CN105565695A - Anticorrosive agent for concrete and anticorrosive concrete - Google Patents
Anticorrosive agent for concrete and anticorrosive concrete Download PDFInfo
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- CN105565695A CN105565695A CN201410535703.4A CN201410535703A CN105565695A CN 105565695 A CN105565695 A CN 105565695A CN 201410535703 A CN201410535703 A CN 201410535703A CN 105565695 A CN105565695 A CN 105565695A
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Abstract
The invention provides an anticorrosive agent for concrete. The anticorrosive agent is a mixture of powder selected from the group consisting of fly ash, blast-furnace water-quenched slag powder, silica fume, light-burnt metakaolin powder, phosphorus slag powder, alum slag powder, natural zeolite powder and the like and a barium compound selected from the group consisting of barium chloride, barium nitrate, barium acetate, barium hydroxide, barium sulfide and the like. The anticorrosive agent for concrete provided by the invention enables Ca(OH)2 by-produced in hydration of cement to bond with SiO2 included in cement so as to produce secondary hydrated calcium silicate, so the strength and impermeability of concrete are improved; barium ions doped into concrete reacts with SO4<2-> from the outside in time to produce inertial and stable secondary barite, so deionization of SO4<2-> is realized and corrosivity of SO4<2-> is eradicated; the secondary barite forms a stable mineral inorganic protection film on the surface layer of concrete, so further invasion of external harmful ions is prevented, the strength, impermeability and corrosion resistance of concrete are further improved, the service life of concrete is substantially prolonged, and economic benefits are increased.
Description
Technical field
The present invention relates to a kind of inhibitor and belong to material of construction class, specifically relate to the corrosion protection concrete (comprising corrosion protection concrete prefabricated element) of a kind of concrete inhibitor and preparation thereof.
Technical background
Concrete Sulfate Attack disease is the long-standing problem of long-standing problem construction industry, and coastal and arid varieties in saline-alkali areas concrete works also increases in recent years greatly by the Case Report of saline and alkaline erosion disease.After particularly repeatedly violent earthquake occurs in recent years, the national competent authorities revised had and issued series engineering specification and product standard: the such as GB50011 (construction work earthquake resistant design code) of China, GB50476 (concrete durability design specifications), GB50082/T (concrete durability inspection criterion method) GB748 (sulphate-resistant cement standard), JC/T1011 (agent on crack resistance of concrete Sulfates corrosion sanitas standard) etc.Although some national regulations require to be greater than 6 or strong wind, flood in seismic intensity, when rubble flow etc. occur, buildings may be impaired, guarantee that these Architectural Equipments do not collapse at once, to guarantee that people can have enough time safety from impaired buildings to withdraw from.This just not only requires that buildings will have enough physical strengths in complete man-hour, and to consider in Building Design military service total life cycle, buildings corrodes by wind and rain and deteriorated environmental chemistry, its intensity can decline to some extent, but still enough residual intensities to be kept, to tackle the generation of various unexpected storms.
The sixties in last century, American scholar found that concrete sulphate attack disease is except ettringite reason, and thaumasite and brucite etc. are also the causes of disease.Subsequently in Europe, Africa and Australia, within 2004, also all to find in Xinjiang of China (South Sinkiang Bachu) and confirm the Engineering Projects of Concrete Sulfate Attack disease of thaumasite type etc.Analyze through the inspection of the scene of a crime and testing laboratory's calibrating, propose the disease chemistry analysis formula about ettringite, brucite and thaumasite:
Ettringite (Ettringite)
3Ca(OH)
2+2Al(OH)
3+3(CaSO
42H
2O)20H
2O--3CaOAl
2O
33CaSO
432H
2O；
Brucite (Brucite)
Ca (OH)
2+ MgSO
4--CaSO
4+ Mg (OH)
2with
Thaumasite (Thumasite)
2Ca(OH)
2+2SiO
4+2CaCO
3+2(CaSO
42H
2O)+22H
2O--2{(CaOSi(OH)
4)2(CaCO
3CaSO
4)24H
2O
Above-mentioned analysis formula discloses the cause understood Concrete Sulfate Attack disease and occur, and is first the Ca (OH) of hydrated cementitious association
2existence.When in cement, aluminium content is more, and there are more water and SO in the concrete external world
4 2-time will produce the spalling disease of ettringite, so traditional sulphate-resistant cement is started with from the aluminium content controlling cement suppress concrete sulphate attack disease.When in cement, containing more magnesium, there are more water and SO in the concrete external world
4 2-, Mg
2+time will produce brucite shortcakeization disease.When containing the CO of more limestone aggregate and limestone powder in concrete
3 2-and there is more water in the concrete external world, wherein again containing more HCO
3 -time will produce the shortcake disease of thaumasite.
The present inventor only controls the sulphate-resistant cement of aluminium content through long-term observation, research, analysis, discovery, very micro-to the disease effect of water prevention magnesite and thaumasite.And with expansive agent for cement slurry and many fly ashs or blast furnace slag powder, silicon ash etc. so that as far as possible by Ca (OH)
2be converted into hydrated calcium silicate, its coefficient of resistance erosion K value is also still hovered between 80-90%, still can not reach the object of radical cure sulphate corrosion.
The present inventor summarizes the experience and lessons of last stage research, determines just to transfer from the thinking of containing improving concrete impermeability the method discongested to.Namely adopt activation Barium ion to mix in concrete, make the SO in the concrete external world
4 2-immediately Yu Barium ionic bond generates the secondary barite of inert stable after infiltrating, thus achieve SO
4 2-deionization, also obtain the effect of corrosion removal, the barite of newborn inertia forms a stable mineral protective membrane at concrete surface layer, further suppress SO simultaneously
4 2-with other harmful ions (Cl
-, HCO3
1-, K
+, Na
+, Mg
2+deng) invasion, on the one hand improve concrete solidity to corrosion, also improve other physicalies (as concrete impermeability and splitting resistance etc.) on the other hand.
Summary of the invention
Concrete inhibitor provided by the invention, its object is not only by the Ca (OH) in concrete
2be converted into useful hydrated calcium silicate, and generate again the stable barite mineral inorganic protective film of one deck at concrete surface layer.To improve concrete intensity, impermeability, splitting resistance and anticorrosive usefulness.
The object of the invention is to realize by following method:
In view of Concrete Sulfate Attack Etiological is;
Ettringite (Ettringite)
3Ca(OH)
2+2Al(OH)
3+3(CaSO
42H
2O)20H
2O--3CaOAl
2O
33CaSO
432H
2O
Brucite (Brucite)
Ca(OH)
2+MgSO
4--CaSO
4+Mg(OH)
2
Thaumasite (Thumasite)
2Ca(OH)
2+2SiO
4+2CaCO
3+2(CaSO
42H
2O)+22H
2O--2{(CaOSi(OH)
4)2(CaCO
3CaSO
4)24H
2O
Above-mentioned analysis formula illustrates: hydrated cementitious can association Ca (OH)
2, be the major prerequisites that concrete erosion disease produces.When in cement, aluminium content is more, and there are more water and SO in the concrete external world
4 2-time will produce the spalling disease of ettringite; When in cement, containing more magnesium, there are more water and SO in the concrete external world
4 2-, Mg
2+time will produce the shortcake disease of brucite; When containing the CO of more limestone aggregate and limestone powder in concrete
3 2-and there is more water in the concrete external world and contains more HCO in water
3 -time will produce the shortcake disease of thaumasite.
For the shortcake disease of the spalling disease of ettringite, brucite and thaumasite, the invention provides following technical scheme to overcome described disease.
Barite is a kind of baric natural mineral, proportion up to 4.3-4.7, there is good radioprotective line usefulness, very stable, the water insoluble and soda acid of chemical property under natural condition, with other materials also not react with, to the chemical stability under special meaningfully its normal temperature of concrete, corrode in occurring in nature weather resistance, good stability does not damage for a long time.
Natural barite (BaSO
4) and coke when high-temperature calcination, its SO
4 2-will be cracked as the barium sulphide of activation, and the barium compound (Huoization Barium ion of obtained various active can be processed further), just make the extraneous SO invaded after mixing concrete
4 2-timely generation secondary barite, and the inorganic mineral protective membrane forming inertia at concrete surface layer, further suppress again the invasion of multiple harmful ion, thus improve concrete anticorrosive durable military service performance.
Although the barium salts such as bariumchloride, nitrate of baryta, barium acetate, hydrated barta are soluble in water, equal Ke Zuo is the source of Barium ion, sufficient than Commercial sources, the barium sulphide price that barite more cheap is again produced or expensive many, should not in a large number for concrete.
The dioxide-containing silica of flyash, blast furnace slag powder, silicon ash, light-burned metakaolinite powder, phosphorus slag powder, alum ground-slag, natural zeolite powder etc. is substantially all at more than 50-70%.The Ca (OH) of hydrated cementitious association
2generate secondary hydration Calucium Silicate powder with silicon dioxde reaction wherein, add concrete intensity and density on the one hand, improve impermeability, weaken again Ca (OH) on the other hand
2the expansion of crystallization is to concrete infringement probability.
Barium compound is combined with silica containing powder, has both made concrete enhance intensity and impervious and erosion resistance, weakened again Ca (OH)
2the expansion of crystallization is to concrete infringement, and the ingenious combination of these two kinds of materials substantially increases concrete comprehensive effectiveness, extends concrete service life, improves the security of concrete works, also substantially increases economic benefit.
One or more powders that concrete inhibitor provided by the invention contains flyash, blast furnace slag powder, silicon ash, light-burned metakaolinite powder, phosphorus slag powder, alum ground-slag and natural zeolite powder are selected, and a kind of barium compound selected from bariumchloride, nitrate of baryta, barium acetate, hydrated barta and barium sulphide.
In preferred concrete inhibitor provided by the invention, described powder is flyash.
In provided by the invention second preferred concrete inhibitor, described barium compound is barium sulphide.
In provided by the invention 3rd preferred concrete inhibitor, described barium sulphide is the barium sulphide prepared with barite.
In provided by the invention 4th preferred concrete inhibitor, described barium compound is the barium sulphide prepared as follows: at 900-1200 DEG C, particle diameter be 5-10mm barite particle, in the 100 mass parts barites barium sulphide more obtained than the coke calcination of 12 mass parts ratios.
In provided by the invention 5th preferred concrete inhibitor, by mass percentage, the amount of described barium compound is 30-20%.
In provided by the invention 6th preferred concrete inhibitor, by mass percentage, the amount of described powder is 70-80%.
In provided by the invention 7th preferred concrete inhibitor, by mass percentage, the amount of described barium compound is 30-20%, and the amount of described powder is 70-80%.
Anticorrosive concrete prepared by concrete inhibitor provided by the invention and anticorrosive concrete prefabricated element, employing be pulverized fuel ash cement, prepared by any one cement of selecting in silicate cement or slag cement.
The using method of concrete inhibitor provided by the invention mixes concrete inhibitor 12kg in every 1 cubic meter of concrete, and stir by the technological operation specification of existing normal concrete, enter mould, vibrate, form removal and maintenance.
With immediate prior art ratio, the present invention has following excellent effect:
Inhibitor provided by the invention makes the Ca (OH) of hydrated cementitious association
2the silicon dioxde reaction contained with it generates secondary hydration Calucium Silicate powder, adds concrete intensity and density on the one hand, improves impermeability, weakens again Ca (OH) on the other hand
2the expansion of crystallization is to concrete infringement probability.
Adopt activation Barium ion to mix in concrete, make the SO in the concrete external world
4 2-after infiltration, Yu Barium ionic bond generates the barite of inert stable immediately, thus is realizing SO
4 2-deionization while also obtain the effect of corrosion removal; newborn inertia barite forms a stable mineral protective membrane at concrete surface layer; alleviate concrete not corrosion resistant problem originally, other physicalies (as concrete intensity, impermeability, splitting resistance etc.) also make moderate progress.
The consistency of inhibitor provided by the invention and other each components of concrete (cement, sandstone and breeze, chemical admixture etc.) is good, and non-interference, is convenient to building site handled easily.
Concrete anticorrosion values of factor K improves, impermeabilisation rate enhances, water-intake rate have dropped, and these three indexs are all improved.
To be described in further details the present invention with specific embodiment below.Those skilled in the art to the technique scheme in this specification sheets when without prejudice to spirit of the present invention, can carry out all changes or amendment with reference to following embodiment.
Embodiment
● inhibitor provided by the invention flyash used, blast furnace slag powder, silicon ash, light-burned metakaolinite powder, phosphorus slag powder, alum ground-slag and natural zeolite powder fineness are 2500 holes/cm
2sieve full by.
● the fineness of the barium sulphide that inhibitor provided by the invention is used is 2500 holes/cm
2sieve full by.
● the preparation of inhibitor:
Barium sulphide and described powder are mixed in proportion and obtain inhibitor of the present invention.
● the concrete preparation of corrosion protection:
In concrete building site or ready mixed concrete station and concrete prefabricated element factory, in mix inhibitor provided by the invention in concrete time, after mixing 12kg anti-salt erosion agent by every cubic meter of concrete, it stirs, transport, enter mould, vibrate, job specification that existing normal concrete is followed in maintenance completely, there is no special requirement especially, and inhibitor provided by the invention is good with component compatibilities such as concrete cement, sandstone, breeze, chemical admixtures, can not mutually disturb, building site is easy to operate.
● the preparation of barium sulphide:
Divide barite and 12 parts of coke ratios by barite particle (particle diameter 5-10mm) and coke in 100 quality, at 900-1200 DEG C, be fired to CO
2release is over (with the calibrating of Ovshinsky gas instrument) completely, and adverse current is filtered and embathed, and first uses 4
0the hot sig water leaching of B é, dense leach liquor is made into 11-13 through dilution
0then B é puts into settling pond, barium sulfide solution leave standstill, filter, evaporation namely obtain barium sulphide powder.
Thereafter add hydrochloric acid, nitric acid, sodium hydroxide etc. again, the barium compounds such as corresponding bariumchloride, nitrate of baryta, hydrated barta can be obtained.
● the mensuration of concrete performance:
The coefficient of resistance erosion K:
With reference to GB/T50082 concrete durability detection method, the concrete test block mixing concrete inhibitor by preparation: 100 × 100 × 100mm
320 ± 2 DEG C, maintenance after 28 days under humidity > 95% standard conditions, immerse by 1000ml pure water, add the simulating nature saline-alkali water that anhydrous sodium sulphate 30g, sodium-chlor 1.65g and seven aqueous magnesium chloride 17.6g obtain compound salt solution in after 4 hours, drying 4 hours is a circulation.Ultimate compression strength after 50-100 circulation like this is with identical proportioning but the normal concrete mark not mixing inhibitor supports the ratio of the ultimate compression strength (as 100%) in the same length of time.
Impermeabilisation aspect ratio:
By upper circular diameter 175mm, the positive round frustum concrete test block of lower circular diameter 185mm and high 150mm, by GB/T50082 standard, under 20 ± 2 DEG C and humidity > 95% standard conditions, maintenance is after 28 days, after frustum week, side paraffin added rosin sealing, loading is with in the steel drum of footpath, on upper and lower steel drum opening and frustum, lower platform maintains an equal level, be positioned over and survey on hydraulic pressure instrument, water-supply pipe is being connected by below the test block of inspection frustum, maintenance 24 hours are continued under pressure of supply water being transferred to 1.2 ± 0.05Mpa in 5 minutes, cut off the water, take out frustum test block, along frustum vertical line frustum test block to be cutd open by the upper and lower center of frustum and do even two halves, equidistantly get 10 points and record the actual permeated height value (being accurate to 0.1mm) of water, the arithmetic average of 10 data is the infiltration height value of this frustum test block.Ice detector once can the infiltration height value of Simultaneously test 6 frustum test blocks, and the arithmetic average of 6 measured values is the infiltration height value of this batch of concrete frustum test block.
The infiltration height value having mixed the concrete frustum test block of inhibitor is by examining concrete impervious height ratio value with the ratio (should be less than 40% time normal) of the infiltration height value (as benchmark 100%) of the concrete frustum test block of not mixing inhibitor.
The mensuration of water-intake rate:
Be 100 × 100 × 100mm by specification
3concrete test block normal curing after 28 days, put into 80 DEG C of drying in oven to constant weight, putting into pure water under room temperature again places after 48 hours, the water that surface is dried in test block is taken out from water, weigh in time, deduct constant weight during former oven dry, its difference and the ratio of former constant weight, be the water-intake rate of 48 hours of this test block.
The concrete test block water-intake rate of 48 hours having mixed inhibitor and the ratio of the concrete test block water-intake rate of 48 hours (as benchmark 100%) of not mixing inhibitor be by examine concrete 48 little time water-intake rate ratio.(time normal, should 75% be less than).
Table 1
Note: a is thaumasite test, and b is brucite test, and c is ettringite test.
In table 11,2 and 3 row refer to the ratio of the concrete mixing inhibitor and the normal concrete (as 100%) not mixing inhibitor.
The data presentation of table 1, inhibitor provided by the invention is to the control of dissimilar salt erosion disease and impervious good effect of integrated pest management.
Table 2
Note: 1 in table 2,2 and 3 row refer to the ratio of the concrete mixing inhibitor and the normal concrete (as 100%) not mixing inhibitor.
The data of table 2 show that the corrosion protection concrete of inhibitor and the dissimilar cement provided shows good impervious and protection against corrosion comprehensive effectiveness.
Table 3
Note: 1 in table 3,2 and 3 row refer to the ratio of the concrete mixing inhibitor and the normal concrete (as 100%) not mixing inhibitor.
When the data of table 3 show that the incorporation of this inhibitor in concrete is between 11.5-12.5%, achieve impervious and good comprehensive effectiveness that is corrosion protection.
Table 4
Note: 1 in table 4,2 and 3 refers to the ratio of the normal concrete (as 100%) mixed inhibitor concrete and do not mix inhibitor.
The data of table 4 show that concrete prepared by inhibitor provided by the invention has good impervious and etch-proof comprehensive effectiveness.
Finally should be noted that: the restriction of above embodiment only for illustration of the technical scheme of the application not to its protection domain; although with reference to above-described embodiment to present application has been detailed description; those of ordinary skill in the field are to be understood that; still all changes, amendment or equivalent replacement can be carried out to the embodiment of application after reading the application; but these change, revise or be equal to replacement, all applying within the claims awaited the reply.
Claims (10)
1. a concrete inhibitor, it is characterized in that described inhibitor comprises that prepared by following component: the powder selected from flyash, blast furnace slag powder, silicon ash, light-burned metakaolinite powder, phosphorus slag powder, alum ground-slag and natural zeolite powder etc., and from a kind of barium compound that bariumchloride, nitrate of baryta, barium acetate, hydrated barta and barium sulphide etc. are selected.
2. a kind of concrete inhibitor according to claim 1, is characterized in that described powder is conventional flyash.
3. a kind of concrete inhibitor according to claim 1, is characterized in that described barium compound is conventional barium sulphide.
4. a kind of concrete inhibitor according to claim 1, is characterized in that described barium sulphide is obtain with the preparation of natural barite mineral.
5. a kind of concrete corrosion protection additive according to claim 4, it is characterized in that described barium compound is for obtaining barium sulphide as follows by natural barite mineral: at 900-1200 DEG C, particle diameter be 5-10mm, in the coke calcination of 100 mass parts barites than 12 mass parts ratios, obtained barium sulphide.
6. a kind of concrete inhibitor according to claim 1, is characterized in that by mass percentage, and described barium compound is 30-20%.
7. a kind of concrete inhibitor according to claim 1, is characterized in that by mass percentage, and described powder is 70-80%.
8. a kind of concrete inhibitor according to claim 1, is characterized in that by mass percentage, and the amount of described barium compound is 30-20%, and the amount of described powder is 70-80%.
9. the modification corrosion protection concrete prepared of arbitrary concrete inhibitor of claim 1-8, described concrete is concrete prepared by any one cement that pulverized fuel ash cement, silicate cement or slag cement etc. are selected.
10. the using method of a kind of concrete inhibitor according to claim 1, is characterized in that every 1 cubic meter of concrete mixes concrete inhibitor 12kg, and stirred by the technological operation specification of existing normal concrete, entered mould, vibrated, form removal and maintenance.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948654A (en) * | 2016-05-12 | 2016-09-21 | 南通科达建材股份有限公司 | High-durability silicate concrete for dam |
| CN108298900A (en) * | 2018-01-29 | 2018-07-20 | 中国电力科学研究院有限公司 | A kind of transmission pole |
| CN109369132A (en) * | 2018-10-17 | 2019-02-22 | 中国路桥工程有限责任公司 | A kind of durable pavement structure concrete material and preparation process |
| CN109705852A (en) * | 2018-12-25 | 2019-05-03 | 西安建筑科技大学 | A method of strontium silicate powder body material is prepared using strontium hydroxide and silicon ash |
| CN110357513A (en) * | 2019-07-26 | 2019-10-22 | 大连海事大学 | A kind of freeze proof anti-crack concrete and preparation method thereof |
| CN112479644A (en) * | 2020-12-18 | 2021-03-12 | 陕西天皓万业混凝土工程有限责任公司 | Zirconium-titanium tailing concrete and preparation method thereof |
| CN113233843A (en) * | 2021-06-08 | 2021-08-10 | 哈尔滨工业大学 | Mortar material with high freezing resistance and high corrosion resistance and preparation method thereof |
| CN113880125A (en) * | 2021-10-29 | 2022-01-04 | 湖北文理学院 | Carbothioxonotlite and preparation method thereof |
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| CN105948654A (en) * | 2016-05-12 | 2016-09-21 | 南通科达建材股份有限公司 | High-durability silicate concrete for dam |
| CN108298900A (en) * | 2018-01-29 | 2018-07-20 | 中国电力科学研究院有限公司 | A kind of transmission pole |
| CN109369132A (en) * | 2018-10-17 | 2019-02-22 | 中国路桥工程有限责任公司 | A kind of durable pavement structure concrete material and preparation process |
| CN109705852A (en) * | 2018-12-25 | 2019-05-03 | 西安建筑科技大学 | A method of strontium silicate powder body material is prepared using strontium hydroxide and silicon ash |
| CN109705852B (en) * | 2018-12-25 | 2021-11-16 | 西安建筑科技大学 | Method for preparing strontium silicate powder material by utilizing strontium hydroxide and silica fume |
| CN110357513A (en) * | 2019-07-26 | 2019-10-22 | 大连海事大学 | A kind of freeze proof anti-crack concrete and preparation method thereof |
| CN112479644A (en) * | 2020-12-18 | 2021-03-12 | 陕西天皓万业混凝土工程有限责任公司 | Zirconium-titanium tailing concrete and preparation method thereof |
| CN113233843A (en) * | 2021-06-08 | 2021-08-10 | 哈尔滨工业大学 | Mortar material with high freezing resistance and high corrosion resistance and preparation method thereof |
| CN113880125A (en) * | 2021-10-29 | 2022-01-04 | 湖北文理学院 | Carbothioxonotlite and preparation method thereof |
| CN113880125B (en) * | 2021-10-29 | 2023-10-10 | 湖北文理学院 | Carbon sulfur tobermorite and preparation method thereof |
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