CN102219425A - Alkali-free liquid accelerating agent and preparation method thereof - Google Patents
Alkali-free liquid accelerating agent and preparation method thereof Download PDFInfo
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- CN102219425A CN102219425A CN 201110095008 CN201110095008A CN102219425A CN 102219425 A CN102219425 A CN 102219425A CN 201110095008 CN201110095008 CN 201110095008 CN 201110095008 A CN201110095008 A CN 201110095008A CN 102219425 A CN102219425 A CN 102219425A
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- 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
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the technical field of tunnel construction, and relates to an alkali-free liquid accelerating agent for tunnel wet jet concrete and a preparation method thereof. The alkali-free liquid accelerating agent is characterized in that aluminium sulphate is adopted to serve as a main accelerating component; aluminium is added to an aluminium sulphate solution to be polymerized in a form of aluminium fluoride; aluminium ions are introduced to the greatest extent so as to reduce other ion introduction; and the accelerating effect is ensured. The alkali-free liquid accelerating agent comprises the following components in percentage by mass: 30-55% of aluminium sulphate, 5-15% of aluminium hydroxide, 10-30% of hydrofluoric acid, 0.5-5% of water glass, 0-0.2% of stabilizing agent, and the balance of water. For jetting concrete, the alkali-free liquid accelerating agent disclosed by the invention has the positive effects that: ordinary cement can be initially solidified within 2 min in lower doping quantity and finally solidified within 4 min; the 1d strength of cement plaster can achieve above 15 MPa; the 28d compressive strength ratio is more than 100%; and the alkali-free liquid accelerating agent has good adaptability to different types of cements.
Description
Technical field
The invention belongs to the tunnel construction technology field, relate to the liquid alkali-free quick-coagulant of a kind of wet spraying concrete, relate in particular to a kind of liquid accelerating chemicals of alkali-free and preparation method thereof that is applied in the tunnel wet shotcreting.
Background technology
Accelerating chemicals is a kind of chemical admixture that can make the cement rapid coagulation, and its use can make cement setting and harden in a short period of time, is mainly used in sprayed concrete and the engineering construction of injection mortar.In recent years, the wet spraying concrete making technology has obtained using widely because construction environment is good, springback capacity is low, high efficient construction and progressively replace traditional dried pressure spray process.And the accelerating chemicals that cooperates this construction technology to use is liquid accelerating chemicals.
The liquid accelerator that the wet spraying concrete is commonly used comprises alkaline liquid accelerating agent and the alkali-free liquid accelerator based on water glass, sodium aluminate at present.Wherein, the alkalinity height of alkaline liquid accelerating agent, easily the health to the construction workman damages, and after it mixes concrete, and endurance quality descends the later strength of sprayed concrete obviously to be reduced and impervious etc.Therefore for the consideration of accelerating chemicals to the influence of aspects such as sprayed concrete mechanical property, workability and constructional method, the liquid accelerating chemicals of alkali-free is the developing direction of main flow accelerating chemicals in the world.
Also successfully developed the liquid accelerating chemicals of some alkali-frees in recent years both at home and abroad.The contriver is through finding that to the prior art and the Searches of Patent Literature the main rapid hardening composition in the liquid accelerating chemicals of present alkali-free is Tai-Ace S 150 mostly.The rapid hardening composition is mainly the Ca(OH that the aluminum ion in the Tai-Ace S 150 can produce with hydrated cementitious) products such as 2 water generation reaction calcium aluminates, aquation calcium sulphoaluminate, cement slurry is produced condense; But the introducing of the sulfate ion in the Tai-Ace S 150 will make the sulfate ion concentration in the hydrated cementitious environment increase, and cause ettringite content increase in the hydrated product, delay the hydration process of cement clinker C3A, prolong time of coagulation.Therefore meet the requirements of and just must use more Tai-Ace S 150 time of coagulation.Therefore at present be that the alkali-free liquid accelerator of main rapid hardening composition uses volume all very big (the highest volume can reach 12%) with Tai-Ace S 150.When the volume of Tai-Ace S 150 is very big, in concrete, can introduce high-load sulfate radical, and the possibility that concrete makes sprayed concrete the secondary ettringite occur when sulphate content is higher increases greatly, the formation of secondary ettringite can form expansion stress, makes concrete cracking even completely lose mechanical property.
Summary of the invention
The present invention provides a kind of liquid accelerating chemicals of the concrete alkali-free of Tunnel Engineering wet spraying and preparation method thereof that is exclusively used in for overcoming deficiency of the prior art.
When the contriver finds to adopt alkali-free or low alkali accelerating chemicals after deliberation, that mainly plays the rapid hardening effect in the composition of accelerating chemicals is aluminium salt, as Tai-Ace S 150, active aluminium hydroxide etc., triturating that therefore we can say alkali-free liquid setting accelerator mainly is to carry out around the stabilizing solution of preparation high aluminium content.
The contriver finds also that after deliberation the existence form of aluminium in solution has: Al
3+, AlOH
2+, Al(OH)
2 +, Al(OH)
3, AlO
2 -Five kinds of forms, if add aluminum ion and other material formation complex ions state, then the form that exists in solution of aluminum ion is more.Take a broad view of various research document and patents, all do not relate to for the electrochemical conditions of aluminum ion stable existence in solution, peak concentration etc. about liquid accelerator.The applicant finds after deliberation: under the condition of alkali-free, make aluminum ion stable existence in the solution, Al in solution
3+Be not converted into Al(OH)
3Crystal can only keep the pH value of solution to be lower than 4 ~ 4.5.At pH value is 6 ~ 9 o'clock, Al(OH)
3Distribution coefficient higher, very easily because Al(OH)
3Concentration surpass saturation concentration and crystallization take place.The development alkali-free liquid accelerator must carry out in sour environment, and synthetic accelerating chemicals afterwards also must be in stable sour environment.And aluminum ion is the amphoteric metal ion, with strong acid, be acid as the salt of formation such as sulfuric acid, hydrochloric acid, can satisfy the condition of stable existence, but take all factors into consideration the Rust of Rebar in Concrete problem, available aluminium salt has only Tai-Ace S 150.
Drawback for fear of single rapid hardening composition Tai-Ace S 150 existence, and the while can be improved the rapid hardening effect of alkali-free quick-coagulant, technical scheme proposed by the invention is: in the liquid accelerating chemicals of alkali-free, adopt Tai-Ace S 150 as main rapid hardening composition, aluminium is added alum liquor with the form of aluminum fluoride carry out polymerization, reach maximum introducing aluminum ion and reduce the purpose that other ion is introduced, guarantee the rapid hardening effect.
In the liquid accelerating chemicals of alkali-free proposed by the invention, adding has water glass to use in the present invention as coordination agent, main purpose is to allow the fluorine in the solution exist with silicofluoride ionic form earlier, thereby reduces the influence to the sprayed concrete early strength as much as possible.
In the liquid accelerating chemicals of alkali-free proposed by the invention, adding has stablizer, makes the accelerating chemicals of preparation crystalline deposit not occur under long-term storage; The stablizer that the present invention uses is carboxylic-acid, amides organism, and one or both that can select formic acid, acetate, vinylformic acid, acrylamide, polyacrylamide for use are mixed with.
The liquid accelerating chemicals of a kind of alkali-free proposed by the invention is made up of Tai-Ace S 150, aluminum fluoride, water glass and stablizer; Wherein aluminum fluoride is made by hydrofluoric acid and aluminium hydroxide reaction; Stablizer is mixed or composite making by carboxylic-acid, amides organism list; The mass percent of each component is: Tai-Ace S 150: 30～55%, and aluminium hydroxide: 5～15%, hydrofluoric acid: 10～30%, water glass: 0.5～5%, stablizer: 0～0.2%, rest part is a water.
The liquid accelerating chemicals raw materials for production of the alkali-free that the present invention proposes are easy to get, equipment used does not have particular requirement, simple to operate, the accelerating chemicals product have doping level few (for cement quality 2～6%), extended storage stability is good, to the extensive characteristics such as (being applicable to ordinary Portland cement, Portland blast powder, coal ash silicate cement and composite Portland cement etc.) of suitability of cement type.
The Tai-Ace S 150 of selecting for use among the present invention is technical grade 18 water Tai-Ace S 150, Al
2O
3Content, can be crushed to Tai-Ace S 150 below the 1mm for improving the dissolution rate of Tai-Ace S 150 greater than 15%.The preferable amount of Tai-Ace S 150 is 40～50% among the present invention.
The aluminium hydroxide that uses among the present invention is commercially available industrial aluminium hydroxide, can be crystalline aluminium hydroxide, also can be powdered amorphous aluminium hydroxide, and alumina content is greater than 60%.In general, the active height of amorphous aluminium hydroxide, easier being dissolved in the hydrofluoric acid.The preferable amount of aluminium hydroxide is 7～10% among the present invention.
Hydrofluoric acid is mainly used in the dissolved hydrogen aluminum oxide, is the technical grade hydrofluoric acid solution, requires HF content 〉=40%.The preferable amount of hydrofluoric acid is 15～25% among the present invention.Hydrofluoric acid and aluminium hydroxide react prepared aluminum fluoride content and are mainly decided by the amount of aluminium hydroxide, and the shared liquid accelerating chemicals mass percent of aluminum fluoride is 5.4%～16%.
Water glass is used in the present invention as a kind of coordination agent, and main purpose is to allow the fluorine in the solution exist with silicofluoride ionic form earlier, thereby reduces the influence to the sprayed concrete early strength as much as possible.Can select the liquid service water glass of modulus M=1.0～1.5 for use.The preferable amount of water glass is 1.5～2.5% among the present invention.
The stablizer that the present invention uses as carboxylic-acid, amides organism list is miserable or composite making, one or both that can select formic acid, acetate, vinylformic acid, acrylamide, polyacrylamide for use are mixed with, and main purpose is to make the accelerating chemicals of preparation crystalline deposit not occur under long-term storage.Preferable amount is 0.05～0.1% among the present invention.
Preparation method of the present invention is easy, can prepare at normal temperatures, has avoided the required heating building-up process of existing accelerating chemicals synthesis technique, and preparation process is simple.Concrete preparation method is as follows:
The first step: take by weighing hydrofluoric acid, place plastic containers, aluminium hydroxide is slowly added in the hydrofluoric acid, after question response is finished, collect reacted aluminun fluoride solution in container;
Second step: Tai-Ace S 150 is added in the entry, stir and make the Tai-Ace S 150 dissolving;
The 3rd step: the aluminun fluoride solution that the first step is made makes solution with second step and mixes, stirs, and slowly adds water glass solution and stablizer, and stirring promptly gets alkali-free liquid state accelerating chemicals of the present invention until the uniform liquid of one-tenth.
Concrete application method of the present invention is: according to ordinary method liquid accelerating chemicals of the present invention is joined in the sprayed concrete mixture at the nozzle place, its consumption is 2～6% of a cement quality, and preferable amount is 3～5%.
The present invention has following positive effect for sprayed concrete:
1. according to the experiment condition of JC477-2005, the present invention can make Portland cement initial set in 2 minutes, final set in 4 minutes in (3～5%) under the lower volume;
2. according to the experiment condition of JC477-2005, the present invention can make the 1d intensity of sand-cement slurry reach more than the 15MPa, and the 28d compressive strength rate is greater than 100%;
3. the liquid accelerating chemicals of alkali-free provided by the present invention has good adaptability to the cement of different varieties.
Embodiment
The liquid accelerating chemicals of a kind of alkali-free, used mass percent is as shown in table 1.
Table 1 preparation embodiment mass percent
| ? | Tai-Ace S 150 | Aluminium hydroxide | Hydrofluoric acid | Water glass | Stablizer | Water |
| Preparation embodiment 1 | 45% | 7% | 20% | 1.5% | 0.05%(vinylformic acid) | Surplus |
| Preparation embodiment 2 | 50% | 5% | 15% | 2% | 0.10%(acetate) | Surplus |
| Preparation embodiment 3 | 40% | 10% | 25% | 2.5% | The 0.05%(acrylamide) | Surplus |
| Preparation embodiment 4 | 55% | 5% | 10% | 0.5% | 0.20%(0.10% vinylformic acid+0.10 polyacrylamide) | Surplus |
| Preparation embodiment 5 | 30% | 15% | 30% | 5% | 0 | Surplus |
The preparation process of the liquid accelerating chemicals of alkali-free of the present invention:
The mass percent of 1 component and proportioning in conjunction with the embodiments:
The first step: take by weighing hydrofluoric acid 200 grams, place plastic containers, 70 gram aluminium hydroxides are slowly added in the hydrofluoric acid, after question response is finished, collect reacted aluminun fluoride solution in container;
Second step: 450 gram Tai-Ace S 150 are added in the entry, stir and make the Tai-Ace S 150 dissolving;
The 3rd step: the aluminun fluoride solution that the first step is made makes solution with second step and mixes, stirs, and slowly adds water glass solutions and 0.5 gram vinylformic acid that weight is 15 grams, and stirring promptly gets alkali-free liquid state accelerating chemicals of the present invention until the uniform liquid of one-tenth.
The preparation process of embodiment 2,3,4,5 is with the mass percent difference of embodiment 1(component)
Application Example
The test of cement paste time of coagulation and sand-cement slurry ultimate compression strength is carried out in requirement according to JC477-2005 " sprayed concrete accelerating chemicals ".Wherein the liquid accelerating chemicals consumption of alkali-free is according to the percentage calculation of cement weight.
Cement paste test time of coagulation:
Cement 400g
Water 160g
The sand-cement slurry intensity test:
Cement 900g
Standard sand 1350g
Water 450g
The accelerating chemicals volume is that 5% of cement weight joins in the cement slurry.Experimental result is as shown in table 2.
Table 2 test-results
Liquid accelerator provided by the invention can make under 5% volume and satisfy the presetting period time of coagulation of cement paste less than the requirement less than 6 minutes of 3 minutes, final setting time, mortar 1d ultimate compression strength is greater than 10MPa, the 28d compressive strength rate is greater than 100%, reach the requirement of accelerating chemicals acceptable end product, and have extraordinary cement adaptability, can make dissimilar cement satisfy the construction requirement of sprayed concrete.
Claims (8)
1. the liquid accelerating chemicals of an alkali-free, it is characterized in that: the liquid accelerating chemicals of described alkali-free, adopt Tai-Ace S 150 as main rapid hardening composition, aluminium is added alum liquor with the form of aluminum fluoride carry out polymerization, reach maximum introducing aluminum ion and reduce the purpose that other ion is introduced, guarantee the rapid hardening effect; The liquid accelerating chemicals of described alkali-free is made up of Tai-Ace S 150, aluminum fluoride, water glass and stablizer; Wherein aluminum fluoride is made by hydrofluoric acid and aluminium hydroxide reaction; The mass percent of each component is: Tai-Ace S 150: 30～55%, and aluminium hydroxide: 5～15%, hydrofluoric acid: 10～30%, water glass: 0.5～5%, stablizer: 0～0.2%, rest part is a water.
2. according to the liquid accelerating chemicals of the described a kind of alkali-free of claim 1, it is characterized in that: the preferable amount of Tai-Ace S 150 is 40～50%.
3. according to the liquid accelerating chemicals of the described a kind of alkali-free of claim 1, it is characterized in that: the preferable amount of aluminium hydroxide is 7～10%.
4. according to the liquid accelerating chemicals of the described a kind of efficient alkali-free of claim 1, it is characterized in that: the preferable amount of aluminum fluoride is 5.4%～16%.
5. according to the liquid accelerating chemicals of the described a kind of alkali-free of claim 1, it is characterized in that: the preferable amount of water glass is 1.5～2.5%.
6. according to the liquid accelerating chemicals of the described a kind of alkali-free of claim 1, it is characterized in that: the preferable amount of stablizer is 0.05～0.1%.
7. according to claim 1 or the liquid accelerating chemicals of 6 described a kind of alkali-frees, it is characterized in that: described stablizer is miserable or composite the making of carboxylic-acid, amides organism list, and one or both that can select formic acid, acetate, vinylformic acid, acrylamide, polyacrylamide for use are mixed with.
8. the preparation method of the liquid accelerating chemicals of an alkali-free, it is characterized in that: concrete preparation process is as follows:
1), take by weighing hydrofluoric acid, place plastic containers, aluminium hydroxide is slowly added in the hydrofluoric acid, after question response is finished, collect reacted aluminun fluoride solution in container;
2), Tai-Ace S 150 is added in the entry, stir and make the Tai-Ace S 150 dissolving;
3), with 1) aluminun fluoride solution that makes of step and second step make solution and mix, stir, and slowly adds water glass solution and stabiliser solution, stir until the uniform liquid of one-tenth and promptly get described alkali-free liquid state accelerating chemicals.
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