CN102745928A - High-activity modified metakaolin-based mineral admixture for concrete and preparation method for mineral admixture - Google Patents
High-activity modified metakaolin-based mineral admixture for concrete and preparation method for mineral admixture Download PDFInfo
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- CN102745928A CN102745928A CN2012102561321A CN201210256132A CN102745928A CN 102745928 A CN102745928 A CN 102745928A CN 2012102561321 A CN2012102561321 A CN 2012102561321A CN 201210256132 A CN201210256132 A CN 201210256132A CN 102745928 A CN102745928 A CN 102745928A
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Abstract
The invention relates to a high-activity modified metakaolin-based mineral admixture for concrete and a preparation method for the mineral admixture. The high-activity modified metakaolin-based mineral admixture for the concrete is prepared by mixing metakaolin and a composite modifying agent according to the mass ratio of 200:1 to 20:1, wherein the composite modifying agent is prepared by mixing 50 to 85 mass percent of stearic acid, 8 to 25 mass percent of calcium stearate and 7 to 25 mass percent of dimethyl silicone oil based on 100 mass percent. The high-activity modified metakaolin-based mineral admixture for the concrete and the preparation method for the mineral admixture have the advantages that 1) the early strength of the concrete can be remarkably strengthened; 2) the working performance of the concrete can be remarkably improved; 3) the osmosis resistance of the concrete can be improved; and 4) the mineral admixture is highly adapted to various kinds of cement and concrete additives.
Description
Technical field
The invention belongs to building material technical field, be specifically related to a kind of high activity modified metakaolin base concrete mineral admixture and preparation method thereof.
Background technology
In recent years; Along with science and technology and the development that generates; The various concrete structures that under rigors, use, like bridge spanning the sea, subbottom tunnel, offshore production platform, nuclear reactor etc., and the construction of the processing of various hazardous and noxious substances need be in continuous increase.Therefore, no matter be from serviceability or endurance quality, concrete all there has been higher requirement.At present, the application of various superfine powders has improved the performance of concrete each side greatly, not only can significantly improve concrete intensity, and has greatly improved the performance of microtexture aspect, has improved the endurance quality of material.Yet, for traditional mineral admixture,,, also there is certain defective though use comparatively maturation like a kind of or two kinds of compositions in silicon ash, flyash and the breeze, for example the price of silicon ash is too high, and demand is greater than output; The early hydration ability of flyash is relatively poor, during single fly ash early age strength of concrete is had certain disadvantageous effect, and volume can the accelerate concrete carbonization when excessive; The performance that slag acts in concrete receives fineness, temperature effect bigger.Therefore, metakaolin more and more receives people's attention as a kind of novel concrete mineral admixture.
At present, be that for metakaolin the practical application in the concrete works does not also have report, but active just day by day as high reactivity supplementary cementitious material of new generation research abroad and application.Metakaolin has excellent pozzolanic activity, can significantly improve early age strength of concrete, and later strength is also in continuous enhancing simultaneously.Even there are some researches show that activity of metakaolin is higher than the silicon ash, and the concrete self-constriction of the importing meeting of silicon ash increases, and the metakaolin concrete has the microdilatancy performance of compensate for shrinkage.In addition, mix the metakaolin concrete and reduce bleeding, quicken the aquation of cement, improve concrete degree of compactness, thereby strengthen concrete anti-permeability performance, improve weather resistance.Comprehensive, metakaolin mix the performance that can significantly improve the concrete each side.
Yet, can significant reduction can be arranged to workability of concrete when singly mixing metakaolin, even influence normal construction.In order to guarantee the concrete serviceability of metakaolin; Have and in the metakaolin Additive, directly sneak into solid-state water reducer in the research as compound Additive; This type compound water reducer in early stage might the bad problem of flexibility occur with between the cement; And might mutual interferential effect occur with the water reducer that uses in the construction process, thereby this way has problems still in actual application.Therefore, the pozzolanic activity that how to improve the concrete serviceability of metakaolin and more effectively excite metakaolin remains further to be studied, and is applied among the actual engineering.
Summary of the invention
The object of the present invention is to provide a kind of metakaolin base mineral admixture and preparation method thereof with higher pozzolanic activity and good working performance; It can more effectively excite the pozzolanic activity of metakaolin; Especially be embodied in the early strength aspect; Also have a better role for concrete serviceability simultaneously, and be adapted to water reducer in different types of cement and the construction process.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of high activity modified metakaolin base concrete mineral admixture; It is mixed with by metakaolin and composite modifier and forms; The mass ratio of metakaolin and composite modifier is 200:1-20:1; Wherein said composite modifier is followed successively by 50%-85%, 8%-25% and 7%-25% mixed preparing by Triple Pressed Stearic Acid, calcium stearate and methyl-silicone oil according to mass percent and forms, and each percentages of ingredients sum is 100%.
Press such scheme, described metakaolin is that kaolin makes through the temperature lower calcination 0.5-6.0 hour postcooling of grinding at 500-1000 ℃.
Press such scheme, SiO in the metakaolin
2With Al
2O
3Quality percentage composition sum>=50wt%, specific surface area>=2300m
2/ kg.
The preparation method of high activity modified metakaolin base concrete mineral admixture is characterized in that including following steps:
1) metakaolin is placed 100 ℃ of baking oven 24h;
2) step 1) is put into ceramic ball mill through the metakaolin of oven dry; Add the composite modifier that Triple Pressed Stearic Acid, calcium stearate and methyl-silicone oil are formed; Milling time is 30-120min, obtains the modification metakaolin, and the mass ratio of metakaolin and composite modifier is 200:1-20:1; Wherein said Triple Pressed Stearic Acid, calcium stearate and methyl-silicone oil are followed successively by 50%-85%, 8%-25% and 7%-25% mixed preparing according to mass percent and form, and each percentages of ingredients sum is 100%.
Press such scheme, described metakaolin is that kaolin makes through the temperature lower calcination 0.5-6.0 hour postcooling of grinding at 500-1000 ℃.
Press such scheme, SiO in the metakaolin
2With Al
2O
3Quality percentage composition sum>=50wt%, specific surface area>=2300m
2/ kg.
In the technical scheme of the present invention; In the modification metakaolin modifying process; Metakaolin is under mechanical effect, and properties-correcting agent is adsorbed on the surface of metakaolin through physical action and chemical action, gets into reunion metakaolin particle gap; It has two significant functions: the one, and the metakaolin of agglomerated fully disperses, and the 2nd, to the modification of metakaolin particle surface.
The invention has the advantages that:
1) the present invention obviously improves concrete early strength, and the volume of modification metakaolin base mineral admixture is 5wt%-10wt% in the ordinary mortar, can significantly improve mortar 7d intensity more than 10%, and the 28d strength growth rate can remain on more than 8% still.When the volume of modification metakaolin was 5%, 7d ultimate compression strength increased more than 12%, and for the unmodified metakaolin of equal volume, its rate of increase is 8%.And the volume of working as the modification metakaolin reaches 10%, and 7d ultimate compression strength increases more than 14%, and for the unmodified metakaolin of equal volume, its rate of increase then is 7%.Metakaolin is as a kind of concrete mineral admixture, because its pozzolanic activity and little filling effect can significantly improve concrete early strength and later stage weather resistance.Yet,, make the modification metakaolin more effectively be scattered in the gelling material owing to be combined in the interaction of the properties-correcting agent on metakaolin surface; Properties-correcting agent discharges from modification metakaolin surface in hydration process; Simultaneously, because Triple Pressed Stearic Acid can combine with calcium ion to generate insoluble calcium salt, this has just quickened hydrated reaction of cement to a certain extent; Improve the secondary hydration effect of metakaolin, and in the further hydration reaction process, gradually calcium ion is discharged.Therefore, the modification metakaolin can significantly improve concrete early strength;
2) the present invention significantly improves concrete serviceability, and when the volume of metakaolin was 5wt%-10wt% in the ordinary mortar, its degree of mobilization descended about 20mm-40mm.Yet when mixing the modification metakaolin of equal volume, its degree of mobilization can remain unchanged basically, even higher.The metakaolin particle surface since with properties-correcting agent generation Chemical bond or physisorption, make modification metakaolin surface contain a large amount of hydrophobic groups, thereby reduced the wetting angle of modification metakaolin widely.Simultaneously, in cement hydration process, properties-correcting agent can discharge from the metakaolin surface, and does not influence the activity of metakaolin;
3) the present invention can improve concrete impermeabilisation ability, and behind the adding modification metakaolin, volcanical ash effect and little filling effect owing to metakaolin can improve concrete compactness greatly in the normal concrete.Simultaneously, the properties-correcting agent that from the modification metakaolin, discharges forms the fine and close hydrophobic film of one deck at concrete surface, can effectively intercept the intrusion of solution and harmful ion.Therefore, the modification metakaolin can improve concrete impermeabilisation ability significantly, thereby improves durability of concrete;
4) the present invention is good to different types of cement and concrete additive flexibility; Usually can occur water reducer and cement in the engineering reality and the bad phenomenon of consistency occur, and modification metakaolin of the present invention the bad problem of flexibility can not occur for the kind of various admixtures and cement.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
A kind of high activity modified metakaolin base concrete mineral admixture, it at first makes metakaolin through grinding at 2 hours postcooling of temperature lower calcination of 850 ℃ by kaolin, wherein, guarantees SiO in the metakaolin
2With Al
2O
3Quality percentage composition sum>=50wt%, specific surface area>=2300m
2/ kg; Then metakaolin is placed 100 ℃ of baking oven 24h; At last metakaolin, properties-correcting agent are obtained the modification metakaolin at grinding in ball grinder 30min; Wherein, the mass ratio of metakaolin and properties-correcting agent is 50:1, and described properties-correcting agent is followed successively by 80%, 10% and 10% mixed preparing according to mass percent and is formed by Triple Pressed Stearic Acid, calcium stearate and methyl-silicone oil.
As investigating object, metakaolin and modification metakaolin all replace gelling material configuration mortar with 5% equivalent with mortar specimen.Selection standard sand, wc is 0.45.Degree of mobilization according to the mixture of GB/T 2429-2005 " Test method for fluidity of cement mortar " test benchmark appearance and embodiment 1; According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar ", with 3 days, 7 days and 28 days ultimate compression strength of omnipotent pressure testing machine test benchmark appearance and embodiment.
The degree of mobilization of mortar specimen embodiment 1 and intensity experiment result see table 1.
The degree of mobilization of table 1 mortar specimen and intensity
Table 1 has been explained: the volume of embodiment 1 modification metakaolin is 5% o'clock, and the degree of mobilization of mortar specimen is compared the metakaolin of equal volume among the embodiment, is significantly improved.Explain that the modification metakaolin has the improvement effect to serviceability.Embodiment 1 and metakaolin are for benchmark appearance, and 3d, 7d and 28d intensity all show tangible growth.And the 7d intensity of comparative example 1 and metakaolin, strength growth rate is respectively 8%, explains that the present invention has promoter action to early strength, and 28d intensity shows later strength development did not influence simultaneously.
Embodiment 2:
A kind of high activity modified metakaolin base concrete mineral admixture, it at first makes metakaolin through grinding at 2 hours postcooling of temperature lower calcination of 850 ℃ by kaolin, wherein, guarantees SiO in the metakaolin
2With Al
2O
3Quality percentage composition sum>=50wt%, specific surface area>=2300m
2/ kg; Then metakaolin is placed 100 ℃ of baking oven 24h; At last metakaolin, properties-correcting agent are obtained the modification metakaolin at grinding in ball grinder 30min; Wherein, the mass ratio of metakaolin and properties-correcting agent is 100:1, and described properties-correcting agent is followed successively by 80%, 10% and 10% mixed preparing according to mass percent and is formed by Triple Pressed Stearic Acid, calcium stearate and methyl-silicone oil.
As investigating object, metakaolin and modification metakaolin all replace gelling material configuration mortar with 5% equivalent with mortar specimen.Selection standard sand, wc is 0.45.Degree of mobilization according to the mixture of GB/T 2429-2005 " Test method for fluidity of cement mortar " test benchmark appearance and embodiment 2; According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar ", with 3 days, 7 days and 28 days ultimate compression strength of omnipotent pressure testing machine test benchmark appearance and embodiment.
The degree of mobilization of mortar specimen embodiment 2 and intensity experiment result see table 2.
The degree of mobilization of table 2 mortar specimen and intensity
Table 2 has been explained: the volume of modification metakaolin is 5% o'clock among the embodiment 2, and the metakaolin that the degree of mobilization of mortar specimen is compared equal volume among the embodiment is significantly improved, and surpasses benchmark appearance.This shows that also the modification metakaolin is to the serviceability effect of having clear improvement.Simultaneously, the 7d intensity of comparative example's 2 test specimens and metakaolin test specimen, strength growth rate is 3.5%, explains that the present invention has promoter action to early strength.
Embodiment 3:
A kind of high activity modified metakaolin base concrete mineral admixture, it at first makes metakaolin through grinding at 6 hours postcooling of temperature lower calcination of 650 ℃ by kaolin, wherein, guarantees SiO in the metakaolin
2With Al
2O
3Quality percentage composition sum>=50wt%, specific surface area>=2300m
2/ kg; Then metakaolin is placed 100 ℃ of baking oven 24h; At last metakaolin, properties-correcting agent are obtained the modification metakaolin at grinding in ball grinder 60min; Wherein, the mass ratio of metakaolin and properties-correcting agent is 50:1, and described properties-correcting agent is followed successively by 50%, 25% and 25% mixed preparing according to mass percent and is formed by Triple Pressed Stearic Acid, calcium stearate and methyl-silicone oil.
With the mortar specimen is to investigate object, and metakaolin and modification metakaolin all replace gelling material configuration mortar with 10% equivalent.Selection standard sand, wc is 0.45.Degree of mobilization according to the mixture of GB/T 2429-2005 " Test method for fluidity of cement mortar " test benchmark appearance and embodiment 3; According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar ", with 3 days, 7 days and 28 days ultimate compression strength of omnipotent pressure testing machine test benchmark appearance and embodiment.
The degree of mobilization of mortar specimen embodiment 3 and intensity experiment result see table 3.
The degree of mobilization of table 3 mortar specimen and intensity
Table 3 has been explained: the volume of modification metakaolin is 10% o'clock among the embodiment 3, and it is as far as the improvement effect of the degree of mobilization metakaolin with respect to equal volume, and is still apparent in view.Simultaneously, with regard to 7d intensity, embodiment 3 reaches 8.2% with respect to the metakaolin rate of increase of equal volume.Explain that the present invention not only can improve serviceability, and can promote the growth of early strength.
Embodiment 4:
A kind of high activity modified metakaolin base concrete mineral admixture, it at first makes metakaolin through grinding at 4 hours postcooling of temperature lower calcination of 750 ℃ by kaolin, wherein, guarantees SiO in the metakaolin
2With Al
2O
3Quality percentage composition sum>=50wt%, specific surface area>=2300m
2/ kg; Then metakaolin is placed 100 ℃ of baking oven 24h; At last metakaolin, properties-correcting agent are obtained the modification metakaolin at grinding in ball grinder 45min; Wherein, the mass ratio of metakaolin and properties-correcting agent is 200:3, and described properties-correcting agent is followed successively by 60%, 15% and 25% mixed preparing according to mass percent and is formed by Triple Pressed Stearic Acid, calcium stearate and methyl-silicone oil.
With the mortar specimen is to investigate object, and metakaolin and modification metakaolin all replace gelling material configuration mortar with 10% equivalent.Choose river sand (crossing the 2.36mm sieve), wc is 0.45, and water reducer (naphthalene is a pulvis) volume is 2%.Degree of mobilization according to the mixture of GB/T 2429-2005 " Test method for fluidity of cement mortar " test benchmark appearance and embodiment 4; According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar ", with 7 days and 28 days ultimate compression strength of omnipotent pressure testing machine test benchmark appearance and embodiment.
The degree of mobilization of table 4 mortar specimen and intensity
Table 4 has been explained: the volume of modification metakaolin is 10% among the embodiment 4, and when the admixture of matched with proper used, its degree of mobilization still had comparatively significantly improvement effect.7d intensity has increased by 5.9% with respect to the metakaolin test specimen of equal volume simultaneously.Explain that the present invention has good flexibility to admixture.
Claims (6)
1. high activity modified metakaolin base concrete mineral admixture; It is mixed with by metakaolin and composite modifier and forms; The mass ratio of metakaolin and composite modifier is 200:1-20:1; Wherein said composite modifier is followed successively by 50%-85%, 8%-25% and 7%-25% mixed preparing by Triple Pressed Stearic Acid, calcium stearate and methyl-silicone oil according to mass percent and forms, and each percentages of ingredients sum is 100%.
2. high activity modified metakaolin base concrete mineral admixture according to claim 1 is characterized in that: described metakaolin is that kaolin makes through the temperature lower calcination 0.5-6.0 hour postcooling of grinding at 500-1000 ℃.
3. high activity modified metakaolin base concrete mineral admixture according to claim 2 is characterized in that: SiO in the metakaolin
2With Al
2O
3Quality percentage composition sum>=50wt%, specific surface area>=2300m
2/ kg.
4. the preparation method of the described high activity modified metakaolin base concrete mineral admixture of claim 1 is characterized in that including following steps:
1) metakaolin is placed 100 ℃ of baking oven 24h;
2) step 1) is put into ceramic ball mill through the metakaolin of oven dry; Add the composite modifier that Triple Pressed Stearic Acid, calcium stearate and methyl-silicone oil are formed; Milling time is 30-120min, obtains the modification metakaolin, and the mass ratio of metakaolin and composite modifier is 200:1-20:1; Wherein said Triple Pressed Stearic Acid, calcium stearate and methyl-silicone oil are followed successively by 50%-85%, 8%-25% and 7%-25% mixed preparing according to mass percent and form, and each percentages of ingredients sum is 100%.
5. the preparation method of high activity modified metakaolin base concrete mineral admixture according to claim 4 is characterized in that: described metakaolin is that kaolin makes through the temperature lower calcination 0.5-6.0 hour postcooling of grinding at 500-1000 ℃.
6. the preparation method of high activity modified metakaolin base concrete mineral admixture according to claim 5 is characterized in that: SiO in the metakaolin
2With Al
2O
3Quality percentage composition sum>=50wt%, specific surface area>=2300m
2/ kg.
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| CN103145371A (en) * | 2013-03-01 | 2013-06-12 | 武汉理工大学 | High-flowability high-strength super-retarded steel tube concrete additive and preparation method thereof |
| CN103214203A (en) * | 2013-05-15 | 2013-07-24 | 务川自治县鹏程建材有限责任公司 | Concrete additive |
| CN104119010A (en) * | 2014-08-15 | 2014-10-29 | 武汉理工大学 | Retarding type high-fluidity high-strength underwater concrete additive and preparation method thereof |
| CN105198296A (en) * | 2015-09-30 | 2015-12-30 | 中国地质大学（武汉） | Metakaolin-based geopolymer with superhydrophobic surface and preparation method thereof |
| CN105731943A (en) * | 2016-01-25 | 2016-07-06 | 茂名高岭科技有限公司 | Compact enhanced mortar waterproofing agent |
| CN106587686A (en) * | 2016-12-15 | 2017-04-26 | 云南省建设投资控股集团有限公司 | Metakaolin-based high-performance concrete composite admixture and application thereof |
| CN108147735A (en) * | 2017-12-01 | 2018-06-12 | 陈合华 | A kind of preparation method of high compressive strength waterproof dry powder mortar |
| CN108249805A (en) * | 2017-12-13 | 2018-07-06 | 镇江建科建设科技有限公司 | A kind of preparation method of mineral admixture and a kind of self-compacting concrete |
| CN109133739A (en) * | 2018-08-25 | 2019-01-04 | 太和县鑫泰高科新型建筑材料有限公司 | A kind of preparation method of rubber powder-metakaolin modified high-strength concrete |
| CN109400001A (en) * | 2018-12-19 | 2019-03-01 | 中建商品混凝土有限公司 | A kind of anti-clogging ecotype pervious concrete additive and preparation method thereof |
| CN111348854A (en) * | 2020-03-12 | 2020-06-30 | 河南天竞骏腾新材料研究院有限公司 | Waterproof and antifreezing additive for mortar and concrete and preparation method thereof |
| CN115448671A (en) * | 2022-10-12 | 2022-12-09 | 中交路桥华南工程有限公司 | Low-heat anti-erosion large-volume marine concrete for sea-crossing bridge bearing platform and preparation method thereof |
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2012
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| CN103145371B (en) * | 2013-03-01 | 2015-04-08 | 武汉理工大学 | High-flowability high-strength super-retarded steel tube concrete additive and preparation method thereof |
| CN103145371A (en) * | 2013-03-01 | 2013-06-12 | 武汉理工大学 | High-flowability high-strength super-retarded steel tube concrete additive and preparation method thereof |
| CN103214203A (en) * | 2013-05-15 | 2013-07-24 | 务川自治县鹏程建材有限责任公司 | Concrete additive |
| CN104119010A (en) * | 2014-08-15 | 2014-10-29 | 武汉理工大学 | Retarding type high-fluidity high-strength underwater concrete additive and preparation method thereof |
| CN105198296A (en) * | 2015-09-30 | 2015-12-30 | 中国地质大学（武汉） | Metakaolin-based geopolymer with superhydrophobic surface and preparation method thereof |
| CN105731943B (en) * | 2016-01-25 | 2017-12-12 | 茂名高岭科技有限公司 | A kind of closely knit enhanced mortar waterproof agent |
| CN105731943A (en) * | 2016-01-25 | 2016-07-06 | 茂名高岭科技有限公司 | Compact enhanced mortar waterproofing agent |
| CN106587686A (en) * | 2016-12-15 | 2017-04-26 | 云南省建设投资控股集团有限公司 | Metakaolin-based high-performance concrete composite admixture and application thereof |
| CN108147735A (en) * | 2017-12-01 | 2018-06-12 | 陈合华 | A kind of preparation method of high compressive strength waterproof dry powder mortar |
| CN108249805A (en) * | 2017-12-13 | 2018-07-06 | 镇江建科建设科技有限公司 | A kind of preparation method of mineral admixture and a kind of self-compacting concrete |
| CN109133739A (en) * | 2018-08-25 | 2019-01-04 | 太和县鑫泰高科新型建筑材料有限公司 | A kind of preparation method of rubber powder-metakaolin modified high-strength concrete |
| CN109400001A (en) * | 2018-12-19 | 2019-03-01 | 中建商品混凝土有限公司 | A kind of anti-clogging ecotype pervious concrete additive and preparation method thereof |
| CN109400001B (en) * | 2018-12-19 | 2021-06-22 | 中建商品混凝土有限公司 | Anti-blocking ecological pervious concrete additive and preparation method thereof |
| CN111348854A (en) * | 2020-03-12 | 2020-06-30 | 河南天竞骏腾新材料研究院有限公司 | Waterproof and antifreezing additive for mortar and concrete and preparation method thereof |
| CN115448671A (en) * | 2022-10-12 | 2022-12-09 | 中交路桥华南工程有限公司 | Low-heat anti-erosion large-volume marine concrete for sea-crossing bridge bearing platform and preparation method thereof |
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Application publication date: 20121024 |