CN104710131A - Cement hydration rate regulation material, and preparation method and application thereof - Google Patents
Cement hydration rate regulation material, and preparation method and application thereof Download PDFInfo
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- CN104710131A CN104710131A CN201510060171.8A CN201510060171A CN104710131A CN 104710131 A CN104710131 A CN 104710131A CN 201510060171 A CN201510060171 A CN 201510060171A CN 104710131 A CN104710131 A CN 104710131A
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Abstract
The invention provides a cement hydration rate regulation material. The cement hydration rate regulation material is water-insoluble polymer wrapped modified dextrin, wherein a mass ratio of the water-insoluble polymer to dextrin is (0.05-10):(90-99.95). The cement hydration rate regulation material has the advantages of simple preparation technology, low cost, and greatly improved cement hydration rate regulation performance. The influence of the hydration rate regulation material on cement hydration is different from that of a traditional micro-molecular retarder, the regulation material has small even no influence on the induction period of hydration, but greatly reduces hydration rate in the acceleration period and the deceleration period, and the traditional micro-molecular retarder prolongs the induction period of cement hydration, and basically has no influence on the hydration rate in the acceleration period and the deceleration period of cement hydration.
Description
Technical field
The invention belongs to concrete admixture field, be specifically related to a kind of hydrated cementitious speed controlled material and preparation method thereof and application.
Background technology
Concrete Crack Control problem is one of problem very important in construction work, and wherein thermal cracking is modal crack form.Hydrated cementitious can release a large amount of heat, and when in concrete, hydrated cementitious institute liberated heat has little time to shed, concrete internal temperature will raise, and further hydration stops, and concrete temperature can be down to again envrionment temperature; This temperature variation can cause volume of concrete to change, and under affined condition, when the tensile stress that temperature deformation is formed exceedes concrete tensile strength, will cause the formation of thermal cracking.
In order to reduce the temperature variation in concrete, just need to regulate and control the hydration process of cement, reduce the hydration rate of cement acceleration period as far as possible, the heat that hydrated cementitious is produced does not concentrate release, for concrete heat radiation is raced against time, and then the temperature rise that reduction concrete causes because of aquation, reduce the thermal stress of inside concrete, and then reduce cracking risk.
Patent JP3729340B2 discloses a kind of blended material being reduced concrete temperature rise by slag and dextrin recombination energy, and the dextrin wherein used is the commercially available dextrin without any modification, its cold water solubility 10 ~ 30%; But, open result display: concrete core temperature reduces amplitude and intensity reduces amplitude scaled versions, although namely this blended material plays the effect of cooling, it makes again concrete strength reduce.
Patent EP1233008A1 discloses a kind of swelling agent material containing dextrin, adopt commercially available without any modification, cold water solubility lower than 70% dextrin for suppressing hydration heat, disclosed result shows it and makes concrete temperature reduced by only 1 DEG C, poor effect.
Patent CN201410010473 discloses a kind of hydration heat controlled material and preparation method thereof and application: the surface crosslinking agent dextrin that it uses, and after result display is crosslinked, effect has a certain upgrade, but complex process and the time longer.
Patent CN201410009447 discloses a kind of moderate-heat portland cement Hydration controlled material, it is made up of dextrin, modified dextrins and oleic acid, the proportioning of disclosed result display optimum can reduce hydrated cementitious maximum rate peak value 66.3%, but it prepared also more complicated.
In sum, although dextrin mentioned by existing patent documentation certain hydration rate adjusting function, dextrin is amylolytic intermediate product, of a great variety, and not every dextrin all has outstanding aquation adjusting function; In current published patent or document, the material preparation process with aquation adjusting function is also loaded down with trivial details, is therefore necessary to develop that a kind of preparation process technique is simple, environmental protection and the hydrated cementitious speed controlled material of final excellent performance.
Summary of the invention
Goal of the invention: in order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of hydrated cementitious speed controlled material.
Technical scheme:
Applicant is found by large quantity research: dextrin effectively can reduce hydrated cementitious speed essential reason and be: dextrin forms one deck adsorption layer at cement particle surface, this layer of adsorption layer reduces the speed of moisture by export-oriented cement granules internal migration, and then reduces the hydration rate of cement; And dextrin is easily hydrolyzed in the basic conditions, generate micromolecular alcohol acid, this makes adsorption layer be destroyed, and then affects its aquation performance of control, and the micromolecular hydroxyl acid that dextrin degradation is formed also causes hydrated cementitious significantly to extend inductive phase.The present invention proposes to utilize more hydrophobic polymerization to the parcel carried out dextrin to a certain degree, reduce the contact area of dextrin and cement alkalescence hole solution, reduce the ratio that dextrin to be degraded in aquation inductive phase, and then reduce dextrin to the impact of aquation inductive phase, the performance improving dextrin can also be promoted simultaneously.
A kind of hydrated cementitious speed controlled material provided by the invention is the dextrin of non-soluble polymer parcel modification.
As preferably, described dextrin number-average molecular weight is 1000 ~ 90000g/mol; Preferably, described dextrin number-average molecular weight is 2000 ~ 60000g/mol; More preferably, described dextrin number-average molecular weight is 5000 ~ 30000g/mol.The present invention can use various dextrin, and its source is unrestricted, and can be obtained through acid or enzymatic hydrolysis by various starch, preparation method can with reference to documents and materials disclosed in this area; The cold water-soluble of dextrin is unrestricted, can be the white dextrin of incomplete cold water solubles, also can be consoluet yellow starch gum or maltodextrin.
Preferred as another kind, described non-soluble polymer kind is unrestricted, but preferred easily film-forming polymer, more preferably ethylene-vinyl acetate copolymer; The number-average molecular weight of described ethylene-vinyl acetate copolymer is 1000-500000g/mol, and vinyl acetate content is 5-60mol%.
Preferred as another kind, the mass ratio (0.05-10) of described non-soluble polymer and dextrin: (90-99.95); Preferably, the massfraction of described non-soluble polymer is 0.05-10%.
The preparation of hydrated cementitious speed controlled material of the present invention adopts following methods: by the suitable organic solvent dissolution of non-soluble polymer, the dextrin adding metering mixes, and removing organic solvent, obtains required aquation controlled material.
Present invention also offers the application of above-mentioned hydrated cementitious speed controlled material in concrete, described hydrated cementitious speed
The volume (consumption relative to glue material) of controlled material is 0.1-2%, more preferably 0.15-1%.
Beneficial effect: simple, with low cost, the applicable suitability for industrialized production of hydrated cementitious speed controlled material preparation technology provided by the invention, it has very large lifting to hydrated cementitious speed performance of control relative to prior art.Simultaneously, this hydration rate controlled material impact on the aquation of cement is different from traditional small molecules retardant, the inductive phase impact of this controlled material on aquation is less even not to be affected, but significantly can reduce the hydration rate of acceleration period and deceleration phase, and traditional small molecules retardant mainly extends hydrated cementitious inductive phase, and on the hydration rate of hydrated cementitious acceleration period and deceleration phase substantially without impact (see Fig. 1).
Accompanying drawing explanation
Fig. 1 is the affecting laws (TAM AIR isothermal calorimeter is tested and obtained) that hydrated cementitious speed controlled material of the present invention is different to hydrated cementitious from conventional set retarder (sucrose)
Embodiment
Following examples have described in more detail prepared according to the methods of the invention hydrated cementitious speed controlled material and performance thereof, and these embodiments provide by way of illustration, but these embodiments do not limit the scope of the invention.
In the embodiment of the present invention, molecular weight adopts Agilent 1200Infinity gel permeation chromatograph to measure.
The monitoring of hydrated cementitious exothermic process adopts U.S. TA company's T AM AIR isothermal calorimeter, and probe temperature is 20 DEG C, and test test specimen be only starch, and water-cement ratio is 0.4, and the interpolation per-cent of hydrated cementitious speed controlled material is relative to the material of glue material.The criterion of amplitude as aquation controlled material performance of the present invention is reduced using maximum heatrelease rate peak value, under the same terms peak heat release rates to reduce amplitude larger, show that hydrated cementitious speed controlled material performance is better, more can avoid the concentrated heat release of hydrated cementitious.
Concrete crushing strength performs with reference to GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete "; Concrete coagulating time performs with reference to GB/T50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard ".
In the embodiment of the present invention, use concrete mix as shown in table 1.Wherein, cement uses conch 42.5 cement; First level flour coal ash; Fine aggregate is river sand, apparent density 2.63g/cm3, and fineness modulus is 2.60; Coarse aggregate is that rubble is joined in the continuous pole of 5 ~ 20mm.
Table 1 concrete foundation proportioning (kg/m
3)
Embodiment 1
Number-average molecular weight is the dextrin of 1000g/mol, adding number-average molecular weight is 30000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 5%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99:1, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 2
Number-average molecular weight is the dextrin of 2000g/mol, adding number-average molecular weight is 30000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 20%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99:1, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 3
Number-average molecular weight is the dextrin of 5000g/mol, adding number-average molecular weight is 30000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 30%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99:1, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 4
Number-average molecular weight is the dextrin of 15000g/mol, adding number-average molecular weight is 30000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 30%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99:1, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 5
Number-average molecular weight is the dextrin of 30000g/mol, adding number-average molecular weight is 30000g/mol, vinyl acetate content is in the ethanolic soln of the ethylene-vinyl acetate copolymer of 40%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99:1, etoh solvent is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 6
Number-average molecular weight is the dextrin of 60000g/mol, adding number-average molecular weight is 30000g/mol, vinyl acetate content is in the ethanolic soln of the ethylene-vinyl acetate copolymer of 50%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99:1, etoh solvent is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 7
Number-average molecular weight is the dextrin of 90000g/mol, adding number-average molecular weight is 30000g/mol, vinyl acetate content is in the ethanolic soln of the ethylene-vinyl acetate copolymer of 40%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99:1, etoh solvent is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Comparative example 1
Do not add clean slurry, the concrete of any admixture.
Comparative example 2
Number-average molecular weight is the dextrin of 1000g/mol and number-average molecular weight is 30000g/mol, vinyl acetate content be 5% ethylene-vinyl acetate copolymer take mass ratio as the mixture that 99:1 direct physical compound obtains.
Comparative example 3
Number-average molecular weight is the dextrin of 2000g/mol and number-average molecular weight is 30000g/mol, vinyl acetate content be 20% ethylene-vinyl acetate copolymer take mass ratio as the mixture that 99:1 direct physical compound obtains.
Comparative example 4
Number-average molecular weight is the dextrin of 5000g/mol and number-average molecular weight is 30000g/mol, vinyl acetate content be 30% ethylene-vinyl acetate copolymer take mass ratio as the mixture that 99:1 direct physical compound obtains.
Comparative example 5
Number-average molecular weight is the dextrin of 15000g/mol and number-average molecular weight is 30000g/mol, vinyl acetate content be 40% ethylene-vinyl acetate copolymer take mass ratio as the mixture that 99:1 direct physical compound obtains.
Comparative example 6
Number-average molecular weight is the dextrin of 30000g/mol and number-average molecular weight is 30000g/mol, vinyl acetate content be 50% ethylene-vinyl acetate copolymer take mass ratio as the mixture that 99:1 direct physical compound obtains.
Comparative example 7
Number-average molecular weight is the dextrin of 60000g/mol and number-average molecular weight is 30000g/mol, vinyl acetate content be 40% ethylene-vinyl acetate copolymer take mass ratio as the mixture that 99:1 direct physical compound obtains.
Comparative example 8
Number-average molecular weight is the dextrin of 90000g/mol and number-average molecular weight is 30000g/mol, vinyl acetate content be 40% ethylene-vinyl acetate copolymer take mass ratio as the mixture that 99:1 direct physical compound obtains.
Comparative example 9
[CN201410009447] disclosed result 0.2% volume, aquation maximum rate peak value reduces by 62.4%.
The hydrated cementitious speed controlled material of embodiment 1 to 7 is added in concrete, the results are shown in Table 2.
Table 2 concrete performance
In table, result can be found out, the hydration rate controlled material prepared by method provided by the invention can reduce aquation maximum rate peak value more than 75%, is better than current published result; It is only blended dextrin and macromolecule organic, and its effect is limited, far below the product prepared by method provided by the invention.
Embodiment 8
Number-average molecular weight is the dextrin of 26000g/mol, adding number-average molecular weight is 8000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 20%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 92:8, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 9
Number-average molecular weight is the dextrin of 26000g/mol, adding number-average molecular weight is 100000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 20%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 95:5, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 10
Number-average molecular weight is the dextrin of 26000g/mol, adding number-average molecular weight is 250000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 20%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99:1, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 11
Number-average molecular weight is the dextrin of 26000g/mol, adding number-average molecular weight is 350000g/mol, vinyl acetate content is in the tetrahydrofuran solution of the ethylene-vinyl acetate copolymer of 20%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99.5:0.5, solvents tetrahydrofurane is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 12
Number-average molecular weight is the dextrin of 26000g/mol, adding number-average molecular weight is 450000g/mol, vinyl acetate content is in the ethanolic soln of the ethylene-vinyl acetate copolymer of 20%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99.9:0.1, etoh solvent is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
The hydrated cementitious speed controlled material of embodiment 8 to 12 is added in concrete, the results are shown in Table 3.
Table 3 concrete performance
Table 3 can be found out: the hydration rate controlled material prepared by method provided by the invention can reduce aquation maximum rate peak value more than 75%, is better than current published result.
Embodiment 13
Number-average molecular weight is the dextrin of 90000g/mol, adding number-average molecular weight is 500000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 60%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 99.95:0.05, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 14
Number-average molecular weight is the dextrin of 60000g/mol, adding number-average molecular weight is 100000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 40%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 95:5, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 15
Number-average molecular weight is the dextrin of 30000g/mol, adding number-average molecular weight is 10000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 20%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 94:6, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
Embodiment 16
Number-average molecular weight is the dextrin of 10000g/mol, adding number-average molecular weight is 1000g/mol, vinyl acetate content is in the dichloromethane solution of the ethylene-vinyl acetate copolymer of 5%, the mass ratio of dextrin and ethylene-vinyl acetate copolymer is 90:10, methylene chloride is removed after stirring 5min, gained solid drying, pulverizes and obtains required aquation controlled material.
The hydrated cementitious speed controlled material of embodiment 13 to 16 is added in concrete, the results are shown in Table 4.
Table 4 concrete performance
Claims (5)
1. a hydrated cementitious speed controlled material, is characterized in that: described hydrated cementitious speed controlled material is the dextrin of non-soluble polymer parcel modification.
2. a kind of hydrated cementitious speed controlled material according to claim 1, is characterized in that: described dextrin number-average molecular weight is 1000 ~ 90000g/mol; Preferably, described dextrin number-average molecular weight is at 2000 ~ 60000g/mol; More preferably, described dextrin number-average molecular weight is at 5000 ~ 30000g/mol.
3. a kind of hydrated cementitious speed controlled material according to claim 1, is characterized in that: described non-soluble polymer is easy film-forming polymer, optimal ethylene-vinyl acetate copolymer; The number-average molecular weight of described ethylene-vinyl acetate copolymer is 1000-500000g/mol, and vinyl acetate content is 5-60mol%.
4. a kind of hydrated cementitious speed controlled material according to claim 1, is characterized in that: the mass ratio (0.05-10) of described non-soluble polymer and dextrin: (90-99.95).
5. the application of hydrated cementitious speed controlled material in concrete described in any one of claim 1-4, is characterized in that: the volume of described hydrated cementitious speed controlled material is 0.1-2%, more preferably 0.15-1%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108585572A (en) * | 2018-02-05 | 2018-09-28 | 武汉优城科技有限公司 | A kind of polymer surface modification sulphoaluminate expander and preparation method thereof |
| CN110963733A (en) * | 2018-09-29 | 2020-04-07 | 镇江苏博特新材料有限公司 | Preparation method of water-based cement hydration rate regulating material |
| CN112551930A (en) * | 2020-12-11 | 2021-03-26 | 河南理工大学 | Coated excitant for alkali slag cement and preparation method thereof |
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| CN103998392A (en) * | 2011-12-16 | 2014-08-20 | 建筑研究和技术有限公司 | Shellac-coated particles of active ingredients with controlled release properties at high PH-values, process for their manufacture and use thereof |
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| JPH07172892A (en) * | 1993-12-22 | 1995-07-11 | Chichibu Onoda Cement Corp | Retarder of heat generation by hydration of cement |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108585572A (en) * | 2018-02-05 | 2018-09-28 | 武汉优城科技有限公司 | A kind of polymer surface modification sulphoaluminate expander and preparation method thereof |
| CN110963733A (en) * | 2018-09-29 | 2020-04-07 | 镇江苏博特新材料有限公司 | Preparation method of water-based cement hydration rate regulating material |
| CN112551930A (en) * | 2020-12-11 | 2021-03-26 | 河南理工大学 | Coated excitant for alkali slag cement and preparation method thereof |
| CN112551930B (en) * | 2020-12-11 | 2021-08-17 | 河南理工大学 | Coated excitant for alkali slag cement and preparation method thereof |
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