CN104609768A - Cement hydration rate regulating material as well as preparation method and application of cement hydration rate regulating material - Google Patents
Cement hydration rate regulating material as well as preparation method and application of cement hydration rate regulating material Download PDFInfo
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- CN104609768A CN104609768A CN201510061749.1A CN201510061749A CN104609768A CN 104609768 A CN104609768 A CN 104609768A CN 201510061749 A CN201510061749 A CN 201510061749A CN 104609768 A CN104609768 A CN 104609768A
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Abstract
The invention provides a cement hydration rate regulating material which is dextrin containing anions. The cement hydration rate regulating material is simple in preparation process and low in cost; the cement hydration rate regulating performance of the cement hydration rate regulating material is greatly improved as comparison with that of the prior art; and the peak value of the maximum heat release rate for cement hydration can be reduced by more than 80%. Meanwhile, the cement hydration rate regulating material can generate a cement hydration influence different from that of the traditional micromolecular retarder; the regulating material has few and even no influences to the induction period of hydration, but can be used for greatly reducing hydration rates in an acceleration period and a deceleration period; however, the traditional micromolecular retarder is mainly used for prolonging the induction period for cement hydration, but has no influences to the hydration rates in the acceleration period and the deceleration period of the 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
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 thermal cracking, must reduce concrete temperature rise, therefore needing 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.
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 effect also deposits deficiency.
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, not every dextrin all has outstanding aquation adjusting function, and in disclosed result aquation performance of control also limited.
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 controlled material.
Technical scheme:
Applicant is found by large quantity research:
First, dextrin effectively can reduce hydrated cementitious speed essential reason: 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 therefore improving dextrin adsorbent layer thickness is exactly improve the key of dextrin hydration rate ability of regulation and control further;
The second, dextrin is adsorbed on cement particle surface by the hydroxyl of self, but hydroxyl neutral, limited sorption capacity; And when introducing electronegative group on dextrin molecular weight, the adsorption efficiency of dextrin significantly can be improved, increase adsorbent layer thickness, and then improve product aquation ability of regulation and control;
3rd, dextrin molecular weight also can have impact to the thickness of adsorption layer: too low molecular weight, and adsorption site is easy desorption less, reduce the obstructing capacity of adsorption layer, and the dextrin of small-molecular-weight easily causes slow setting; Too high molecular weight again reduces saturated adsorption rate, and adsorption efficiency is reduced.
Therefore to obtain the aquation controlled material of excellent performance, must control amount of charge in molecular weight of product, molecular chain.
A kind of hydrated cementitious controlled material provided by the invention is the dextrin containing negatively charged ion.
As preferably, described negatively charged ion is carboxyl or sulfonic group.
Preferred as another kind, described dextrin number-average molecular weight is at below 90000g/mol, and number-average molecular weight accounts for the per-cent of whole dextrin within 10% at the dextrin of below 1000g/mol; Preferably, described dextrin number-average molecular weight is at below 60000g/mol, and number-average molecular weight accounts for the per-cent of whole dextrin within 5% at the dextrin of below 1000g/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 hydrated cementitious controlled material reacts obtained by anionization properties-correcting agent and dextrin.Syntheti c route of the present invention: choose the dextrin that molecular weight is moderate, and in molecular chain, introduce suitable anionic group, as carboxyl, sulfonic group.And the introducing method of anionic group can with reference to method disclosed in starch field, available anionization properties-correcting agent, as Mono Chloro Acetic Acid, maleic anhydride, chlorsulfonic acid, to utilize on itself and dextrin hydroxyl reaction and then introduces anionic group.
As preferred further, described anionization properties-correcting agent is Mono Chloro Acetic Acid, maleic anhydride or chlorsulfonic acid.
As preferred further, the quality of described anionization properties-correcting agent is the 0.2-50% of dextrin quality, preferred 1-10%.
Present invention also offers the application of above-mentioned hydrated cementitious controlled material in concrete, the volume (consumption relative to glue material) of described hydrated cementitious controlled material is 0.05-3%, preferred 0.1-2%, more preferably 0.15-1%.
Beneficial effect: hydrated cementitious controlled material preparation technology provided by the invention is simple, with low cost, and it has very large lifting to hydrated cementitious speed performance of control relative to prior art, can reduce hydrated cementitious maximum heatrelease rate peak value more than 80%.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.
Adiabatic temperature rise of concrete uses Boyuan Science & Technology Development Co. Ltd., Zhoushan City BY-ATC/JR type thermal insulation warming instrument.Without special instruction in embodiment, during thermal insulation warming test, initial temperature is 15 DEG C.
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, concrete mix is as shown in table 1.Wherein, cement uses little wild field 52.5 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 1.1 concrete foundation proportioning (kg/m
3)
Embodiment 1
100g number-average molecular weight is the dextrin of 5000g/mol, dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 8%, join in 500ml acetone, add 5g Mono Chloro Acetic Acid again, and then add 4.5gNaOH, under 35 DEG C of conditions, react 1h, through filtering, washing, drying, pulverizing obtain required aquation controlled material.
Embodiment 2
100g number-average molecular weight is the dextrin of 12000g/mol, dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 7%, join in 500ml acetone, add 5g Mono Chloro Acetic Acid again, and then add 4.5gNaOH, under 35 DEG C of conditions, react 1h, through filtering, washing, drying, pulverizing obtain required aquation controlled material.
Embodiment 3
100g number-average molecular weight is the dextrin of 30000g/mol, dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 5%, join in 500ml acetone, add 5g Mono Chloro Acetic Acid again, and then add 4.5gNaOH, under 35 DEG C of conditions, react 1h, through filtering, washing, drying, pulverizing obtain required aquation controlled material.
Embodiment 4
100g number-average molecular weight is the dextrin of 54000g/mol, dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 3%, join in 500ml acetone, add 5g Mono Chloro Acetic Acid again, and then add 4.5gNaOH, under 35 DEG C of conditions, react 1h, through filtering, washing, drying, pulverizing obtain required aquation controlled material.
Embodiment 5
100g number-average molecular weight is the dextrin of 80000g/mol, dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 3%, join in 500ml acetone, add 5g Mono Chloro Acetic Acid again, and then add 4.5gNaOH, under 35 DEG C of conditions, react 1h, through filtering, washing, drying, pulverizing obtain required aquation controlled material.
Comparative example 1
Do not add clean slurry, the concrete of any admixture.
Comparative example 2
100g number-average molecular weight is the dextrin of 5000g/mol, and dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 8%.Comparative example 3
100g number-average molecular weight is the dextrin of 12000g/mol, and dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 7%.Comparative example 4
100g number-average molecular weight is the dextrin of 30000g/mol, and dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 5%.Comparative example 5
100g number-average molecular weight is the dextrin of 54000g/mol, and dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 3%.Comparative example 6
100g number-average molecular weight is the dextrin of 80000g/mol, and dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 3%.Comparative example 7
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 5 is added in concrete, the results are shown in Table 2.
Table 2 concrete performance
Embodiment 6
The preparation method of sample is identical with embodiment 3, but simultaneously with reference to the testing method of the concrete match ratio when thermal insulation warming of [CN201410010473].
Comparative example 8
The embodiment 10 of patent CN201410010473.
The hydrated cementitious speed controlled material of embodiment 6 is added in concrete, the results are shown in Table 3.
Table 3 concrete performance
Embodiment 7
100g number-average molecular weight is the dextrin of 30000g/mol, and dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 5%; 1g maleic anhydride is dissolved in 15g water then to spray and adds in above-mentioned dextrin, mixes under being placed on 130 DEG C of temperature, reacts and obtain required aquation controlled material after 4 hours.
Embodiment 8
100g number-average molecular weight is the dextrin of 30000g/mol, and dextrin middle-molecular-weihydroxyethyl is lower than 1000g/mol part accounting 5%; 0.5g maleic anhydride is dissolved in 15g water then to spray and adds in above-mentioned dextrin, mixes under being placed on 130 DEG C of temperature, reacts and obtain required aquation controlled material after 4 hours.
Embodiment 9
100g number-average molecular weight is the dextrin of 30000g/mol, and dextrin middle-molecular-weihydroxyethyl, lower than 1000g/mol part accounting 5%, joins in 500ml acetone, slowly add 2g chlorsulfonic acid again, be warming up to 50 DEG C of reactions after 1.5 hours, then filter, drying obtains required aquation controlled material.
Embodiment 10
100g number-average molecular weight is the dextrin of 30000g/mol, and dextrin middle-molecular-weihydroxyethyl, lower than 1000g/mol part accounting 5%, joins in 500ml acetone, slowly add 25g chlorsulfonic acid again, be warming up to 50 DEG C of reactions after 1.5 hours, then filter, drying obtains required aquation controlled material.
Embodiment 11
100g number-average molecular weight is the dextrin of 30000g/mol, and dextrin middle-molecular-weihydroxyethyl, lower than 1000g/mol part accounting 5%, joins in 500ml acetone, slowly add 45g chlorsulfonic acid again, be warming up to 50 DEG C of reactions after 1.5 hours, then filter, drying obtains required aquation controlled material.
The hydrated cementitious speed controlled material of embodiment 7 to 11 is added in concrete, the results are shown in Table 4.
Table 4 concrete performance
Embodiment 12
100g number-average molecular weight is the dextrin of 90000g/mol, and dextrin middle-molecular-weihydroxyethyl, lower than 1000g/mol part accounting 10%, joins in 500ml acetone, slowly add 50g chlorsulfonic acid again, be warming up to 50 DEG C of reactions after 1.5 hours, then filter, drying obtains required aquation controlled material.
Embodiment 13
100g number-average molecular weight is the dextrin of 60000g/mol, and dextrin middle-molecular-weihydroxyethyl, lower than 1000g/mol part accounting 3%, joins in 500ml acetone, slowly add 0.2g chlorsulfonic acid again, be warming up to 50 DEG C of reactions after 1.5 hours, then filter, drying obtains required aquation controlled material.
Embodiment 14
100g number-average molecular weight is the dextrin of 60000g/mol, and dextrin middle-molecular-weihydroxyethyl, lower than 1000g/mol part accounting 3%, joins in 500ml acetone, slowly add 1g chlorsulfonic acid again, be warming up to 50 DEG C of reactions after 1.5 hours, then filter, drying obtains required aquation controlled material.
Embodiment 15
100g number-average molecular weight is the dextrin of 60000g/mol, and dextrin middle-molecular-weihydroxyethyl, lower than 1000g/mol part accounting 3%, joins in 500ml acetone, slowly add 10g chlorsulfonic acid again, be warming up to 50 DEG C of reactions after 1.5 hours, then filter, drying obtains required aquation controlled material.
The hydrated cementitious speed controlled material of embodiment 12 to 15 is added in concrete, the results are shown in Table 5.
Table 5 concrete performance
Claims (7)
1. a hydrated cementitious controlled material, is characterized in that: described hydrated cementitious controlled material is the dextrin containing negatively charged ion.
2. a kind of hydrated cementitious controlled material according to claim 1, is characterized in that: described negatively charged ion is carboxyl or sulfonic group.
3. a kind of hydrated cementitious controlled material according to claim 1, is characterized in that: described dextrin number-average molecular weight is at below 90000g/mol, and number-average molecular weight accounts for the per-cent of whole dextrin within 10% at the dextrin of below 1000g/mol; Preferred: described dextrin number-average molecular weight is at below 60000g/mol, and number-average molecular weight accounts for the per-cent of whole dextrin within 5% at the dextrin of below 1000g/mol.
4. a kind of hydrated cementitious controlled material according to claim 1, is characterized in that: described hydrated cementitious controlled material reacts obtained by anionization properties-correcting agent and dextrin.
5. a kind of hydrated cementitious controlled material according to claim 1, is characterized in that: described anionization properties-correcting agent is Mono Chloro Acetic Acid, maleic anhydride or chlorsulfonic acid.
6. a kind of hydrated cementitious controlled material according to claim 1-5, is characterized in that: the quality of described anionization properties-correcting agent is the 0.2-50% of dextrin quality, preferred 1-10%.
7. the application of hydrated cementitious controlled material in concrete described in any one of claim 1-6, is characterized in that: the volume of described hydrated cementitious controlled material is 0.05-3%, preferred 0.1-2%, more preferably 0.15-1%.
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| CN201510061749.1A CN104609768B (en) | 2015-02-05 | 2015-02-05 | A kind of hydrated cementitious speed controlled material and preparation method and application |
| HK15110526.5A HK1209721A1 (en) | 2015-02-05 | 2015-10-26 | A cement hydration-regulating material, the preparation process and the usage thereof |
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| CN201510061749.1A CN104609768B (en) | 2015-02-05 | 2015-02-05 | A kind of hydrated cementitious speed controlled material and preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964149A (en) * | 2018-09-29 | 2020-04-07 | 镇江苏博特新材料有限公司 | Preparation method of cement hydration heat regulating and controlling material with internal curing function |
| CN115745452A (en) * | 2021-09-02 | 2023-03-07 | 江苏苏博特新材料股份有限公司 | Concrete anti-cracking material, preparation method and application thereof |
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- 2015-02-05 CN CN201510061749.1A patent/CN104609768B/en active Active
- 2015-10-26 HK HK15110526.5A patent/HK1209721A1/en unknown
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| CN101260176A (en) * | 2006-07-21 | 2008-09-10 | 国家淀粉及化学投资控股公司 | Sulfonated graft copolymers |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964149A (en) * | 2018-09-29 | 2020-04-07 | 镇江苏博特新材料有限公司 | Preparation method of cement hydration heat regulating and controlling material with internal curing function |
| CN115745452A (en) * | 2021-09-02 | 2023-03-07 | 江苏苏博特新材料股份有限公司 | Concrete anti-cracking material, preparation method and application thereof |
| CN115745452B (en) * | 2021-09-02 | 2024-03-29 | 江苏苏博特新材料股份有限公司 | Concrete anti-cracking material, preparation method and application thereof |
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| HK1209721A1 (en) | 2016-04-08 |
| CN104609768B (en) | 2017-10-10 |
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