylamide and an organic water reducing agent, controlling the temperature at 40-60 ℃, stirring at 300-500 rpm/min, and reacting for 60-90 min, and filtering to obtain the early high strength composite alkali-free liquid accelerator.
By adopting the early high-strength composite alkali-free liquid accelerator, the following positive effects are achieved:
1. the coagulation promoting effect is good. According to the requirements of GB/T35159-2017 accelerator for sprayed concrete, the alkali-free liquid accelerator is used for carrying out a cement paste test, and under the condition of low mixing amount (3-5% of cement mass), the initial setting time is about 2min, and the final setting time is within 6 min.
2. The early strength and the later strength are high. According to the requirements of GB/T35159-2017 accelerator for sprayed concrete, cement mortar tests are carried out, the strength of the cement mortar is about 15MPa in 1 day, and the compression strength ratio of the cement mortar reaches or even exceeds 100 percent in 28 days.
3. The stability is good. The alkali-free liquid accelerator can keep the high concentration of the solution above 65 percent without generating precipitation and crystallization.
4. The adaptability is good. The alkali-free liquid accelerator has good adaptability to cement of different brands in different producing areas.
5. In the construction process, the rebound quantity and the dust quantity of the sprayed concrete can be effectively reduced, the supporting effect is effectively improved, and the deformation of surrounding rocks is controlled.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
Example 1
The early high-strength composite alkali-free liquid accelerator comprises the following components in percentage by mass: 50% of aluminum sulfate, 10% of active aluminum hydroxide, 8% of sodium fluoride, 2% of diethanolamine, 1% of triethanolamine, 0.5% of polyacrylamide, 2% of an organic water reducing agent, 0.8% of a stabilizer and 25.7% of water.
The preparation method of the early high-strength composite alkali-free liquid accelerator comprises the following steps:
① firstly weighing 25.7% water, adding sodium fluoride into water at normal temperature, rapidly stirring for 20min, then adding diethanolamine, and continuing stirring for 10min to obtain sodium fluoride solution;
② heating sodium fluoride solution to 60 deg.C, adding aluminum sulfate and active aluminum hydroxide for multiple times, shearing and stirring at 600rpm/min, adding stabilizer, controlling temperature at 70 deg.C, stirring for 120min to obtain alkali-free accelerator mother liquor;
③, compounding the alkali-free accelerator mother liquor, adding triethanolamine, polyacrylamide and an organic water reducing agent, controlling the temperature at 40 ℃, stirring at 500rpm/min, and reacting for 60min, and filtering to obtain the early high-strength composite alkali-free liquid accelerator.
Example 2
The early high-strength composite alkali-free liquid accelerator comprises the following components in percentage by mass: 45% of aluminum sulfate, 10% of active aluminum hydroxide, 10% of sodium fluoride, 1% of diethanolamine, 1% of triethanolamine, 1% of polyacrylamide, 2% of an organic water reducing agent, 1% of a stabilizer and 29% of water.
The preparation method of the early high-strength composite alkali-free liquid accelerator comprises the following steps:
① weighing 29% water, adding sodium fluoride into water at room temperature, stirring rapidly for 30min, adding diethanolamine, and stirring for 10min to obtain sodium fluoride solution;
② heating the sodium fluoride solution to 60 ℃, adding aluminum sulfate and active aluminum hydroxide for multiple times, shearing and stirring at a high speed of 800rpm/min, then adding a stabilizer, controlling the temperature at 75 ℃, and stirring for 150min to obtain an alkali-free accelerator mother liquor preliminarily;
③, compounding the alkali-free accelerator mother liquor, adding triethanolamine, polyacrylamide and an organic water reducing agent, controlling the temperature at 50 ℃, stirring at 400rpm/min, and reacting for 75min, and filtering to obtain the early high-strength composite alkali-free liquid accelerator.
Example 3
The early high-strength composite alkali-free liquid accelerator comprises the following components in percentage by mass: 55% of aluminum sulfate, 5% of active aluminum hydroxide, 5% of sodium fluoride, 2% of diethanolamine, 1% of triethanolamine, 0.5% of polyacrylamide, 1.5% of an organic water reducing agent, 0.8% of a stabilizer and 29.2% of water.
The preparation method of the early high-strength composite alkali-free liquid accelerator comprises the following steps:
① firstly weighing 29.2% water, adding sodium fluoride into water at normal temperature, rapidly stirring for 15min, then adding diethanolamine, and continuing stirring for 15min to obtain sodium fluoride solution;
② heating sodium fluoride solution to 65 ℃, adding aluminum sulfate and active aluminum hydroxide for multiple times, shearing and stirring at a high speed of 600rpm/min, then adding a stabilizer, controlling the temperature at 70 ℃, and stirring for 120min to obtain an alkali-free accelerator mother liquor preliminarily;
③, compounding the alkali-free accelerator mother liquor, adding triethanolamine, polyacrylamide and an organic water reducing agent, controlling the temperature at 45 ℃, stirring at 400rpm/min, and reacting for 80min, and filtering to obtain the early high-strength composite alkali-free liquid accelerator.
Example 4
The early high-strength composite alkali-free liquid accelerator comprises the following components in percentage by mass: 45% of aluminum sulfate, 8% of active aluminum hydroxide, 7% of sodium fluoride, 1.5% of diethanolamine, 1% of triethanolamine, 1% of polyacrylamide, 3% of an organic water reducing agent, 0.8% of a stabilizer and 32.7% of water.
The preparation method of the early high-strength composite alkali-free liquid accelerator comprises the following steps:
① firstly weighing 32.7% water, adding sodium fluoride into water at normal temperature, rapidly stirring for 15min, then adding diethanolamine, and continuing stirring for 15min to obtain sodium fluoride solution;
② heating sodium fluoride solution to 65 ℃, adding aluminum sulfate and active aluminum hydroxide for multiple times, shearing and stirring at a high speed of 600rpm/min, then adding a stabilizer, controlling the temperature at 70 ℃, and stirring for 120min to obtain an alkali-free accelerator mother liquor preliminarily;
③, compounding the alkali-free accelerator mother liquor, adding triethanolamine, polyacrylamide and an organic water reducing agent, controlling the temperature at 45 ℃, stirring at 400rpm/min, and reacting for 80min, and filtering to obtain the early high-strength composite alkali-free liquid accelerator.
Example 5
The early high-strength composite alkali-free liquid accelerator comprises the following components in percentage by mass: 50% of aluminum sulfate, 5% of active aluminum hydroxide, 7% of sodium fluoride, 2% of diethanolamine, 0.5% of triethanolamine, 0.5% of polyacrylamide, 2.5% of an organic water reducing agent, 1% of a stabilizer and 31.5% of water.
The preparation method of the early high-strength composite alkali-free liquid accelerator comprises the following steps:
① weighing 31.5% water, adding sodium fluoride into water at room temperature, stirring rapidly for 15min, adding diethanolamine, and stirring for 10min to obtain sodium fluoride solution;
② heating the sodium fluoride solution to 60 ℃, adding aluminum sulfate and active aluminum hydroxide for multiple times, shearing and stirring at a high speed of 500rpm/min, then adding a stabilizer, controlling the temperature at 70 ℃, and stirring for 150min to obtain an alkali-free accelerator mother liquor preliminarily;
③, compounding the alkali-free accelerator mother liquor, adding triethanolamine, polyacrylamide and an organic water reducing agent, controlling the temperature at 45 ℃, stirring at 300rpm/min, and reacting for 90min, and filtering to obtain the early high-strength composite alkali-free liquid accelerator.
Comparative example 6
The accelerator comprises the following components in percentage by weight: 55% of aluminum sulfate, 5% of aluminum hydroxide, 2% of diethanolamine, 0.5% of triethanolamine, 0.5% of polyacrylamide, 1% of stabilizer and 36% of water.
Comparative example 7
The accelerator comprises the following components in percentage by weight: 55% of aluminum sulfate, 8% of sodium fluoride, 1% of diethanolamine, 0.5% of triethanolamine, 0.5% of polyacrylamide, 1% of stabilizer and 34% of water.
Comparative example 8
Commercially available alkali-free liquid accelerator: basf Haoke mining chemical (China) Co., Ltd, alkali-free liquid accelerator, MeiguoSA160, which is obtained by tests, the mixing amount is 6-10%, the initial setting time is 3min, the final setting time is about 10min, and the 28-day strength retention rate is 87%.
The invention obtains satisfactory technical effect through test and trial, and the effective test data is as follows:
and (3) carrying out tests on the setting time of the cement paste and the compressive strength of the cement mortar according to the requirements of GB/T35159-2017 accelerator for sprayed concrete. The mixing amount of the liquid accelerator is calculated according to the weight percentage of the cement, the liquid accelerator is the product prepared in the embodiment 1-5, 6-7 are comparative example accelerators, and 8 is a commercially available alkali-free liquid accelerator.
And (3) measuring the setting time of the cement paste:
cement 400g
140g of water (water content in the liquid accelerator should be subtracted)
And (3) determining the compressive strength of cement mortar:
cement 900g
Standard sand 1350g
450g of water
The test results are shown in table 1:
TABLE 1 Effect of the alkali-free liquid accelerator
As can be seen from Table 1, all indexes of the alkali-free liquid accelerator meet the requirements of GB/T35159-2017 Accelerator for sprayed concrete, the setting time is short, the early strength of the mortar can be effectively improved, and the later strength is basically not lost.
In order to verify the adaptability of the alkali-free liquid accelerator to different cements, 5 types of cements commonly used in engineering are selected, the setting time and the mortar strength are respectively measured, and the test results are shown in table 2. Sample 1 was selected as the accelerator, and the cements were standard cement, landscape cement, sea snail cement, lion cement and three gorges cement.
TABLE 2 application Effect of the accelerator on different cements
As can be seen from Table 2, the set accelerators all meet the requirements of the specification for these 5 cements. Through calculation, the adaptive coefficient of the alkali-free liquid accelerator to different cements is 0.3 and is less than the standard value of 0.8, which indicates that the alkali-free liquid accelerator has better adaptability to the 5 cements. Because the cement has certain representativeness and is applied in field engineering in a large amount, the accelerator has good adaptability to different cements.
TABLE 3 application Effect of the comparative examples 6, 7 and 8 setting accelerator on different cements
The liquid setting accelerators of comparative examples 6, 7 and 8 selected from Table 3 are respectively mixed into the 5 different cements according to the respective optimal mixing amount, and the data in the table can obtain that on one hand, the liquid setting accelerator of the comparative examples is used, the mixing amount is larger than that of the liquid setting accelerator of the embodiment, the setting time is longer than that of the embodiment, and the mortar strength is lower than that of the embodiment; on the other hand, the adaptive coefficient of the accelerator 6 to different cements is 1.3, the adaptive coefficient of the accelerator 7 to different cements is 1.45, and the adaptive coefficient of the accelerator 8 to different cements is 1.31, which are both larger than the standard value of 0.8. The adaptability of the accelerating agents to different types of cement is poor.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (10)
1. An early high-strength composite alkali-free liquid accelerator is characterized in that: the alkali-free liquid accelerator comprises the following components in parts by weight:
45 to 55 percent of aluminum sulfate;
5 to 10 percent of active aluminum hydroxide;
5 to 10 percent of fluoride salt;
1.5 to 4 percent of alcohol amine;
0.5 to 1 percent of polyacrylamide;
1-3% of organic water reducing agent;
0.8 to 1 percent of stabilizer;
25 to 35 percent of water.
2. The early high strength composite alkali-free liquid accelerator as claimed in claim 1, wherein: the fluoride salt is selected from one or more of sodium fluoride, potassium fluoride and magnesium fluoride.
3. The early high strength composite alkali-free liquid accelerator as claimed in claim 1, wherein: the alcohol amine is selected from one or more of diethanolamine, triethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine and ethyldiethanolamine.
4. The early high strength composite alkali-free liquid accelerator as claimed in claim 3, wherein: the triethanolamine comprises 0.5 to 1 weight percent of triethanolamine.
5. The early high-strength composite alkali-free liquid accelerator as claimed in claim 3 or 4, wherein: the alcohol amine comprises 1-3% of diethanolamine by weight.
6. The early high strength composite alkali-free liquid accelerator as claimed in claim 1, wherein: the organic water reducing agent is polyethylene glycol polycondensate.
7. The early high strength composite alkali-free liquid accelerator as claimed in claim 1, wherein: the stabilizing agent is hydrous magnesium silicate.
8. A method for preparing the early high strength composite alkali-free liquid accelerator according to any one of claims 1 to 7, comprising the steps of:
step 1: mixing fluoride salt, diethanolamine and water to obtain fluoride salt solution;
step 2: heating the fluoride solution to 60-70 ℃, adding aluminum sulfate, active aluminum hydroxide and a stabilizer, and stirring at a high speed to obtain an alkali-free accelerator mother liquor;
and step 3: and adding alcohol amine, polyacrylamide and an organic water reducing agent into the alkali-free accelerator mother liquor, controlling the temperature to be 40-60 ℃, and filtering to obtain the early high-strength composite alkali-free liquid accelerator.
9. The method for preparing the early high-strength composite alkali-free liquid accelerator as claimed in claim 8, further comprising one or more of the following technical characteristics:
A1) in the step 1, sodium fluoride is added into water at normal temperature, the mixture is rapidly stirred for 10-30 min, then diethanolamine is added, and the stirring is continued for 10-20 min, so that a sodium fluoride solution is obtained;
A2) in the step 2, when the sodium fluoride solution is heated to 60-70 ℃, aluminum sulfate and active aluminum hydroxide are added for multiple times, high-speed shearing stirring is carried out at 500-800 rpm/min, then a stabilizer is added, the temperature is controlled to be about 70 ℃, the stirring time is 90-150 min, and an alkali-free accelerator mother liquor is obtained preliminarily;
A3) and 3, compounding the alkali-free accelerator mother liquor, adding triethanolamine, polyacrylamide and an organic water reducing agent, controlling the temperature at 40-60 ℃, stirring at 300-500 rpm/min, and reacting for 60-90 min, and filtering to obtain the early high-strength composite alkali-free liquid accelerator.
10. A shotcrete, comprising: the sprayed concrete comprises the early high-strength composite alkali-free liquid accelerator as defined in any one of claims 1-7, wherein the mixing amount of the alkali-free liquid accelerator is 3-5% of the mass of cement in the sprayed concrete;
cement variety adaptation coefficient c of alkali-free liquid acceleratoraLess than 0.8 of the total weight of the composition,
the method for testing the cement variety adaptive coefficient comprises the following steps:
applying the alkali-free liquid accelerator to five test cement varieties in a mixing amount of 4%, and acquiring the dispersion coefficient of each subentry index aiming at different cement varieties, wherein the subentry indexes comprise an initial setting time index, a final setting time index, a 1d strength index and a 28d strength ratio index, and the adaptive coefficient caIs the sum of the discrete coefficients of each of the fractional indicators.
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Application publication date: 20190910 |