CN1792982A - Silicate cement of precenting chlorate corrosion - Google Patents

Silicate cement of precenting chlorate corrosion Download PDF

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Publication number
CN1792982A
CN1792982A CN 200510101480 CN200510101480A CN1792982A CN 1792982 A CN1792982 A CN 1792982A CN 200510101480 CN200510101480 CN 200510101480 CN 200510101480 A CN200510101480 A CN 200510101480A CN 1792982 A CN1792982 A CN 1792982A
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slag
cement
silicate cement
agent
precenting chlorate
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CN100441537C (en
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杨医博
梁松
莫海鸿
陈尤雯
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

A silicate cement able to resist against corrosion of Cl salt is proportionally prepared from silicate cement clinker, mixture material, gypsum, assistant and optional short fibers through proportional mixing.

Description

A kind of silicate cement of precenting chlorate corrosion
Technical field
The invention belongs to the silicate cement field, be specifically related to a kind of silicate cement of precenting chlorate corrosion.
Background technology
In bar in chlorine salt solution (in and contain in the soil environment etc. of a large amount of chlorions), adopt skeleton construction to have and go up century-old history as ocean environment, deicer salts environment, saltings environment and water, but when preparing concrete with ordinary Portland cement, because concrete resisting chloride ion penetration erosional competency is relatively poor, the very fast corrosion of reinforcing bar in the structure, thereby the too early destruction that causes buildings.According to investigations, adopt the skeleton construction of ordinary Portland cement preparation, often have only the endurance life in ocean environment about 20 years, far can not reach 50 years endurance lives even longer requirement.
For addressing this problem, be to adopt slag cement at first, research and engineering practice all show the endurance life of adopting the scoriaceous slag cement of big volume can improve buildings in the ocean environment.But slag cement has the big shortcoming of bleeding rate, and this makes that the application of slag cement is very limited.The very important problem of another of slag cement is that slag cement is to evaluate with intensity, because the variation of slag quality and volume, its resisting chloride ion penetration performance is also unstable.In China, in the slag cement fine slag contents usually below 50%, some in addition have only 20%~3O%, this resisting chloride ion penetration performance that also causes slag cement is improved less than Portland cement.
Select the method for cement can not solve concrete precenting chlorate corrosion problem owing to only adopt, adopt the mineral admixture technology to solve the main developing direction that concrete precenting chlorate corrosion problem becomes 20th century middle and late.After the nineties in 20th century, the proposition of high performance concrete notion and to the increase of concrete durability attention degree, the application of mineral admixture in concrete such as flyash, slag micropowder, silicon ash obtain very big development, and develop technology such as big volume slag micropowder resisting chloride ion penetration corrosion concrete, flyash in great mixed amount resisting chloride ion penetration corrosion concrete, silicon ash resisting chloride ion penetration corrosion concrete, complex mineral blending material resisting chloride ion penetration corrosion concrete gradually.
At present, the concrete mode of production of precenting chlorate corrosion still mainly is to carry out at building-site with the method for one or more parts replacement cement in slag micropowder, flyash, the silicon ash mineral admixture, there are problems in this method, as the quality-guarantee of mineral admixtures such as flyash, effective control or the like of homogeneity, mineral admixture and the cement of its proportioning and the consistency between the admixture, mineral admixture volume when the multi mineral adulterant uses jointly.The existence of these problems has seriously restricted the engineering of anti-chlorine salt corrosion concrete and has used.
For addressing the above problem, a spot of producer complex mineral blending material that is prefabricated in the factory is also arranged at present, stir preparation anti-seawater corrosion concrete jointly to starting material such as building-site and cement, sandstone, chemical admixtures then.This anti-seawater corrosion concrete preparation method has had certain progress than the method for the composite complex mineral blending material of building-site, but still has following three problems.
(1) because the cement quality that different manufacturers is produced is irregular, performance is different, so the method for employing prefabrication complex mineral blending material does not fundamentally solve the compatibility problem between cement, mineral admixture and the admixture yet, still need carry out a large amount of verification experimental verifications, thereby waste a large amount of manpower and materials, increase engineering cost.
(2) the mineral admixture volume is difficult to control, because mineral admixture need be transported outward usually, its price is high than cement often, and unit in charge of construction often is reduction concrete production cost, and reduces the mineral admixture consumption privately.
(3) because the cement quality that different manufacturers is produced is different with the mineral admixture quality, therefore each concrete engineering all will be studied the consistency of cement, mineral admixture and chemical admixture, and need carry out special precenting chlorate corrosion mix Design, this has increased cost on the one hand, also caused the technical threshold of anti-chlorine salt corrosion concrete too high on the other hand, can only in heavy construction, be applied, be difficult to big area and promote the use of.
In order thoroughly to solve the problem of reinforced concrete structure durability under the bar in chlorine salt solution, big area is promoted anti-chlorine salt corrosion concrete in the bar in chlorine salt solution area, it is relatively low just the precenting chlorate corrosion concrete must to be become a kind of price, and the technology that realizes easily, anti-villaumite silicate cement is exactly the key of realizing this goal.
Summary of the invention
The object of the present invention is to provide a kind of silicate cement of precenting chlorate corrosion, this silicate cement not only has enough intensity and volume stability, and what is more important has the resisting chloride ion penetration erosional competency.
The silicate cement of precenting chlorate corrosion of the present invention, be optimization proportioning, by the general special cement with resisting chloride ion penetration performance of certain independent grinding, common grinding and hybrid technique production by Portland clinker, mixing material, gypsum and auxiliary agent.
The silicate cement of precenting chlorate corrosion has high resisting chloride ion penetration erosional competency, concrete with its preparation (is tested and with concrete proportioning is: cement 410kg, medium sand 660kg, 5-25mm rubble 1180kg, water 148kg, concrete slump is 40-60mm, but the admixture naphthalene series high-efficiency water-reducing agent requires to satisfy concrete workability) 56d resisting chloride ion penetration in length of time performance (ASTM1202 coulometry) is less than 1500 coulombs.According to charge value, anti-villaumite silicate cement (charge value is 1000~1500 coulombs) and high anti-villaumite silicate cement (charge value is less than 1000 coulombs) in it can being divided into.
The component and the content of the silicate cement of precenting chlorate corrosion of the present invention are as follows:
Component concentration (weight %)
Portland clinker 14~94
Mixing material 5~85
Gypsum 1~10
Auxiliary agent 0~15
Described mixing material is one or more in granulated blast-furnace slag, flyash, pozzolana mixed material, silicon ash, metakaolin, zeolite powder, slag, granulation refining ferrochrome slag, granulation calcium enriched cyclone-furnace slag, iron-tion slag, granulation carbon ferrochrome slag, granulation blast furnace titanium slag, Wingdale, sandstone, waste ceramic, the kiln ash.
When adopting granulated blast-furnace slag, slag, granulation refining ferrochrome slag, granulation calcium enriched cyclone-furnace slag, iron-tion slag, granulation carbon ferrochrome slag, granulation blast furnace titanium slag as mixing material, should be with its independent grinding, specific surface area should be at 200~2000m 2In/kg the scope.
Mostly these mixing materials are industrial residue or natural materials, and the consumption for reducing cement clinker alleviates carrying capacity of environment, realize that sustainable development of cement industry is significant.The mixing material of some kind (as granulated blast-furnace slag, flyash, silicon ash, metakaolin etc.) has the effect that improves cement resisting chloride ion penetration performance, and the mixing material of other kinds (as Wingdale etc.) then has and replaces cement clinker, adjusts the strength of cement grade, improves the effect of cement granules grating.By the optimization proportioning of these mixing material kinds and quantity, can guarantee that cement has higher resisting chloride ion penetration performance, has enough intensity and volume stability on the one hand; Can utilize industrial residue and local starting material to greatest extent on the other hand, thereby reduce cost and protect environment.
Described auxiliary agent is one or more in grinding aid, tensio-active agent, exciting agent, the concrete admixture.Wherein grinding aid mainly plays a part to quicken grinding process, as trolamine, diethanolamine etc.; Tensio-active agent mainly plays dissemination, as alkyl carboxylate, naphthalenesulfonate etc.; Exciting agent mainly works the composition activity effect that excites, as calcium sulfate etc.; Concrete admixture mainly works to regulate the cement applications performance, as improve concrete mix rheological property, regulate cement setting time, improve concrete durability etc., its principal item has water reducer, high efficiency water reducing agent, hardening accelerator, retardant, air entrapment agent, rust inhibitor, swelling agent, water-holding agent, economization agent etc., is in them one or more.
In addition, can be as required in cement again admixture volume volume be 0~2% chopped strand, with the crack resistance of refinforced cement.
According to the kind of selected mixing material and auxiliary agent, can select to mix with other materials again behind common again grinding, the independent grinding of part material behind the common grinding of all material, the independent grinding of part material, produce with method such as other materials mixing again behind the common grinding of part material.
The anti-villaumite silicate cement of producing by above-mentioned certain production method is carried out the physicals test, and test result sees Table 1.
The contrast of table 1 cement physical properties
Project P.O 32.5R P.II 42.5R The silicate cement 1 of middle precenting chlorate corrosion The silicate cement 1 of high precenting chlorate corrosion
Fineness [1] 4.4% 326m 2/kg 2.8% 3.2%
Time of coagulation Presetting period 5h10min 1h25min 3h45min 3h15min
Final setting time 5h55min 2h15min 4h40min 4h20min
Stability (boiling process) Qualified Qualified Qualified Qualified
Folding strength, MPa 3d 5.0 7.7 4.5 5.2
28d 7.5 9.6 7.8 8.0
Ultimate compression strength, MPa 3d 22.5 40.1 18.5 22.4
28d 40.0 60.4 40.4 42.0
Concrete [2]The 56d charge value, coulomb 3370 1982 1105 850
Annotate: except that the fineness of P.II 42.5R cement was represented with specific surface area, all the other cement fineness were 80 microns and tail over [1].
[2] concrete proportioning of test usefulness is: cement 410kg, and medium sand 660kg, 5-25mm rubble 1180kg, water 148kg, concrete slump are 40-60mm, but the admixture naphthalene series high-efficiency water-reducing agent is to satisfy the concrete workability requirement.
By table 1 as seen, physical performance indexs such as the fineness of the silicate cement 1 of middle precenting chlorate corrosion and the silicate cement 1 of high precenting chlorate corrosion, time of coagulation, stability, intensity satisfy the requirement of ordinary Portland cement 32.5R strength grade, and with the concrete resisting chloride ion penetration erosion performance of its preparation (charge value is more than 800 coulombs the time, charge value is more little, and then the resisting chloride ion penetration ability is strong more; When charge value was lower than 800 coulombs, concrete had very high resisting chloride ion penetration ability) to be much better than the ordinary Portland cement that strength grade is 32.5R, also the II type silicate cement than the 42.5R strength grade is excellent.
Requirement according to the standard CC ES 01-2004 of China Civil Engineering Society " concrete structure durability design and construction guide "; (environmental rating is divided into six grades of A~F to be used for design life and to be the D level environment in 50 years; wherein A level environmental activity degree can be ignored; F level environmental activity degree is extremely serious, the district under water of D level environment such as coastal waters or ocean environment etc.) in the concrete 56d charge value in the length of time of concrete steel building need less than 1500 coulombs.According to the result of table 1,32.5R ordinary Portland cement commonly used and 42.5R II type silicate cement all can not reach this requirement, and promptly the concrete of preparing with these cement can not be used for the concrete steel building under these environment.
The concrete 56d charge value of silicate cement 1 preparation of precenting chlorate corrosion is lower than 1200 coulombs in the employing; according to the requirement of the standard CC ES 01-2004 of China Civil Engineering Society " concrete structure durability design and construction guide ", it is concrete steel building in the D level (as the district under water of coastal waters or ocean environment etc.) in 100 years and the following environment that this concrete can be used for design life.
Adopt the concrete 56d charge value of silicate cement 1 preparation of high precenting chlorate corrosion to be lower than 1000 coulombs; requirement according to the standard CC ES 01-2004 of China Civil Engineering Society " concrete structure durability design and construction guide "; it is concrete steel building in the E level (spattering district etc. as the coastal waters of non-hot area or the change of level district and the wave of ocean environment) in 50 years and the following environment that this concrete can be used for design life, also can be used for design life and be concrete steel building in the D level in 100 years and the following environment.
The advantage of the silicate cement of precenting chlorate corrosion of the present invention is as follows:
(1) the present invention uses easily, as long as index of control water cement ratio just can make the concrete of resisting chloride ion penetration excellent property very easily, thereby makes the silicate cement big area popularization of precenting chlorate corrosion become possibility;
(2) the easier assurance of the quality of the silicate cement of precenting chlorate corrosion, because building-site no longer carries out the collocation of cement and mineral admixture, thereby can effectively solve problems such as the quality stability problem of compatibility problem, mineral admixture and cement of mineral admixture and cement and mineral admixture volume deficiency;
(3) cost of the silicate cement of precenting chlorate corrosion is lower, because anti-villaumite cement is to be produced by the cement mill mass-producing, and can make full use of local starting material, thus the price of reduction gelling material that can maximum possible;
(4) behind the silicate cement of employing precenting chlorate corrosion, owing to mineral admixture and cement need not be stored separately and mixing, the storage of concrete raw material and metering outfit can more be simplified, and the concrete churning time can shorten, thereby further reduce construction costs;
(5) the easier detection of quality of concrete of the precenting chlorate corrosion of the silicate cement preparation of usefulness precenting chlorate corrosion, for specific anti-villaumite silicate cement, concrete strength with its preparation is directly related with water-cement ratio, thereby can be very easily from the concrete resisting chloride ion penetration erosional competency of prediction of strength;
(6) adopt the present invention, can promote the popularization of bulk cement, reduce the consumption of cement and mineral admixture packing bag;
(7) adopt the present invention, can significantly improve the resisting chloride ion penetration erosional competency of cement, thereby significantly improve the endurance life of concrete steel building in the chlorion erosion environment, reduce the number of times that demolishing buildings is rebuild, a large amount of starting material and construction investment, economic benefit and social benefit highly significants such as cement clinker, sandstone aggregate saved.
Specific implementation method
The present invention is further elaborated below by embodiment, but do not limit content of the present invention.
Embodiment 1
The raw material quality of the silicate cement 1 of middle precenting chlorate corrosion is than being cement clinker: granulated blast-furnace slag: flyash: Wingdale: gypsum=26: 35: 27: 5: 7.Its performance test value sees Table 1.
Embodiment 2
The raw-material mass ratio of the silicate cement 1 of high precenting chlorate corrosion is a cement clinker: granulated blast-furnace slag: flyash: Wingdale: gypsum: grinding aid=26: 50: 14: 4: 5: 1, grinding aid was a trolamine.Its performance test value sees Table 1.
Embodiment 3
The raw material quality of the silicate cement 2 of middle precenting chlorate corrosion is than being cement clinker: flyash: gypsum: rust inhibitor: swelling agent: grinding aid=54: 30: 4: 8: 3: 1, grinding aid was a diethanolamine.Its performance test value sees Table 2.
Embodiment 4
The raw material quality of the silicate cement 2 of high precenting chlorate corrosion is than being cement clinker: silicon ash: gypsum: high efficiency water reducing agent: grinding aid=91.5: 5: 2: 0.5: 1, grinding aid was a trolamine.Its performance test value sees Table 2.
Embodiment 5
The raw material quality of the silicate cement 3 of middle precenting chlorate corrosion is than being cement clinker: granulated blast-furnace slag: flyash: Wingdale: gypsum: grinding aid: tensio-active agent=25: 60: 4: 5: 5: 0.7: 0.3; and the chopped strand of admixture cement volume ratio 0.5%; grinding aid is a diethanolamine, and tensio-active agent is the alkyl carboxylate.Its performance test value sees Table 2.
Embodiment 6
The raw material quality of the silicate cement 3 of high precenting chlorate corrosion is than being cement clinker: granulated blast-furnace slag: flyash: silicon ash: Wingdale: pozzolana mixed material: slag: gypsum: grinding aid: tensio-active agent: exciting agent=18: 34: 25: 5: 5: 5: 3: 3.5: 0.7: 0.3: 0.5; and the chopped strand of admixture cement volume ratio 1.5%; grinding aid is a diethanolamine; tensio-active agent is a naphthalenesulfonate, and exciting agent is a calcium sulfate.Its performance test value sees Table 2.
The silicate cement physicals of table 2 precenting chlorate corrosion
Project In anti-villaumite cement 2 High anti-villaumite cement 2 In anti-villaumite cement 3 High anti-villaumite cement 3
Fineness (80 microns tail over) 3.6% 2.8% 4.0% 4.9%
Time of coagulation Presetting period 3h15min 1h45min 3h40min 3h45min
Final setting time 4h30min 2h35min 5h10min 4h40min
Stability (boiling process) Qualified Qualified Qualified Qualified
Folding strength, MPa 3d 4.2 6.9 4.0 4.0
28d 7.0 8.7 6.8 7.2
Ultimate compression strength, MPa 3d 16.8 29.1 16.5 17.6
28d 38.6 51.8 36.9 39.0
Concrete [1]The 56d charge value, coulomb 1309 690 1158 926
Annotate: the concrete proportioning of [1] test usefulness is: cement 410kg, and medium sand 660kg, 5-25mm rubble 1180kg, water 148kg, concrete slump are 40-60mm, but the admixture naphthalene series high-efficiency water-reducing agent is to satisfy the concrete workability requirement.
By table 2 as seen, physical performance index such as the fineness of the silicate cement 3 of the silicate cement of precenting chlorate corrosion and high precenting chlorate corrosion, time of coagulation, stability, intensity satisfies the requirement of ordinary Portland cement 32.5R strength grade in two kinds; Physical performance indexs such as the fineness of the silicate cement 2 of high precenting chlorate corrosion, time of coagulation, stability, intensity satisfy the requirement of ordinary Portland cement 42.5R strength grade.The concrete of the silicate cement preparation of four kinds of precenting chlorate corrosions all has higher precenting chlorate corrosion ability.
According to envrionment conditions and buildings endurance life, select for use high anti-villaumite silicate cement or in anti-villaumite silicate cement, water-cement ratio is in accordance with regulations just used can make the resisting chloride ion penetration corrosion concrete easily, thereby promote the large-scale popularization of resisting chloride ion penetration corrosion concrete to use, improve the endurance life of concrete steel building under the bar in chlorine salt solution.

Claims (9)

1. the silicate cement of a precenting chlorate corrosion is characterized in that component and content are as follows:
Component concentration (weight %)
Portland clinker 14~94
Mixing material 5~85
Gypsum 1~10
Auxiliary agent 0~15.
2. the silicate cement of precenting chlorate corrosion according to claim 1 is characterized in that described mixing material is one or more in granulated blast-furnace slag, flyash, pozzolana mixed material, silicon ash, metakaolin, zeolite powder, slag, granulation refining ferrochrome slag, granulation calcium enriched cyclone-furnace slag, iron-tion slag, granulation carbon ferrochrome slag, granulation blast furnace titanium slag, Wingdale, sandstone, waste ceramic, the kiln ash.
3. the silicate cement of precenting chlorate corrosion according to claim 2; it is characterized in that when adopting granulated blast-furnace slag, slag, granulation refining ferrochrome slag, granulation calcium enriched cyclone-furnace slag, iron-tion slag, granulation carbon ferrochrome slag, granulation blast furnace titanium slag as mixing material; will be with its independent grinding, specific surface area is at 200~2000m 2In/the kg.
4. the silicate cement of precenting chlorate corrosion according to claim 2 is characterized in that described auxiliary agent is one or more in grinding aid, tensio-active agent, exciting agent, the concrete admixture.
5. the silicate cement of precenting chlorate corrosion according to claim 4 is characterized in that described grinding aid is trolamine or diethanolamine.
6. the silicate cement of precenting chlorate corrosion according to claim 4 is characterized in that described tensio-active agent is alkyl carboxylate or naphthalenesulfonate.
7. the silicate cement of precenting chlorate corrosion according to claim 4 is characterized in that described exciting agent is a calcium sulfate.
8. the silicate cement of precenting chlorate corrosion according to claim 4 is characterized in that described concrete admixture is one or more in water reducer, high efficiency water reducing agent, hardening accelerator, retardant, air entrapment agent, rust inhibitor, swelling agent, water-holding agent, the economization agent.
9. according to the silicate cement of claim 2 or 3 or 4 described precenting chlorate corrosions, it is characterized in that in silicate cement that again it is 0~2% chopped strand that admixture has the volume volume.
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