CN105503016A - High-strength sulfur-free alkali-free liquid accelerator and preparation method thereof - Google Patents
High-strength sulfur-free alkali-free liquid accelerator and preparation method thereof Download PDFInfo
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- CN105503016A CN105503016A CN201510957363.9A CN201510957363A CN105503016A CN 105503016 A CN105503016 A CN 105503016A CN 201510957363 A CN201510957363 A CN 201510957363A CN 105503016 A CN105503016 A CN 105503016A
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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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- 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
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- 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
The invention discloses a high-strength sulfur-free alkali-free liquid accelerator and a preparation method and application thereof. The high-strength sulfur-free alkali-free liquid accelerator is prepared from, by weight, nano aluminum oxide 10-25%, nano silicon dioxide 15-27%, trifluoroacetic acid 5-12%, organic dispersant 1-5%, a stabilizing agent 1-3%, a suspending agent 0.5-1.5% and the balance water, wherein the total weight is complemented to reach 100%. The high-strength sulfur-free alkali-free liquid accelerator can be used in the sprayed concrete wet-spraying industry, the alkali content of the accelerator is smaller than 1%, a stable phase is more than 6 months, the 1d compressive strength is up to 23.7 MPa, the 28d compressive strength ratio is as high as 125%, the technical requirements of JC477-2005 'accelerators for shotcrete' can be met when the mixing amount is 4-5%, and the high-strength sulfur-free alkali-free liquid accelerator is a high-strength alkali-free accelerator and can be widely used for primary supporting and first-aid repair of highways, railways, coal mines, municipal administration and other projects.
Description
Technical field
The invention belongs to additive for building material technical field, particularly relate to a kind of tunnel and tunnel wet spraying concrete construction high-strength without sulphur alkali-free liquid accelerator and its preparation method and application.
Background technology
Accelerating chemicals is the admixture that cement concrete rapid coagulation is hardened, and is mainly used in tunnel construction of shotcrete and mortar first-aid repair construction.Domesticly at present generally use alkaline pulvis accelerating chemicals, although the short solidifying effect of these powder accelerators is fine, low price, but because its alkalinity is high, more serious corrosion is caused to construction worker's eyes and skin, later strength loss is large, easily causes the problems such as rebound degree is high, dust pollution is serious in alkali, construction.
In recent years, along with the development of wet spraying concrete technology, wet spraying process just progressively replaces dry process, and liquid accelerator also arises at the historic moment, but these accelerating chemicalss are mostly in strong basicity, there are the problems such as later strength loss is large, corrodibility is strong, poor durability, injection springback capacity are high equally.
The appearance of alkali-free quick-coagulant solves the series of problems of conventional alkaline accelerating chemicals alkali content height initiation, advantages such as having safety and environmental protection, corrosion-free, good endurance, mechanical property are good, injection resilience is low.In the world, the accelerating chemicals being accustomed to alkali content to be less than or equal to 1% is called alkali-free quick-coagulant.Because the development of alkali-free quick-coagulant is at the early-stage, technical development is also immature, and alkali-free quick-coagulant still exists urgent problem.
1. alkali content is high.From patent disclosed in current, partial monopoly is called alkali-free quick-coagulant, but the alkali introduced in its formula is often beyond 1%.Shenyang University of Technology's publication (200910220171.4), its alkali content is up to 29.51%; China Railway Tunnel Group Co's publication (201110095008.7), alkali-free quick-coagulant by name, and in actual formula, alkali content reaches as high as 2.54%.The accelerating chemicals that alkali content is relatively higher, not only corrodes the health of construction worker, late strength of concrete also can be caused to lose, affect concrete weather resistance.
2. volume is large.The starting material major part preparing alkali-free quick-coagulant is at present Tai-Ace S 150, and the solubleness of Tai-Ace S 150 is limited, and what alkali-free quick-coagulant solid content can not be done is very high, otherwise very easily occurs wild effect.The patent (200610098296.0) of Jiangsu Botexin Materials Co., Ltd's application; The patent (WO00/78688A1) of MBT Holding AG of Switzerland application, its accelerating chemicals prepared volume in concrete is large, usual volume is the 7-10% of cement, have even up to 12%, concrete production cost is high, to such an extent as to construction party cannot accept the alkali-free quick-coagulant of high additive high price.
3. sulfate radical content is large.Patent disclosed in Chinese patent 200510107216.9, main component is vitriol, and the sulfate radical wherein introduced reaches as high as 25%.The introducing of a large amount of sulfate radical can cause the generation of secondary ettringite in concrete, forms great expansion stress at inside concrete, and then causes concrete cracking even to lose mechanical property.
4. stationary phase is short.The main short solidifying component of alkali-free quick-coagulant is aluminum ion, and aluminum ion can occur to be hydrolyzed coagulation in aqueous, causes accelerating chemicals that irreversible deposit to get crystal phenomenon occurs.Easily there is deposit to get crystal phenomenon in lay up period.The disclosed a kind of alkali-free quick-coagulant of United States Patent (USP) (US2012/0085266A1), stationary phase is only one month; The disclosed a kind of alkali-free quick-coagulant of United States Patent (USP) (US8118930B2), stationary phase is 8 weeks.Stationary phase is too short, and under transport and the condition not in time of use, accelerating chemicals is once irreversible precipitation occurs cannot re-use.
5. early strength is low.At present, many investigators begin one's study and use novel material as the main short solidifying component of accelerating chemicals, and wherein fluorochemical enjoys favor.The disclosed a kind of alkali-free quick-coagulant of Chinese patent (201210495755.4), main component is Tai-Ace S 150, magnesium sulfate and magnesium silicofluoride.The alkali-free quick-coagulant of this kind of fluoride, volume is low, and accelerating chemicals is effective, but due to the special role of fluorion, a small amount of fluorion can play the effect of enhancing, but the product that a large amount of fluorion makes the hydrated cementitious initial stage be formed wraps up cement granules, hinders C
3the aquation of S, cause Behavior of Hardened Cement Paste early strength on the low side, even intensity is defective.
Summary of the invention
The object of the invention is to solve above-mentioned alkali-free quick-coagulant problems faced, and provide a kind of high-strength without sulphur alkali-free liquid accelerator; Another object of the present invention is to provide the preparation method of above-mentioned high-strength without sulphur alkali-free liquid accelerator, and the present invention also has an object to be to provide above-mentioned high-strength without the application of sulphur alkali-free liquid accelerator in sprayed concrete.
Technical scheme of the present invention is: a kind of high-strength is without sulphur alkali-free liquid accelerator, and the weight percent that its feed composition and each component account for raw material total amount is as follows:
Nano aluminium oxide: 10-25%,
Nano silicon: 15-27%,
Trifluoroacetic acid: 5-12%,
Organic dispersing agent: 1-5%
Stablizer: 1-3%,
Suspension agent: 0.5-1.5%,
Surplus is water, and gross weight supplies 100%.
The weight percent that its feed composition preferred and each component account for raw material total amount is as follows: nano aluminium oxide: 15-20%,
Nano silicon: 18-24%,
Trifluoroacetic acid: 7-10%,
Organic dispersing agent: 2-4%
Stablizer: 1.5-2.5%,
Suspension agent: 0.7-1%,
Surplus is water, and gross weight supplies 100%.
The particle diameter of preferably above-mentioned nano aluminium oxide is between 5-20nm, and it is as main short solidifying component, preferably active high γ-Al
2o
3.
The particle diameter of preferably above-mentioned nano silicon is between 20-100nm, and it is as main enhancement component.
The effect of above-mentioned trifluoroacetic acid is to dissolve nano aluminium oxide and nano silicon, and meanwhile, the introducing of a small amount of fluorine contributes to shortening cement setting time.
Preferably above-mentioned organic dispersing agent is any one in propylene glycol, ethylene glycol or ethylene glycol monobutyl ether, and its effect makes nano particle be homogeneously dispersed state.
Preferably above-mentioned stablizer is a-amino acid; Be more preferably any one in glycine or L-Ala.Its effect is the stationary phase being extended accelerating chemicals storage by complex reaction, keeps dispersion liquid long-term storage and without obvious sediment.
Preferably above-mentioned suspension agent is any one in polyoxyethylene glycol or polyacrylamide.Its effect is by absorption and Coulomb repulsion or sterically hinderedly makes Granular composite.
Present invention also offers the method for above-mentioned high-strength without sulphur alkali-free liquid accelerator, its concrete steps are as follows:
1) water is added in water bath containers be heated to 65-75 DEG C;
3) under Keep agitation condition, nano aluminium oxide and nano silicon are added to the water;
4) slowly drip trifluoroacetic acid with constant flow pump, time for adding completes at 1.5-2h;
5) under heat-retaining condition, add stablizer, Keep agitation 0.5-1h to be translucent suspension to liquid phase;
6) translucent suspension is transferred in the normal high-speed shearing emulsion machine in laboratory;
7) add organic dispersing agent and suspension agent, start high-speed shearing emulsion machine, rotating speed is between 5000-8000r/min, and emulsification times is 0.5-1h, obtains high-strength without sulphur alkali-free liquid accelerator.
Present invention also offers above-mentioned high-strength without the application of sulphur alkali-free liquid accelerator in sprayed concrete.Conveniently join in sprayed concrete mixture without sulphur alkali-free liquid accelerator at nozzle place by high-strength, its volume is generally the 4-5% of cement quality.
The invention provides a kind of wet spraying the reinforcement of concrete without sulphur alkali-free liquid accelerator, be characterized in: use nano aluminium oxide, silicon-dioxide, trifluoroacetic acid, amino acid etc. to prepare liquid accelerator for main raw material innovatively, the present invention compared with prior art has the following advantages:
1. alkali-free is corrosion-free.Alkali-free liquid accelerator alkali content of the present invention is less than 1%, greatly reduces the possibility of sprayed concrete generation alkali, improves concrete durability; In addition, alkali-free is safe concerning construction worker, can not corrode workman's health.
2. high strength.Liquid accelerator prepared by the present invention, mortar 1d intensity is up to more than 20MPa, and later strength not only can not be lost, and also have and increase, wherein mortar 28d compressive strength rate is up to more than 120%.For in concrete, while having higher early strength, can also ensure that later strength increases to some extent, be safe to permanent construction member.
3. stationary phase is long more than 6 months.Liquid accelerator prepared by the present invention is with the change of envrionment temperature, light, and it to ensure after 6 months still not crystallization, precipitation, and result of use is constant.
4. volume is low.When high-strength prepared by the present invention is 4% of cement quality without sulphur alkali-free liquid accelerator volume, the requirement of salable product in JC477-2005 " sprayed concrete accelerating chemicals " can be met; When volume is 5% of cement quality, can meet the requirement of acceptable end product, volume is far below prior art level.
5. sulfate radical-free ion.The sulfate radical of nearly all alkali-free quick-coagulant all containing various dose in the market, a large amount of sulfate radicals can cause the generation of secondary ettringite, then concrete expansion cracking.The present invention prepare without sulphur alkali-free quick-coagulant not containing sulfate radicals, substantially increase the erosion resistance of sprayed concrete.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further details.
Described percentage concentration is mass percent concentration if no special instructions.
Embodiment is implemented under premised on technical solution of the present invention, gives detailed embodiment and concrete operating process, and embodiment will contribute to understanding the present invention, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1-5, prepare high-strength without sulphur alkali-free liquid accelerator
Embodiment 1-5 high-strength is as shown in table 1 without the composition of raw materials of sulphur alkali-free liquid accelerator and comparative example, and preparation method is as shown in table 2:
Table 1 embodiment 1-5 high-strength is without the composition of raw materials of sulphur alkali-free liquid accelerator
Table 2 embodiment 1-5 high-strength is without preparation method's parameter of sulphur alkali-free liquid accelerator and comparative example
Application examples 1
Often kind of accelerating chemicals of preparation embodiment 1-5 is added in cement paste or sand-cement slurry sample with the amount of the 4-5% accounting for cement weight respectively, according to standard testing time of coagulation and the ultimate compression strength of JC477-2005 " sprayed concrete accelerating chemicals ", the performance index of this standard-required are in table 3.Alkali content and sulfate radical content is tested according to GB/T8077-2012 " Methods for testing uniformity of concrete admixture ".With comparative example and the more advanced alkali-free quick-coagulant (MEYCOSA160) of external performance for contrast, not add any accelerating chemicals for blank.
Cement paste is tested proportioning and be time of coagulation: reference cement: water=400:160.
Sand-cement slurry intensity test proportioning is: reference cement: standard sand: water=900:1350:450.
Above water comprises the water in accelerating chemicals, and during preparation, the water yield should according to the consumption of the water in actual measurement accelerating chemicals solid content deduction accelerating chemicals.
Table 3 is mixed accelerating chemicals and is only starched and the performance requriements of hardened mortar
Table 4 correlated performance detected result
Test result is as shown in table 4, and each embodiment alkali content is all less than 1%, belongs to alkali-free chlorine-free type accelerating chemicals; Each embodiment sulfate radical content does not all detect, and belongs to without sulfur type.According to the standard analysis of JC477-2005, alkali-free quick-coagulant volume prepared by the present invention can meet salable product requirement 4%, can meet the requirement of acceptable end product during volume 5%.In addition, the feature of alkali-free quick-coagulant prepared by the present invention is that intensity is high, as in embodiment 5, mortar 1d intensity up to 23.7MPa, 28d strength ratio up to 125%.In a comparative example, prepared accelerating chemicals is the shortest for time of coagulation, but 1d intensity is minimum, this mainly in comparative example trifluoroacetic acid volume too high, excessive fluorion can hinder the normal hydrated of cement, and the nano silicon volume playing enhancement is lower, both actings in conjunction cause mortar strength to reduce.And in contrast, the alkali-free quick-coagulant MEYCOSA160 volume be purchased just can meet the demands up to 8-10%.By contrast, alkali-free quick-coagulant volume prepared by the present invention is lower, intensity is higher, illustrates and alkali-free quick-coagulant time of coagulation prepared by the present invention and strength property are better than same kind of products at abroad (MEYCOSA160).
The stability of test example 2, detection liquid accelerator of the present invention
Test method performs by the method mentioned in patent disclosed in China Building Material Scientific Research General Institute (201310450025.7), and wherein placing condition is physical environment.Test-results is as shown in table 5, and the stability of liquid accelerator of the present invention within storage period is all more than 6 months, and some is even more than 7 months.Comparative example stationary phase is one month, and MEYCOSA160 stationary phase is two months.
Table 5 liquid accelerator of the present invention is in internal stability test-results storage period
Claims (10)
1. high-strength is without a sulphur alkali-free liquid accelerator, and the weight percent that its feed composition and each component account for raw material total amount is as follows:
Nano aluminium oxide: 10-25%,
Nano silicon: 15-27%,
Trifluoroacetic acid: 5-12%,
Organic dispersing agent: 1-5%
Stablizer: 1-3%,
Suspension agent: 0.5-1.5%,
Surplus is water, and gross weight supplies 100%.
2. high-strength according to claim 1 is without sulphur alkali-free liquid accelerator, it is characterized in that: the weight percent that its feed composition and each component account for raw material total amount is as follows: nano aluminium oxide: 15-20%,
Nano silicon: 18-24%,
Trifluoroacetic acid: 7-10%,
Organic dispersing agent: 2-4%
Stablizer: 1.5-2.5%,
Suspension agent: 0.7-1%,
Surplus is water, and gross weight supplies 100%.
3. high-strength according to claim 1 is without sulphur alkali-free liquid accelerator, it is characterized in that: the particle diameter of described nano aluminium oxide is between 5-20nm.
4. high-strength according to claim 1 is without sulphur alkali-free liquid accelerator, it is characterized in that: the particle diameter of described nano silicon is between 20-100nm.
5. high-strength according to claim 1 is without sulphur alkali-free liquid accelerator, it is characterized in that: described organic dispersing agent is any one in propylene glycol, ethylene glycol or ethylene glycol monobutyl ether.
6. high-strength according to claim 1 is without sulphur alkali-free liquid accelerator, it is characterized in that: described stablizer is a-amino acid.
7. high-strength according to claim 1 is without sulphur alkali-free liquid accelerator, it is characterized in that: described stablizer is any one in glycine or L-Ala.
8. high-strength according to claim 1 is without sulphur alkali-free liquid accelerator, it is characterized in that: described suspension agent is any one in polyoxyethylene glycol or polyacrylamide.
9. prepare the method for high-strength as claimed in claim 1 without sulphur alkali-free liquid accelerator, its concrete steps are as follows:
1) water is added in water bath containers be heated to 65-75 DEG C;
3) under Keep agitation condition, nano aluminium oxide and nano silicon are added to the water;
4) slowly drip trifluoroacetic acid with constant flow pump, time for adding completes at 1.5-2h;
5) under heat-retaining condition, add stablizer, Keep agitation 0.5-1h to be translucent suspension to liquid phase;
6) translucent suspension is transferred in the normal high-speed shearing emulsion machine in laboratory;
7) add organic dispersing agent and suspension agent, start high-speed shearing emulsion machine, rotating speed is between 5000-8000r/min, and emulsification times is 0.5-1h, obtains high-strength without sulphur alkali-free liquid accelerator.
10. a high-strength as claimed in claim 1 is without the application of sulphur alkali-free liquid accelerator in sprayed concrete.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107244825A (en) * | 2017-07-15 | 2017-10-13 | 王宇青 | Without sulphur alkali-free liquid accelerator |
| CN107935432A (en) * | 2017-11-28 | 2018-04-20 | 湖北腾辰科技股份有限公司 | A kind of new organic-inorganic acid synthesis alkali-free quick-coagulant and preparation method thereof |
| CN109761532A (en) * | 2019-01-21 | 2019-05-17 | 江苏奥莱特新材料股份有限公司 | The low rebound of one kind, high early-strength alkali-free liquid accelerator and preparation method thereof |
| CN110255955A (en) * | 2019-04-11 | 2019-09-20 | 武汉理工大学 | A kind of alkali-free liquid accelerator and its preparation method and application |
| CN111253108A (en) * | 2020-01-08 | 2020-06-09 | 五家渠格辉新材料有限责任公司 | Sulfur-free alkali-free accelerator beneficial to durability of sprayed concrete and preparation method thereof |
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| CN1974466A (en) * | 2006-12-07 | 2007-06-06 | 江苏博特新材料有限公司 | Alkali-free liquid setting accelerator for spray concrete |
| CN101648785A (en) * | 2009-09-14 | 2010-02-17 | 江苏博特新材料有限公司 | Alkali-free liquid setting accelerator |
| CN104446090A (en) * | 2014-12-08 | 2015-03-25 | 江苏奥莱特新材料有限公司 | Durable alkali-free liquid setting accelerator and preparation method thereof |
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2015
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| CN1974466A (en) * | 2006-12-07 | 2007-06-06 | 江苏博特新材料有限公司 | Alkali-free liquid setting accelerator for spray concrete |
| CN101648785A (en) * | 2009-09-14 | 2010-02-17 | 江苏博特新材料有限公司 | Alkali-free liquid setting accelerator |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107244825A (en) * | 2017-07-15 | 2017-10-13 | 王宇青 | Without sulphur alkali-free liquid accelerator |
| CN107935432A (en) * | 2017-11-28 | 2018-04-20 | 湖北腾辰科技股份有限公司 | A kind of new organic-inorganic acid synthesis alkali-free quick-coagulant and preparation method thereof |
| CN109761532A (en) * | 2019-01-21 | 2019-05-17 | 江苏奥莱特新材料股份有限公司 | The low rebound of one kind, high early-strength alkali-free liquid accelerator and preparation method thereof |
| CN109761532B (en) * | 2019-01-21 | 2021-06-15 | 江苏奥莱特新材料股份有限公司 | Low-resilience high-early-strength alkali-free liquid accelerator and preparation method thereof |
| CN110255955A (en) * | 2019-04-11 | 2019-09-20 | 武汉理工大学 | A kind of alkali-free liquid accelerator and its preparation method and application |
| CN110255955B (en) * | 2019-04-11 | 2021-09-21 | 武汉理工大学 | Alkali-free liquid accelerator and preparation method and application thereof |
| CN111253108A (en) * | 2020-01-08 | 2020-06-09 | 五家渠格辉新材料有限责任公司 | Sulfur-free alkali-free accelerator beneficial to durability of sprayed concrete and preparation method thereof |
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