CN105254196A - Cement concrete modifying agent resistant to sulfate erosion and preparation method thereof - Google Patents
Cement concrete modifying agent resistant to sulfate erosion and preparation method thereof Download PDFInfo
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- CN105254196A CN105254196A CN201510706442.2A CN201510706442A CN105254196A CN 105254196 A CN105254196 A CN 105254196A CN 201510706442 A CN201510706442 A CN 201510706442A CN 105254196 A CN105254196 A CN 105254196A
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Abstract
The invention discloses a cement concrete modifying agent resistant to sulfate erosion and a preparation method thereof. The cement concrete modifying agent resistant to sulfate erosion is formed by mixing metakaolin, calcined hydrotalcite, fly ash and lime stone powder, wherein the admixture amount of the metakaolin is 50-70%, the admixture amount of the calcined hydrotalcite is 15-30%, the admixture amount of the fly ash is 10-20%, and the admixture amount of the lime stone powder is 0-10%. When metakaolin is doped in cement concrete, the metakaolin reacts with calcium hydroxide in cement hydrated products, a large amount of hydrated calcium silicate and hydrated calcium aluminate are generated, holes in the concrete is filled with the hydrated calcium silicate and the hydrated calcium aluminate, transfer of harmful sulfate ions in the concrete is delayed, and therefore the sulfate erosion resistance of the cement concrete is improved. According to the cement concrete modifying agent resistant to sulfate erosion, the sulfate erosion resistance and the compressive strength of the concrete can be remarkably improved at low admixture amount, and meanwhile the working performance of the concrete is not affected.
Description
Technical field
The present invention relates to building material technical field, be specifically related to a kind of cement concrete resisting erosion of sulfate properties-correcting agent and preparation method thereof.
Background technology
In recent years, the endurance issues of cement concrete comes into one's own day by day, and the erosion damage that wherein vitriol causes is one of important factor in order of concrete durability.In China, northwest, south China and coastland, all have a large amount of saline soil and sulfuric acid solonchak, and meanwhile, seawater, acid rain and trade effluent etc. also bring sulfate ion harmful to concrete in a large number.Abroad, the country such as Germany, Japan, Canada, the U.S. also has the phenomenon of sulphate attack concrete structure, thus brings serious financial loss.Based on this, the concrete corrosion that vitriol causes destroys to need badly and is resolved.
Concrete sulphate attack is physical and chemical process concrete being played to destruction occurred between the mineral in sulfate ion and hydrolysis product of cement, swelling cracking caused by the expansion reaction that reason occurs at inside concrete for sulfate ion, and the concrete strength that in hydrated product, Ca (OH) 2 and the stripping of C-S-H gel cause declines.Common vitriol comprises Na2SO4, MgSO4, (NH4) 2SO4, K2SO4 etc.
The degree that sulphate attack destroys depends primarily on cement tricalcium aluminate content, cement consumption and concrete degree of compactness in concrete.At present, the method improving Concrete Resist Reinforcing Sulfate Corrosion mainly concentrates on and uses mineral admixture to improve concrete degree of compactness, delays the transmission of sulfate ion at inside concrete.Meanwhile, mix mineral admixture and decrease cement consumption in concrete, further improve concrete sulphate-corrosion resistance energy.But the use of a large amount of mineral admixture all has disadvantageous effect to mechanical performance of concrete and anti-carbonation properties, still lack a kind of resisting erosion of sulfate properties-correcting agent efficiently in current engineering, improve concrete sulphate-corrosion resistance energy.
Metakaolin a kind ofly in concrete application, has the mineral admixture of large quantity research, and slough water and hydroxyl by kaolin and formed, along with the rising of calcining temperature, kaolin laminate structure is destroyed, and defines the transition phase that degree of crystallinity is very poor, is metakaolin.Metakaolin is widely used as mineral admixture in concrete, its filling effect and volcano ash effect can promote its hydration in cement-based material, improve concrete early strength and later strength, strengthen its anti-permeability performance and volume stability.Intercalated houghite is a kind of new function material of laminate structure, the structural unit of its principal character to be laminated body structure be positively charged, and interlayer is tradable negatively charged ion.When being heated to 450 ~ 550 DEG C, interlayer anion is sloughed and destroys its veneer structure, but under the environment having negatively charged ion and water to exist, intercalated houghite can adsorpting anion to rebuild veneer structure.Therefore, there is through the intercalated houghite of roasting the effect of adsorpting anion.Flyash and limestone powder are conventional mineral admixture, can improve concrete weather resistance.Above-mentioned adulterant all has the effect improving Sulfate Resistance of Concrete energy, but its net effect still requires study.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of cement concrete resisting erosion of sulfate properties-correcting agent and preparation method thereof, the invention solves the sulphate-corrosion resistance energy and the concrete weather resistance technical problem of comprehensive improvement that how to improve cement concrete.
The present invention is achieved through the following technical solutions:
A kind of cement concrete resisting erosion of sulfate properties-correcting agent, be prepared from by metakaolin, calcined hydrotalcite, flyash, limestone powder, wherein metakaolin volume is 50 ~ 70%, calcined hydrotalcite volume is 15% ~ 30%, doping quantity of fly ash is 10 ~ 20%, limestone powder volume is 0 ~ 10%, is more than mass percentage.
According to such scheme, described metakaolin makes to obtain with the following method: bulk kaolin is put into the grinding that ball mill carries out 20 ~ 40 minutes by (1), obtains kaolin powder; (2) kaolin powder is calcined 1 ~ 5 hour at 500 ~ 800 DEG C, be cooled fast to room temperature, and carry out the grinding of 20 ~ 40 minutes in ball mill, obtain metakaolin.
According to such scheme, described calcined hydrotalcite makes to obtain with the following method: cooling is obtained fast after the roasting temperature 0.5-6h of 300 DEG C-750 DEG C for magnalium carbonate hydrotalcite, the Al of calcined hydrotalcite
2o
3with between content of MgO 50wt%-60wt%, the mass median diameter of particle is less than 10 μm.
According to such scheme, described flyash is the flying dust captured in the flue gas after thermal power plant coal burning, and its 45 μm of square hole sieves tail over and are not more than 12%, and water demand ratio is not more than 95%.
According to such scheme, described limestone powder be Wingdale levigate after powder, its specific surface area is not more than 400m
2/ kg.
Above-mentioned a kind of cement concrete resisting erosion of sulfate properties-correcting agent and preparation method thereof, comprises the steps:
(1) prepare burden: metakaolin volume is 40 ~ 60%, and calcined hydrotalcite volume is 10% ~ 30%, and doping quantity of fly ash is 10 ~ 20%, and limestone powder volume is 0 ~ 10%.
(2) after hydrotalcite, flyash, limestone powder being mixed, compound is mixed with metakaolin, after mixing, obtain cement concrete resisting erosion of sulfate properties-correcting agent.
The present invention compared with prior art, has following obvious advantage:
One, metakaolin and calcined hydrotalcite are carried out compound by the present invention, are aided with flyash and limestone powder as adulterant, for the sulphate-corrosion resistance energy of modified cement-concrete.Wherein, metakaolin is kaolin calcined obtained by bulk, is stripped of the OH-in structure in calcination process, and crystalline structure destroys, thus has very high pozzolanic activity.When mixing metakaolin in cement concrete, calcium hydroxide in metakaolin and hydrolysis product of cement reacts, generate a large amount of hydrated calcium silicates and drated calcium aluminate, be filled with the hole of inside concrete, delay the transmission of harmful sulfate ion at inside concrete, thus improve the sulphate-corrosion resistance energy of cement concrete.
Two, calcined hydrotalcite used in the present invention, by magnalium carbonate hydrotalcite, after the roasting temperature 0.5-6h of 300 DEG C-750 DEG C, cooling is obtained fast, hydrotalcite after roasting at high temperature laminate structure destroys, and under the environment having negatively charged ion and water to exist, then can rebuild with negatively charged ion and form laminate structure.When mixing calcined hydrotalcite in cement concrete, first negatively charged ion reacts with calcined hydrotalcite after entering concrete, thus consume the extraneous harmful sulfate ion invaded, delay the vitriol reaction of cement concrete inside, thus improve the sulphate-corrosion resistance energy of cement concrete.
Three, flyash used in the present invention and limestone powder, specific surface area comparatively cement granules is larger, can play significant filling effect, increase the degree of compactness of cement concrete, delayed the transmission of sulfate ion at inside concrete in cement concrete.Flyash enhances the degree of compactness in cement concrete later stage at the volcano ash effect in hydrated cementitious later stage, can improve the poor flow quality because metakaolin and calcined hydrotalcite water requirement cause greatly simultaneously, improve the serviceability of cement concrete mixing thing.
Four, calcined hydrotalcite is used for the sulphate-corrosion resistance energy improving cement concrete by the present invention, and before changing, single dependence improves coagulating cement soil compactness and the thinking changing chemistry of cement composition.The present invention utilizes calcined hydrotalcite to adsorb the sulfate ion of extraneous intrusion and inside concrete, has significantly delayed the reaction of sulfate ion and hydrolysis product of cement.The solidification anion effect of calcined hydrotalcite is formed with the optimization pore structure effect of metakaolin, flyash, limestone powder and superposes, and significantly improves the sulphate-corrosion resistance energy of cement concrete.
Five, mix the concrete after resisting erosion of sulfate properties-correcting agent of the present invention, serviceability is without obvious reduction, and its slump reduced rate is all lower than 15%, and wherein numbering 3 properties-correcting agent mixes rear slump reduced rate below 5%; Concrete crushing strength has remarkable increase, and wherein 3 days ultimate compression strength on average increases by more than 67%, and within 7 days, ultimate compression strength on average increases by more than 40%, and within 28 days, ultimate compression strength on average increases by more than 20%; After drying and watering cycle, loss of strength significantly reduces, and significantly improves concrete sulphate-corrosion resistance energy.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
A kind of cement concrete resisting erosion of sulfate properties-correcting agent, is prepared from by metakaolin, calcined hydrotalcite, flyash, limestone powder.Metakaolin is calcined and to be cooled grinding after 4 hours and obtain at 700 DEG C, and calcined hydrotalcite calcine cooling after 4 hours and obtained at 500 DEG C.For modified cement-concrete sulphate-corrosion resistance can modifier than as shown in table 1.
The proportioning of table 1 cement concrete resisting erosion of sulfate properties-correcting agent
With reference to the regulation of GB/T749-2008 " Sulphate resistance test for cement ", the present invention uses cement concrete resisting erosion of sulfate properties-correcting agent and cement, dihydrate gypsum compound to prepare cement mortar test block, experiment water-cement ratio is 0.36, and test block is of a size of 25 × 25 × 280 millimeters.By a certain amount of dihydrate gypsum of admixture in cement, make the SO in cement
3content reaches 7.0%, makes excessive SO
4 2-directly with cement in affect sulphate-corrosion resistance energy mineral react to generate and expand.The present invention, by measuring different ratio properties-correcting agent to the impact of glue sand test specimen different larval instar rate of expansion, weighs the sulphate-corrosion resistance energy of cement mortar.
Resisting erosion of sulfate properties-correcting agent shown in table 1 is mixed in cement according to the method for mixing outward, mass percent is 10%, the water that the test block of glue sand is placed in 20 ± 1 DEG C is soaked maintenance, the length of test maintenance test block after 14 days, 42 days, 70 days, calculate the rate of expansion of cement mortar test specimen, and contrast in check sample.Calculation result is as shown in table 2.
The rate of expansion of table 2 modified water earth rubber sand test specimen
Test result shows, the sulfate ion in the adsorbable hydrolysis product of cement of resisting erosion of sulfate properties-correcting agent that the present invention uses, improves the potential sulphate-corrosion resistance energy of cement mortar.Wherein, the sample rate of expansion of numbering 3,4,5 significantly reduces, and shows that in this proportioning, properties-correcting agent has more excellent resisting erosion of sulfate modified effect.
Embodiment 2
A kind of cement concrete resisting erosion of sulfate properties-correcting agent, is prepared from by metakaolin, calcined hydrotalcite, flyash, limestone powder.Metakaolin is calcined and to be cooled grinding after 4 hours and obtain at 700 DEG C, and calcined hydrotalcite calcine cooling after 4 hours and obtained at 500 DEG C.Prepare cement concrete resisting erosion of sulfate properties-correcting agent according to numbering in table 13,4,5, substitute cement add in cement concrete according to the proportioning of 0,5% and 10% respectively, cement concrete proportioning is as shown in table 3.
Table 3 concrete mix
According to the method for GB/T50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard ", the slump of test concrete mix, test result is as shown in table 4.
Table 4 concrete slump
Test result shows, mixes the concrete after resisting erosion of sulfate properties-correcting agent, and the impact of its serviceability is not obvious, meets engineering service requirements.
Embodiment 3
A kind of cement concrete resisting erosion of sulfate properties-correcting agent, is prepared from by metakaolin, calcined hydrotalcite, flyash, limestone powder.Metakaolin is calcined and to be cooled grinding after 4 hours and obtain at 700 DEG C, and calcined hydrotalcite calcine cooling after 4 hours and obtained at 500 DEG C.Prepare cement concrete resisting erosion of sulfate properties-correcting agent according to numbering in table 13,4,5, substitute cement add in cement concrete according to the proportioning of 5% and 10% respectively, cement concrete proportioning is as shown in table 3.
According to GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ", method, test concrete 3 days, 7 days and 28 days ultimate compression strength, test result is as shown in table 5.
Table 5 concrete crushing strength test result
Test result shows, mixes the concrete of resisting erosion of sulfate properties-correcting agent, and ultimate compression strength has and comparatively significantly promotes, and early strength rises particularly evident.
Embodiment 4
A kind of cement concrete resisting erosion of sulfate properties-correcting agent, is prepared from by metakaolin, calcined hydrotalcite, flyash, limestone powder.Metakaolin is calcined and to be cooled grinding after 4 hours and obtain at 700 DEG C, and calcined hydrotalcite calcine cooling after 4 hours and obtained at 500 DEG C.Prepare cement concrete resisting erosion of sulfate properties-correcting agent according to numbering in table 13, substitute cement add in cement concrete according to the proportioning of 5% and 10% respectively, cement concrete proportioning is as shown in table 3.
Regulation with reference to GBT50082-2009 " Standard for test methods of longterm performance and durability of ordinary concrete standard " carries out Testing Resistance of Concrete To Sulfate.Test block maintenance 28 days under physical environment, dries the Na being placed on 2mol/L
2sO
4carry out drying and watering cycle experiment in solution, drying and watering cycle system is: the baking oven being placed in 60 DEG C is dried after 24 hours, at Na
2sO
4soak 48 hours in solution, in this, as a drying and watering cycle.Experiment tests its ultimate compression strength after each loop cycle, and contrasts with check sample.Test result is as shown in table 6.
The loss of strength of table 6 concrete under condition of sulfate
Test result shows, mixes the concrete of resisting erosion of sulfate properties-correcting agent, and the loss of strength value after drying and watering cycle significantly reduces, and significantly improves concrete sulphate-corrosion resistance energy.
Technique means disclosed in the present invention program is not limited only to the technique means disclosed in above-mentioned embodiment, also comprises the technical scheme be made up of above technical characteristic arbitrary combination.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (7)
1. for a resisting erosion of sulfate properties-correcting agent for cement concrete, it is characterized in that: mixed by metakaolin, calcined hydrotalcite, flyash and limestone powder.
2. as claimed in claim 1 for the resisting erosion of sulfate properties-correcting agent of cement concrete, it is characterized in that: metakaolin volume is 50 ~ 70%, calcined hydrotalcite volume is 15% ~ 30%, and doping quantity of fly ash is 10 ~ 20%, limestone powder volume is 0 ~ 10%, is more than mass percentage.
3. as claimed in claim 1 or 2 for the resisting erosion of sulfate properties-correcting agent of cement concrete, it is characterized in that: its blending means is: after hydrotalcite, flyash, limestone powder are mixed, compound is mixed with metakaolin, after mixing, obtains cement concrete resisting erosion of sulfate properties-correcting agent.
4. as claimed in claim 1 or 2 for the resisting erosion of sulfate properties-correcting agent of cement concrete, it is characterized in that: described metakaolin makes to obtain with the following method: bulk kaolin is put into the grinding that ball mill carries out 20 ~ 40 minutes by (1), obtains kaolin powder; (2) kaolin powder is calcined 1 ~ 5 hour at 500 ~ 800 DEG C, be cooled fast to room temperature, and carry out the grinding of 20 ~ 40 minutes in ball mill, obtain metakaolin.
5. as claimed in claim 1 or 2 for the resisting erosion of sulfate properties-correcting agent of cement concrete, it is characterized in that: described calcined hydrotalcite makes to obtain with the following method: cooling is obtained fast after the roasting temperature 0.5-6h of 300 DEG C-750 DEG C for magnalium carbonate hydrotalcite, the Al of calcined hydrotalcite
2o
3with between content of MgO 50wt%-60wt%, the mass median diameter of particle is less than 10 μm.
6. as claimed in claim 1 or 2 for the resisting erosion of sulfate properties-correcting agent of cement concrete, it is characterized in that: described flyash is the flying dust captured in the flue gas after thermal power plant coal burning, its 45 μm of square hole sieves tail over and are not more than 12%, and water demand ratio is not more than 95%.
7., as claimed in claim 1 or 2 for the resisting erosion of sulfate properties-correcting agent of cement concrete, it is characterized in that: described limestone powder be Wingdale levigate after powder, its specific surface area is not more than 400m
2/ kg.
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| CN112028531A (en) * | 2020-08-24 | 2020-12-04 | 潍坊纵横建材有限公司 | Concrete corrosion-proof rust-proof composite additive and preparation method thereof |
| CN112028531B (en) * | 2020-08-24 | 2022-06-17 | 潍坊纵横建材有限公司 | Concrete corrosion-proof rust-proof composite additive and preparation method thereof |
| CN116396007A (en) * | 2023-03-24 | 2023-07-07 | 青岛理工大学 | Anti-segregation agent for concrete and application thereof and application method of anti-segregation agent for concrete |
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Application publication date: 20160120 |